[Federal Register Volume 69, Number 66 (Tuesday, April 6, 2004)]
[Proposed Rules]
[Pages 18166-18226]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 04-6427]
[[Page 18165]]
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Part II
Environmental Protection Agency
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40 CFR Part 122, et al.
Guidelines Establishing Test Procedures for the Analysis of Pollutants
Under the Clean Water Act; National Primary Drinking Water Regulations;
and National Secondary Drinking Water Regulations; Analysis and
Sampling Procedures; Proposed Rule
Federal Register / Vol. 69, No. 66 / Tuesday, April 6, 2004 /
Proposed Rules
[[Page 18166]]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Parts 122, 136, 141, 143, 403, 430, 455, and 465
[FRL-7638-9]
RIN 2040-AD71
Guidelines Establishing Test Procedures for the Analysis of
Pollutants Under the Clean Water Act; National Primary Drinking Water
Regulations; and National Secondary Drinking Water Regulations;
Analysis and Sampling Procedures
AGENCY: Environmental Protection Agency (EPA).
ACTION: Proposed rule.
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SUMMARY: EPA is proposing changes to analysis and sampling procedures
in wastewater regulations. These changes include proposal of vendor-
developed methods; new EPA and voluntary consensus standard bodies
(VCSB) methods; updated versions of currently approved methods; revised
method modification and analytical requirements; withdrawal of certain
outdated methods; and changes to sample collection, preservation, and
holding time requirements. EPA also is proposing changes to drinking
water analysis and monitoring. These changes include proposal of
vendor-developed methods; new EPA and VCSB methods; and updated VCSB
methods. The addition of new and updated methods to the wastewater and
drinking water regulations will provide increased flexibility to the
regulated community and laboratories in the selection of analytical
methods. Finally, EPA is soliciting comment on the guidance document
EPA Microbiological Alternate Test Procedure (ATP) Protocol for
Drinking Water, Ambient Water, and Wastewater Monitoring Methods.
DATES: Comments must be postmarked, delivered by hand, or
electronically mailed on or before June 7, 2004. Comments provided
electronically will be considered timely if they are submitted
electronically by 11:59 p.m. Eastern Time on June 7, 2004.
ADDRESSES: Comments may be submitted by mail to Water Docket, U.S.
Environmental Protection Agency (4101T), 1200 Pennsylvania Avenue NW.,
Washington DC 20460, or electronically through EPA Dockets at http://www.epa.gov/edocket/, Attention Docket ID No. OW-2003-0070. See Section
C of the SUPPLEMENTARY INFORMATION section for additional ways to
submit comments and more detailed instructions.
FOR FURTHER INFORMATION CONTACT: For information regarding the proposed
changes to wastewater regulations contact Marion Kelly, Engineering and
Analysis Division (4303T), USEPA Office of Science and Technology, 1200
Pennsylvania Ave., NW., Washington, DC 20460, 202-566-1045 (e-mail:
[email protected]). For information regarding the proposed changes
to drinking water regulations, contact Herbert J. Brass, Technical
Support Center (MS 140), USEPA, Office of Ground Water and Drinking
Water, 26 West Martin Luther King Drive, Cincinnati, OH 45268, 513-569-
7936 (e-mail: [email protected]). For information on the guidance
document EPA Microbiological Alternate Test Procedure (ATP) Protocol
for Drinking Water, Ambient Water, and Wastewater Monitoring Methods
contact Robin K. Oshiro, Engineering and Analysis Division (4303T),
USEPA Office of Science and Technology, 1200 Pennsylvania Ave., NW.,
Washington, DC 20460, 202-566-1075 (e-mail: [email protected]).
SUPPLEMENTARY INFORMATION:
A. Potentially Regulated Entities
1. Clean Water Act
EPA Regions, as well as States, Territories and Tribes authorized
to implement the National Pollutant Discharge Elimination System
(NPDES) program, issue permits that comply with the technology-based
and water quality-based requirements of the Clean Water Act (CWA). In
doing so, NPDES permitting authorities, including States, Territories,
and Tribes, make several discretionary choices when they write a
permit. These choices include the selection of pollutants to be
measured and, in many cases, limited in permits. If EPA has
``approved'' (i.e., promulgated through rulemaking) procedures for
analysis of pollutants (i.e., test procedures), the NPDES permit must
include one of the approved testing procedures or an approved alternate
test procedure. Similarly, if EPA has approved sampling requirements,
measurements taken under an NPDES permit must comply with these
requirements. Therefore, entities with NPDES permits could potentially
be regulated by the proposed actions in this rulemaking. In addition,
when an authorized State, Territory, or Tribe certifies Federal
licenses under CWA section 401, they must use the standardized analysis
and sampling procedures. Categories and entities that could potentially
be regulated include:
------------------------------------------------------------------------
Examples of potentially
Category regulated entities
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State, Territorial, and Indian Tribal States, Territories, and Tribes
Governments. authorized to administer the
NPDES permitting program;
States, Territories, and
Tribes providing certification
under Clean Water Act section
401.
Industry............................... Facilities that must conduct
monitoring to comply with
NPDES permits.
Municipalities......................... POTWs that must conduct
monitoring to comply with
NPDES permits.
------------------------------------------------------------------------
This table is not intended to be exhaustive, but rather provides a
guide for readers regarding entities likely to be regulated by this
action. This table lists types of entities that EPA is now aware could
potentially be regulated by this action. Other types of entities not
listed in the table could also be regulated. To determine whether your
facility is regulated by this action, you should carefully examine the
applicability language at 40 CFR 122.1, (NPDES purpose and scope), 40
CFR 136.1 (NPDES permits and CWA), 40 CFR 403.1 (Pretreatment standards
purpose and applicability), 40 CFR 430.00 (Pulp, paper, and paperboard
point source category applicability), 40 CFR 455.20, 455.30, 455.40,
455.60 (Pesticide point source category applicability), and 40 CFR
465.01 (Coil coating point source category applicability). If you have
questions regarding the applicability of this action to a particular
entity, consult the appropriate person listed in the preceding FOR
FURTHER INFORMATION CONTACT section.
2. Safe Drinking Water Act
Public water systems are the regulated entities required to conduct
analyses to measure for contaminants in water samples. However, EPA
Regions, as well as States, and Tribal governments with primacy to
administer the regulatory program for public water systems under the
Safe Drinking Water Act, sometimes conduct analyses to measure for
contaminants in water samples. If EPA has established a maximum
contaminant level (``MCL'') for a given drinking water contaminant, the
Agency also approves (i.e., promulgates through rulemaking)
standardized testing procedures for analysis of the contaminant. Once
EPA standardizes such test procedures, analysis using a standard test
procedure (or approved alternate test procedures) is generally
required. Public water systems required to test water samples must use
one of the approved standardized test
[[Page 18167]]
procedures. Categories and entities that may ultimately be regulated
include:
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Examples of
Category potentially regulated NAICS1\1\
entities
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State, Local, & Tribal Governments. States, local and 924110
tribal governments
that analyze water
samples on behalf of
public water systems
required to conduct
such analysis;
States, local and
tribal governments
that themselves
operate community and
non-transient non-
community water
systems required to
monitor.
Industry........................... Private operators of 221310
community and non-
transient non-
community water
systems required to
monitor.
Municipalities..................... Municipal operators of 924110
community and non-
transient non-
community water
systems required to
monitor.
------------------------------------------------------------------------
\1\North American Industry Classification System.
This table is not intended to be exhaustive, but rather provides a
guide for readers regarding entities likely to be regulated by this
action. The table lists types of entities that EPA is now aware could
potentially be regulated by this action. Other types of entities not
listed in the tables could also be regulated. To determine whether your
facility is regulated by this action, you should carefully examine the
applicability language at 40 CFR 141.2 (definition of public water
system). If you have questions regarding the applicability of this
action to a particular entity, consult the appropriate person listed in
the preceding FOR FURTHER INFORMATION CONTACT section.
B. How Can I Get Copies of This Document and Other Related Information?
1. Docket
EPA has established an official public docket for this action under
Docket ID No. OW-2003-0070. The official public docket consists of the
documents specifically referenced in this action, any public comments
received, and other information related to this action. Although a part
of the official docket, the public docket does not include Confidential
Business Information (CBI) or other information whose disclosure is
restricted by statute. The official public docket is the collection of
materials that is available for public viewing at the Water Docket in
the EPA Docket Center, EPA West Building, Room B102, 1301 Constitution
Avenue NW., Washington, DC. The EPA Docket Center Public Reading Room
is open from 8:30 a.m. to 4:30 p.m., Monday through Friday, excluding
legal holidays. The telephone number for the Public Reading Room is
(202) 566-1744, and the telephone number for the Water Docket is (202)
566-2426. For access to docket materials, please call ahead to schedule
an appointment. Every user is entitled to copy 266 pages per day before
incurring a charge. The Docket may charge 15 cents per page for each
page over the page limit plus an administrative fee of $25.00.
2. Electronic Access
You may access this Federal Register document electronically
through the EPA Internet under the ``Federal Register'' listings at
http://www.epa.gov/fedrgstr/. An electronic version of the public
docket is available through EPA's electronic public docket and comment
system, EPA Dockets. You may use EPA Dockets at http://www.epa.gov/edocket/ to submit or view public comments, access the index listing of
the contents of the official public docket, and to access those
documents in the public docket that are available electronically. Once
in the system, select ``search,'' then key in the appropriate docket
identification number.
Certain types of information will not be placed in the EPA Dockets.
Information claimed as CBI and other information whose disclosure is
restricted by statute, which is not included in the official public
docket, will not be available for public viewing in EPA's electronic
public docket. EPA's policy is that copyrighted material will not be
placed in EPA's electronic public docket but will be available only in
printed, paper form in the official public docket. Although not all
docket materials may be available electronically, you may still access
any of the publicly available docket materials through the docket
facility identified in Section B.1.
For public commenters, it is important to note that EPA's policy is
that public comments, whether submitted electronically or in paper,
will be made available for public viewing in EPA's electronic public
docket as EPA receives them and without change, unless the comment
contains copyrighted material, CBI, or other information for which
disclosure is restricted by statute. When EPA identifies a comment
containing copyrighted material, EPA will provide a reference to that
material in the version of the comment that is placed in EPA's
electronic public docket. The entire printed comment, including the
copyrighted material, will be available in the public docket.
Public comments submitted on computer disks that are mailed or
delivered to the docket will be transferred to EPA's electronic public
docket. Public comments that are mailed or delivered to the Docket will
be scanned and placed in EPA's electronic public docket. Where
practical, physical objects will be photographed, and the photograph
will be placed in EPA's electronic public docket along with a brief
description written by the docket staff.
C. How and To Whom Do I Submit Comments?
You may submit comments electronically, by mail, or through hand
delivery/courier. To ensure proper receipt by EPA, identify the
appropriate docket identification number in the subject line on the
first page of your comment. Please ensure that your comments are
submitted within the specified comment period. Comments received after
the close of the comment period will be marked ``late.'' EPA is not
required to consider these late comments.
1. Electronically
If you submit an electronic comment as prescribed below, EPA
recommends that you include your name, mailing address, and an e-mail
address or other contact information in the body of your comment. Also
include this contact information on the outside of any disk or CD ROM
you submit, and in any cover letter accompanying the disk or CD ROM.
This ensures that you can be identified as the submitter of the comment
and allows EPA to contact you in case EPA cannot read your comment due
to technical difficulties or needs further information on the substance
of your comment. EPA's policy is that EPA will not edit your comment,
and any
[[Page 18168]]
identifying or contact information provided in the body of a comment
will be included as part of the comment that is placed in the official
public docket, and made available in EPA's electronic public docket. If
EPA cannot read your comment due to technical difficulties and cannot
contact you for clarification, EPA may not be able to consider your
comment.
i. EPA Dockets. Your use of EPA's electronic public docket to
submit comments to EPA electronically is EPA's preferred method for
receiving comments. Go directly to EPA Dockets at http://www.epa.gov/edocket, and follow the online instructions for submitting comments.
Once in the system, select ``search,'' and then key in Docket ID No.
OW-2003-0070. The system is an ``anonymous access'' system, which means
EPA will not know your identity, e-mail address, or other contact
information unless you provide it in the body of your comment.
ii. E-mail. Comments may be sent by electronic mail (e-mail) to:
[email protected], Attention Docket ID No. OW-2003-0070. In
contrast to EPA's electronic public docket, EPA's e-mail system is not
an ``anonymous access'' system. If you send an e-mail comment directly
to the Docket without going through EPA's electronic public docket,
EPA's e-mail system automatically captures your e-mail address. E-mail
addresses that are automatically captured by EPA's e-mail system are
included as part of the comment that is placed in the official public
docket, and made available in EPA's electronic public docket.
iii. Disk or CD ROM. You may submit comments on a disk or CD ROM
that you mail to the mailing address identified in Section C.2. These
electronic submissions will be accepted in WordPerfect or ASCII file
format. Avoid the use of special characters and any form of encryption.
2. By Mail
Send an original and three copies of your comments to Water Docket,
U.S. Environmental Protection Agency (4101T), 1200 Pennsylvania Avenue
NW., Washington, DC 20460, Attention Docket ID No. OW-2003-0070.
3. By Hand Delivery or Courier
Deliver your comments to the Water Docket in the EPA Water Center,
EPA West Building, Room B102, 1301 Constitution Avenue NW., Washington,
DC, Attention Docket ID No. OW-2003-0070. Such deliveries are only
accepted during the Docket's normal hours of operation as identified in
Section B.1.
D. How Should I Submit CBI to the Agency?
Do not submit information that you consider to be CBI
electronically through EPA's electronic public docket or by e-mail. You
may claim information that you submit to EPA as CBI by marking any part
or all of that information as CBI (if you submit CBI on disk or CD ROM,
mark the outside of the disk or CD ROM as CBI and then identify
electronically within the disk or CD ROM the specific information that
is CBI). Information so marked will not be disclosed except in
accordance with procedures set forth in 40 CFR part 2.
In addition to one complete version of the comment that includes
any information claimed as CBI, a copy of the comment that does not
contain the information claimed as CBI must be submitted for inclusion
in the public docket and EPA's electronic public docket. If you submit
the copy that does not contain CBI on disk or CD ROM, mark the outside
of the disk or CD ROM clearly that it does not contain CBI. Information
not marked as CBI will be included in the public docket and EPA's
electronic public docket without prior notice. If you have any
questions about CBI or the procedures for claiming CBI, please consult
the person identified in the FOR FURTHER INFORMATION CONTACT section.
E. What Should I Consider as I Prepare My Comments for EPA?
You may find the following suggestions helpful for preparing your
comments:
1. Explain your views as clearly as possible.
2. Describe any assumptions that you used.
3. Provide any technical information and/or data you used that
support your views.
4. If you estimate potential burden or costs, explain how you
arrived at your estimate.
5. Provide specific examples to illustrate your concerns.
6. Offer alternatives.
7. Make sure to submit your comments by the comment period
deadline.
8. To ensure proper receipt by EPA, identify the appropriate docket
identification number in the subject line on the first page of your
response. It would also be helpful if you provided the name, date, and
Federal Register citation related to your comments.
F. Abbreviations and Acronyms Used in the Preamble and Proposed Rule
ASTM: ASTM International
ATP: Alternate Test Procedure
CIE-UV: Capillary Ion Electrophoresis with Indirect Ultraviolet
Detection
CWA: Clean Water Act
EMMC: Environmental Monitoring Management Council
EPA: Environmental Protection Agency
FLAA: Flame Atomic Absorption Spectroscopy
GC-MS: Gas Chromatography with Mass Spectrometry Detection
IC: Ion Chromatography
ICP-AES: Inductively Coupled Plasma-Atomic Emission Spectroscopy
ICP-MS: Inductively Coupled Plasma-Mass Spectroscopy
ISE: Ion Selective Electrode
NPDES: National Pollutant Discharge Elimination System
NPDWR: National Primary Drinking Water Regulations
NSDWR: National Secondary Drinking Water Regulations
SDWA: Safe Drinking Water Act
STGFAA: Stabilized Temperature Graphite Furnace Atomic Absorption
Spectroscopy
Table of Contents
I. Statutory Authority
A. Clean Water Act
B. Safe Drinking Water Act
II. Explanation of Today's Action
A. Methods for NPDES Compliance Monitoring
B. Sampling, Sample Preservation, and Holding Times for NPDES
Compliance Monitoring
C. Editorial Changes to 40 CFR Part 136
D. Methods for NPDWR and NSDWR Compliance Monitoring and Monitoring
Requirements
E. Microbiological ATP Protocol
III. Summary of Proposed Revisions to Wastewater Regulations
A. Analytical Methods for NPDES Compliance Monitoring
B. Sample Collection, Preservation, and Holding Time
Requirements for NPDES Compliance Monitoring and Pretreatment
C. Editorial Revisions and Clarifications to 40 CFR Parts 122,
136, 455, and 465
IV. Summary of Proposed Revisions to Drinking Water Regulations
A. Vendor Developed Methods
B. EPA Method for Chlorine Dioxide by Colorimetry
C. New and Updated VCSB Methods
D. Withdrawal of Immunoassay Method for Atrazine
V. Request for Comment on Microbiological ATP Protocol
VI. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review
B. Paperwork Reduction Act
C. Regulatory Flexibility Act
D. Unfunded Mandates Reform Act
E. Executive Order 13132: Federalism
F. Executive Order 13175: Consultation and Coordination with
Indian Tribal Governments
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G. Executive Order 13045: Protection of Children From
Environmental Health Risks and Safety Risks
H. Executive Order 13211: Actions that Significantly Affect
Energy Supply, Distribution, or Use
I. National Technology Transfer and Advancement Act
I. Statutory Authority
A. Clean Water Act
EPA is proposing this action pursuant to the authority of sections
301(a), 304(h), and 501(a) of the Clean Water Act (``CWA'' or the
``Act''), 33 U.S.C. 1311(a), 1314(h), 1361(a). Section 301(a) 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 of the Act.
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 this function under [the
Act].'' EPA generally publishes test procedure regulations (including
analysis and sampling requirements) for CWA programs at 40 CFR part
136, though some specific requirements are in other sections (e.g., 40
CFR Chapter I, Subchapters N and O).
B. Safe Drinking Water Act
The Safe Drinking Water Act (SDWA), as amended in 1996, requires
EPA to promulgate national primary drinking water regulations (NPDWRs)
that specify maximum contaminant levels (MCLs) or treatment techniques
for drinking water contaminants (SDWA section 1412 (42 U.S.C. 300g-1)).
NPDWRs apply to public water systems pursuant to SDWA sections
1401(1)(A) (42 U.S.C. 300f(1)(A)). According to SDWA section
1401(1)(D), NPDWRs include ``* * * criteria and procedures to assure a
supply of drinking water which dependably complies with such maximum
contaminant levels; including accepted methods for quality control and
testing procedures * * *'' (42 U.S.C. 300f(1)(D)). In addition, SDWA
section 1445(a) authorizes the Administrator to establish regulations
for monitoring to help determine whether persons are acting in
compliance with the requirements of the SDWA (42 U.S.C. 300j-4). EPA's
promulgation of analytical methods for NPDWRs is authorized under these
sections of the SDWA as well as the general rulemaking authority in
SDWA section 1450(a) (42 U.S.C. 300j-9(a)).
The SDWA also authorizes EPA to promulgate national secondary
drinking water regulations (NSDWRs) for contaminants in drinking water
that primarily affect the aesthetic qualities relating to the public
acceptance of drinking water (SDWA section 1412 (42 U.S.C. 300g-1)).
These regulations are not Federally enforceable but are guidelines for
the States (40 CFR 143.1). The NSDWRs also include analytical
techniques for determining compliance with the regulations (40 CFR
143.4). EPA's promulgation of analytical methods for NSDWRs is
authorized under general rulemaking authority in SDWA section 1450(a)
(42 U.S.C. 300j-9(a)).
II. Explanation of Today's Action
A. Methods for NPDES Compliance Monitoring
EPA approves analytical methods for measuring regulated pollutants
in wastewater. Regulated and regulatory entities use these approved
methods for determining compliance with an NPDES permit or other
monitoring requirement. Often, these entities have a choice in deciding
which approved method they will use to measure a pollutant because
multiple approved methods are available.
This rule proposes to add to the list of approved test procedures
for a number of pollutants. Some proposed methods introduce new
technologies to the NPDES program, while others are updated versions of
previously approved methods. EPA believes that these additions will
improve data quality and provide the regulated community with greater
flexibility. Furthermore, many of the additions will promote
consistency between the NPDES (wastewater) and NPDWRs/NSDWRs (drinking
water) compliance monitoring programs by adopting the same versions of
methods for both programs--allowing laboratories to use a single
version of a method to satisfy multiple water compliance monitoring
needs.
This rule also proposes to allow increased method flexibility by
explicitly allowing certain technical changes (e.g., allowing the use
of capillary columns in gas chromatography methods, allowing the
addition of salts--under certain conditions--to resolve interferences
in extraction procedures). Finally, this rule proposes to remove
certain outdated methods, including chlorofluorocarbon-based oil and
grease methods.
B. Sampling, Sample Preservation, and Holding Times for NPDES
Compliance Monitoring
EPA publishes sampling, sample preservation, and holding time
requirements in regulations to help ensure that samples collected for
NPDES compliance monitoring provide a representative measurement of the
pollutants in wastestreams. This rule proposes to update these
requirements to reflect new information and create consistency among
CFR sections.
C. Editorial Changes to 40 CFR Part 136
This rule proposes editorial changes to 40 CFR part 136 to correct
errors and update information.
D. Methods for NPDWR and NSDWR Compliance Monitoring and Monitoring
Requirements
EPA approves analytical methods for monitoring contaminants in
drinking water. The drinking water industry uses these approved methods
for determining compliance with NPDWRs and NSDWRs. Because multiple
methods are generally available, public water systems often have a
choice in deciding which approved method they will use to measure a
drinking water contaminant.
This rule proposes to add a new means of monitoring for compliance
with a radiological contaminant limit, and new methods for chemical
contaminant monitoring. These additions will provide greater monitoring
flexibility.
E. Microbiological ATP Protocol
EPA is soliciting comments on ``EPA Microbiological Alternate Test
Procedure (ATP) Protocol for Drinking Water, Ambient Water, and
Wastewater Monitoring Methods--Guidance'' (July 2003; EPA-821-B-03-004)
(Protocol).
III. Summary of Proposed Revisions to Wastewater Regulations
A. Analytical Methods for NPDES Compliance Monitoring
1. Chemical Alternate Test Procedures
To promote method flexibility, EPA maintains a program whereby
stakeholders (e.g., instrument manufacturers, environmental
laboratories, regulated entities) can apply for EPA approval of
alternate test procedures. The Alternate Test Procedure (ATP) program
is codified at 40 CFR 136.4 and 136.5 for wastewater. This rule
proposes to approve three alternate test procedures at 40 CFR part 136
for monitoring chemical pollutants:
``Test Method for Determination of Dissolved
Inorganic Anions in Aqueous Matrices Using Capillary Ion
[[Page 18170]]
Electrophoresis and Chromate Electrolyte'' (D6508, Rev. 2) by Waters
Corporation.
``Digestion and Distillation of Total Cyanide in
Drinking and Wastewaters using MICRO DIST and determination of cyanide
by flow injection analysis'' (QuikChem Method 10-204-00-1-X) by Lachat
Instruments.
``Kelada Automated Test Methods for Total
Cyanide, Acid Dissociable Cyanide, and Thiocyanate'' (Kelada-01) by Dr.
Nabih Kelada.
This rule also proposes to approve one method in the pulp, paper,
and paperboard point source category regulations at 40 CFR 430.02:
``Chlorinated Phenolics in Water by In situ
Acetylation and GC/MS Determination'' (Method CP-86.07) by the National
Council for Air and Stream Improvement (NCASI).
Each of the above-listed ATPs offers substantial advantages over
currently approved methods, and their approval will give analysts
additional flexibility in meeting monitoring requirements.
a. Anions by Capillary Ion Electrophoresis With Indirect Ultraviolet
Detection (CIE-UV)
Waters Corporation's ``Test Method for Determination of Dissolved
Inorganic Anions in Aqueous Matrices Using Capillary Ion
Electrophoresis and Chromate Electrolyte'' (Method D6508, Rev. 2) is a
new method that uses capillary ion electrophoresis to determine common
anions--bromide, chloride, fluoride, nitrate, nitrite, orthophosphate,
and sulfate--in drinking water and wastewater. Method D6508 appears to
provide an acceptable technological alternative to ion chromatography
and wet chemical methods in terms of method performance and is
equivalent to other approved methods in the working range. In addition,
the method is relatively easy to use (the CIE-UV system has fewer
moving parts and components than an ion chromatography system making it
easier to operate and maintain), involves relatively low cost equipment
(the cost of a CIE-UV capillary column is $30 compared to an ion
chromatography column that can be greater than $800), and generally
reduces laboratory wastes (less than 100 milliliters of waste is
generated daily).
Capillary ion electrophoresis (CIE) employs the same general
principle of ``separation followed by detection'' common to all
chromatography methods. Anions migrate through a silica capillary
column containing an electrolyte solution under the influence of an
electric field. With CIE, anions in the sample separate according to
their equivalent ionic conductance and mobility, and are measured using
indirect ultraviolet (UV) detection: the UV absorbing electrolyte anion
is displaced charge-for-charge by analyte anion. The corresponding
decrease in background absorption is proportional to the concentrations
of anions.
An 11-laboratory validation study characterized the performance of
Method D6508. Eight concentration levels included analyses of reagent
water, ``substitute'' wastewater, ``real'' wastewater, and drinking
water matrix types. The range of Method D6508 is 0.2 to 50 mg/L for all
analytes but fluoride, for which the range is 0.2 to 25 mg/L. The
method provides precision and recovery data for all analytes in all
matrices. For example, across all analytes at concentrations of
approximately 3 mg/L in real wastewater, the range of multilaboratory
recovery was 84-100%, and relative standard deviation was 6-26%. Waters
Corp. generated quality control limits in the method from the study
data available in the docket supporting this proposal.
ASTM International (ASTM) adopted a previous version of Method
D6508. If the updated version of the method included in the docket is
adopted by ASTM prior to publication of the final rule, the ASTM method
also may be approved.
A copy of Method D6508 and the method validation study report are
in the docket for this proposed rule. In addition, copies of Method
D6508 may be obtained from Waters Corporation. Contact: Jim Krol,
Waters Corp., 34 Maple St, Milford, MA 01757, 508/482-2131 (Office),
508/482-3625 (FAX), and [email protected].
b. Cyanide Microdistillation
Lachat Instrument's ``Digestion and Distillation of Total Cyanide
in Drinking and Wastewaters using MICRO DIST and Determination of
Cyanide by Flow Injection Analysis'' (QuikChem Method 10-204-00-1-X) is
a method that determines total cyanide in drinking water and
wastewater. The method employs the MICRO DIST distillation apparatus, a
reduced-volume and disposable counterpart to other distillation
apparatuses. MICRO DIST substantially reduces distillation time (by 50%
as compared with the currently approved macrodistillation) and
laboratory wastes (because it requires small sample and reagent volumes
required). It easily allows multiple simultaneous distillations (one
distillation heating block accommodates 21 MICRO DIST apparatuses).
MICRO DIST also has lower costs than some other cyanide distillations
due to time saved (in analysis and sample throughput) and reduced waste
disposal costs.
Using MICRO DIST, total cyanide is determined by distilling the
sample and measuring cyanide generated using a technique for cyanide
ion detection (e.g., colorimetry). Six milliliters of sample are added
to a distillation tube along with standard cyanide distillation
reagents (sulfuric acid, magnesium chloride). A cyanide collector tube,
which consists of a gas permeable membrane and sodium hydroxide
absorber solution, is attached to the distillation tube; the
distillation and collector tubes together comprise the MICRO DIST
apparatus. The sample is heated for one-half hour, during which
hydrogen cyanide gas distills from the sample, passes through the gas
permeable membrane, and collects in the sodium hydroxide absorber
solution. QuikChem Method 10-204-00-1-X provides instructions for
measuring cyanide in the absorber solution using an automated
colorimeter. However, the Method specifies that the absorber solution
may be analyzed using another procedure (e.g., manual colorimetry) as
well, provided all requirements in the Method are followed (e.g., pH of
the absorber solution and standards are adjusted to match). This rule
proposes both Method 10-204-00-1-X as a stand alone method, and the
MICRO DIST distillation procedure found in that method as an
alternative to other approved distillation procedures.
Method performance was characterized by two single laboratory
studies, and a nine-laboratory validation study. Lachat and the
Research Triangle Institute performed single laboratory studies that
demonstrated that recovery of complex cyanides using MICRO DIST was
equivalent to recovery with a conventional distillation apparatus. The
nine-laboratory validation study demonstrated that Method 10-204-00-1-X
with the MICRO DIST apparatus provided equivalent performance to EPA-
approved total cyanide methods across laboratories.
In validation of MICRO DIST, EPA reviewed data on recoveries of
free cyanide from wastewater matrices, and the recovery of complex
cyanides. EPA did not receive data on the recovery of particulate
cyanide, but other factors suggest that particulate cyanide will not
pose a problem with the method. These factors include (1) the
performance of the method in recovering complex cyanides, (2) the
increasing reagent concentrations in the solution during distillation
(due to sample transfer during distillation), and (3) the fact that
[[Page 18171]]
MICRO DIST employs a hard distillation versus a reflux distillation.
EPA requests comments on the issue of the distillation and solicits
data regarding MICRO DIST's recovery of particulate cyanide.
A copy of QuikChem Method 10-204-00-1-X and the method validation
study report are in the docket for this proposed rule. In addition,
copies of QuikChem Method 10-204-00-1-X may be obtained from Lachat
Instruments, 6645 W. Mill Rd., Milwaukee, WI 53218, USA. Phone: 414-
358-4200.
c. Cyanide by UV-digestion/Flash Distillation/Colorimetry
Dr. Nabih Kelada's ``Kelada Automated Test Methods for Total
Cyanide, Acid Dissociable Cyanide, and Thiocyanate,'' EPA 821-B-01-009
(Kelada-01) is an automated procedure that determines total cyanide and
acid dissociable cyanide in drinking water and wastewater. The
procedure uses a two-stage sample digestion system to determine total
cyanide. A sample is introduced into a flow analysis system. The sample
then passes through an irradiation coil, where it is exposed to intense
ultraviolet (UV) light from a high power (e.g., 550 Watt) UV
photochemical bulb. The UV light breaks down cyanide complexes
(including strong ferro- and ferri-cyanide complexes) to free cyanide.
The irradiated sample containing free cyanide then passes though a
distillation coil from which the free cyanide is distilled into a flow
colorimetry system (similar to that used in EPA Methods 335.3 and
335.4), and cyanide concentration is determined. All complex cyanides
recovered using the total cyanide manual distillation are recovered
using Kelada-01.
When the irradiation coil is by-passed--exposing sample only to a
distillation coil--``acid dissociable'' cyanide is determined. The
complexes measured are equivalent to those measured using cyanide
amenable to chlorination (CATC) and ``available'' cyanide procedures,
according to single laboratory studies performed by the Metropolitan
Water Reclamation District of Greater Chicago.
Kelada-01 offers a number of substantial advantages over currently
approved methods, such as a reduced analysis time (from one to two
hours to minutes), and substantially reduced effects of many
interferences encountered with manual distillation methods. Kelada-01
also produced very precise and accurate results, as demonstrated in
single laboratory validation studies by the Metropolitan Water
Reclamation District of Greater Chicago, an interlaboratory study
managed by Environment Canada, and an ASTM ``round-robin''
(interlaboratory) validation study. These studies generally showed
total and acid dissociable cyanide recoveries from samples between 90%
and 110%, and relative standard deviations of less than 10%. The
reported lower limit of detection is 0.5 [mu]g/L.
For determination of total cyanide, Kelada-01 can be configured to
use UV-irradiation under alkaline conditions (alkaline mode) or acidic
conditions (acidic mode). EPA has reviewed data on recoveries of free
cyanide and complex cyanides from a variety of wastewater matrices in
both modes. Given the successful recovery of cyanide complexes from a
variety of effluents, opacity does not appear to effect the recovery of
cyanide complexes. In addition, side-by-side comparative data on high
particulate samples (e.g., sludge) in the article Automated Direct
Measurements of Total Cyanide Species and Thiocyanate, and their
Distribution in Wastewater and Sludge (Journal WPCF, 61-3, pp. 350-56,
March 1989) demonstrating Kelada-01's superior recovery of cyanide
(relative to manual distillation) when running in alkaline mode,
supporting the conclusion that particulate cyanide recovery is not a
concern with this method. Corresponding data for use in acidic mode is
not available. However, EPA requests comment on whether the use of
Kelada-01 for determination of total cyanide should be restricted to
alkaline mode or should allow determinations in both alkaline and
acidic mode.
A copy of Kelada-01 and the method validation study report are in
the docket for this proposed rule. In addition, copies of Kelada-01 are
available from the National Technical Information Service (NTIS), 5285
Port Royal Road, Springfield, VA 22161 [Order Number PB 2001-108275].
Phone: 800-553-6847.
d. Phenolics in Bleach Plant Filtrate by Gas Chromatography-Mass
Spectrometry (GC-MS)
NCASI Method CP-86.07, ``Chlorinated Phenolics in Water by In situ
Acetylation and GC/MS Determination'' (January 2002) for determining
chlorinated phenols, chlorinated guaiacols, chlorinated catechols,
chlorinated benzaldehydes (i.e., vanillins and syringaldehydes), and
trichlorsyringol in bleach plant filtrate is an ATP to EPA Method 1653.
The complete list of analytes to which Method CP-86.07 is applicable is
provided in the method.
A 300-mL aliquot of aqueous sample is spiked with internal
standards and surrogates and is treated to form phenolate ions at a pH
of 9 to 11.5. The phenolate ions are converted in situ (i.e., in the
aqueous matrix) to their acetate derivatives which are then extracted
with hexane. The extract is analyzed using GC/MS.
EPA is proposing Method CP-86.07 specifically for use under the
regulations at 40 CFR part 430 (for the pulp and paper industry). NCASI
Method CP-86.07 was developed to reduce analytical costs (by $200 to
$300 per analysis) and the need for several isotopically labeled
standards, reduce sample and reagent volumes (e.g., sample volume is
reduced over 300% from EPA Method 1653), and addresses certain
interferences in pulp and paper effluent. With regard to performance,
participants in a four-laboratory validation study met the quality
control (QC) acceptance criteria specified in EPA Method 1653,
demonstrating equivalent performance.
NCASI Method CP-86.07 is available from the Publications
Coordinator, NCASI, P.O. Box 13318, Research Triangle Park, NC 27709-
3318. Phone 919-588-1987. You can also find a copy of the method and
the validation study report in the docket for this proposed rule.
2. Whole Effluent Toxicity Alternate Test Procedure--Microtox[reg] 1010
By today's notice, EPA invites comments on whether to approve a
standardized testing procedure measuring acute toxicity of aqueous test
samples to bacteria. Specifically, in response to a request from
Strategic Diagnostics, Inc. (SDI), EPA requests comment on whether to
approve, under 40 CFR part 136, SDI's ``Method for Measuring the Acute
Toxicity of Wastewater and Receiving Water with the Vibrio fischeri
(NRRL B-11177) Microtox[reg] Test System'' (Microtox[reg] 1010) for
determining the acute toxicity of wastewater, receiving waters, and
other aqueous samples. In this test, multiple, one-milliliter sample
dilutions (minimum of five) are added to sample wells containing about
one million saltwater bioluminescent bacteria, Vibrio fischeri strain
NRRL B-11177. The bacterial bioluminescence is a by-product of cellular
respiration correlating to organism health, and is measured in each
well using a photometer. Measurements at the various dilutions,
referenced against a control well, are taken over 15 minutes and used
to calculate the concentration at which the organisms manifest a 50%
effect (EC50), in this case, a decrease in
[[Page 18172]]
bioluminescence. The EC50 is the concentration of sample at
which a 50% reduction in bioluminescence occurs, and it is analogous to
the 50% inhibition concentration (IC50) used in other
toxicity tests.
Approval of Microtox[supreg] 1010 will add a new phylogenic
category which can be used to measure toxicity, specifically bacteria.
EPA proposes to approve the use of Microtox[supreg] 1010 to screen
discharges to freshwater for acute toxicity. EPA invites comment on the
appropriateness of including a bacteriological test to measure toxicity
for regulation in permits. EPA also invites comments on two options for
the use of Microtox[supreg] 1010 in discharges to marine and estuarine
waters.
Advantages of Microtox[supreg] 1010 Relative to Other Toxicity Test
Methods
Microtox[supreg] 1010 may be useful as a screening level test for
discharges to both freshwater and marine and estuarine waters when it
is used in conjunction with EPA's current whole effluent toxicity (WET)
test methods.
Microtox[supreg] 1010 also may be useful as a definitive test for
discharges to marine and estuarine waters. The Microtox[supreg] 1010
method employs a very large number of organisms (one million bacteria),
and as such, the test is not influenced by the responses of a small
number of test organisms. The method requires small sample volumes,
making the collection and shipment of samples simpler and more
affordable. The analysis time is short (15 minutes), and the method is
relatively inexpensive ($50-$150, compared to $300-$600 for the
currently approved acute toxicity tests).
While Microtox[supreg] 1010 would be an addition to the suite of
EPA WET methods, the technology is not new. Extensive research and
validation have been conducted using Vibrio fischeri, culminating in
more than 350 peer-reviewed papers (including 17 authored by EPA staff)
and adoption of ASTM Standard D5660-96, ``Standard Test Method for
Assessing the Microbial Detoxification of Chemically Contaminated Water
and Soil Using a Toxicity Test with a Luminescent Bacterium.'' In
response to previous EPA concerns about a lack of information on
Microtox[supreg] 1010 (see a Supplementary Information Document
[Response-to-Comments Document] from the 1995 WET rule [60 FR 53529,
53536; October 16, 1995]), SDI's predecessor, Azur Environmental,
conducted a validation study (ATP Application SL97-0002).
Approval of Microtox[supreg] 1010 for measurement as a pollutant
parameter under 40 CFR part 136 would allow toxicity evaluation to be
expanded to an important phylogenetic group and trophic level that is
not now addressed in the WET program. Bacteria are ecologically
relevant links in nutrient and energy cycling and, consequently, are
generally important to assessing the health of the environment.
EPA anticipates, however, there are some limitations for using the
Microtox[supreg] 1010 method for WET testing which are discussed below.
Limitations
Adding Microtox[supreg] 1010 to the suite of WET test procedures
poses challenges for the National Pollutant Discharge Elimination
System (NPDES) WET program. First, Microtox[supreg] 1010 employs a
saltwater bacterium, and therefore, the salinity of the samples to
which the method is applied needs to be adjusted to near that of
seawater to avoid artificial stressors to the test organisms. As such,
the modified sample may not represent the characteristics of the actual
effluent.
Second, Microtox[supreg] 1010 is less sensitive to some common
contaminants (certain metals and ammonia) than the currently approved
WET procedures. Conversely, Microtox[supreg] 1010 may be more sensitive
than the currently approved WET procedures to other sources of
toxicity, for example, sulfur and sulfur compounds. Currently, EPA
guidance in the ``Technical Support Document for Water Quality-based
Toxics Control'' (TSD, 1991) recommends that initial effluent testing
using species from three different phyla for the purpose of identifying
the most sensitive test species. Bacteria would be a fourth phylum. EPA
is concerned that economic pressure to implement a cheaper and quicker
test (e.g., Microtox[supreg] 1010) may cause some regulatory
authorities to abandon the recommended guidance for initial testing and
selection of the species that is most sensitive to the toxicity of a
particular effluent. For these reasons, EPA also invites comment on the
following uses of the Microtox[supreg] 1010 test to measure samples and
protect water quality.
Use in Discharges to Freshwater
Using the Microtox[supreg] 1010 to evaluate discharges to
freshwaters may not be appropriate, because the required salinity
adjustment itself could affect the toxicity of the sample, and the
salinity of the adjusted sample would not represent either the effluent
being discharged or the receiving water.
Therefore, EPA invites comment on the use of Microtox[supreg] 1010
as a ``screening'' test for freshwater. Under this approach, NPDES
permits for discharges to freshwater would not set limits based on
acute toxicity to bacteria determined by the Microtox[supreg] 1010
test. Instead, the test would be used to provide a ``snapshot'' for
toxicity potential of uncharacterized test samples to decide whether
further toxicity evaluation seems warranted. For example, EPA
anticipates the test would be very useful in situations where test
samples display intermittent toxicity or for a toxicity reduction
evaluation (TRE). Alternatively, operators of POTW pretreatment
programs could use the test for rapid analysis of the toxicity of
samples from users of the POTW. For these uses, EPA would not need to
approve the Microtox[supreg] 1010 test for use in 40 CFR part 136.
Use in Discharges to Marine and Estuarine Water
EPA is considering two options for the use of Microtox[supreg]
1010.
Option (1)--Use as a Screening Procedure
Under this option, Microtox[supreg] 1010 would be implemented for
discharges to marine and estuarine water in the same manner as proposed
for discharges to freshwater. As such, EPA would not need to approve
the test for use under 40 CFR part 136.
Option (2)--Use as a Definitive Test
Under this option, the Microtox[supreg] 1010 test would be used to
establish NPDES permit limits (in lieu of other WET test procedures) if
the Microtox[supreg] 1010 test organisms are the most sensitive in
detecting toxicity of a given test sample. This option would rely on
bacteria as an additional phylogenetic group by which to evaluate a
sample's toxicity. To assist EPA in determining whether to incorporate
bacteria as an additional phylogenetic group for which toxicity should
be evaluated, the Agency invites comment on whether adjusting the
salinity of discharges to marine and estuarine waters inappropriately
introduces a variable to the measurement of acute toxicity.
EPA solicits comments on all aspects of the Microtox[supreg] 1010
proposal, but is particularly interested in comment on the following
issues.
What is the most appropriate for the use of
Microtox[supreg] 1010 with marine and estuarine waters? A screening
test? A definitive test? Both? Neither?
Should the use of Microtox[supreg] 1010 be
precluded where toxicity in discharges is known to be due primarily to
metals and/or ammonia?
[[Page 18173]]
Should EPA approve this proprietary test
procedure? EPA does not generally endorse particular products or
services. If EPA does approve use of Microtox[reg] 1010 under 40 CFR
part 136, how should the Agency reflect the essential attributes of the
test that are not proprietary if it promulgates a final regulation
approving the procedure?
Will the regulated community require additional
guidance from EPA regarding the implementation of Microtox[reg] 1010 in
the WET monitoring scheme?
Should testing with Microtox[reg] 1010 and three
other species in the currently approved WET test procedures (e.g.,
fish, invertebrates, and plants) be conducted quarterly for one year to
address concerns of sensitivity to metals, ammonia, and/or unidentified
toxicants?
Are there additional bacteria-based methods that
EPA should consider?
A copy of Microtox[reg] 1010 and the method validation study report
are in the docket for this proposed rule. In addition copies, of
Microtox[reg] 1010 are available from Strategic Diagnostics, Inc., 111
Pencander Drive, Newark, DE 19702-3322, Phone: 800-544-8881, Fax: 302-
456-6789.
3. New Methods and Method Practices Proposed on October 18, 1995
The methods that EPA proposes to approve in NPDES regulations at 40
CFR part 136 include technologies that have been in use for many years.
Many of the methods have been used in the NPDES monitoring program on a
limited basis or have been used in other EPA programs (such as the
NPDWR program). Among the methods EPA proposes to approve are a group
of methods (or earlier revisions of the methods) that EPA initially
proposed for approval on October 18, 1995 (60 FR 53987, hereinafter
referred to as the ``10-18 proposal''). Although EPA did not take final
action on the 10-18 proposal, NPDES-approval for these methods has been
granted to individual applicants on a case-by-case basis under the ATP
program provisions at 40 CFR 136.4 and 136.5.
EPA proposes these methods again (along with updated equivalent
methods), instead of publishing a final rule, because over eight years
have passed since EPA's initial proposal and a significant quantity of
new valuable information on the effectiveness of these methods in NPDES
monitoring has become available, based on the use of these methods by
many laboratories. The information on the success (or failure) of these
methods in environmental laboratories is relevant to determining
whether these methods should be promulgated at 40 CFR part 136.
Therefore, EPA requests any relevant information on the performance of
these methods.
Furthermore, the 10-18 proposal was published before enactment of
the National Technology Transfer Advancement Act (NTTAA) of 1996. NTTAA
requires EPA to consider standards developed by voluntary consensus
standards bodies (VCSBs). EPA considers it appropriate to consider the
VCSB methods described later in this preamble (many of which were
revised after the 10-18 proposal), along with the other methods EPA is
proposing to approve.
EPA intends to consider comments submitted on this proposal only
when formulating the final rule. To the extent that anyone believes
that comments submitted in response to the 10-18 proposal are still
relevant, and wants EPA to consider them, such comments should be
resubmitted in response to today's proposal.
a. Total Recoverable Elements Digestion
EPA proposes a broad-purpose digestion procedure (as described in
EPA Method 200.2) for ``total recoverable'' elements for use with:
Inductively Coupled Plasma-Atomic Emission
Spectroscopy (ICP-AES)
Inductively Coupled Plasma-Mass Spectroscopy
(ICP-MS)
Stabilized Temperature Graphite Furnace Atomic
Absorption Spectroscopy (STGFAA), and
Flame Atomic Absorption Spectroscopy (FLAA)
methods.
The total recoverable procedure uses a combination of nitric and
hydrochloric acids (aqua regia) to prepare samples for analysis and is
compatible with several measurement techniques. This generally allows
laboratories to save some cost by reducing preparations and increasing
flexibility in their choice of analytical techniques after digestion.
The total recoverable digestion is less labor intensive than the
approved (and equivalent) ``total'' digestion method described in
Methods for Chemical Analysis of Water and Wastes (MCAWW) ``Metals
(Atomic Absorption Methods)'' Section 4.1.3, while providing equivalent
recovery of metals.
The total recoverable digestion procedure was incorporated into EPA
Methods 200.7 (ICP-AES), 200.8 (ICP-MS) and 200.9 (STGFAA). It is
published as the stand-alone Method 200.2, ``Sample Preparation
Procedure for Spectrochemical Determination of Total Recoverable
Elements' (Rev. 2.8, 1994). EPA proposes total recoverable digestion
for 200.7, 200.8, and 200.9 and allows the use of Method 200.2 as a
digestion procedure in measuring some pollutants by FLAA, and VCSB-
equivalents to EPA Methods 200.7, 200.8, and 200.9. However, Method
200.2 is not proposed for use with any standard GFAA methods due to the
potential chloride interference. For GFAA methods, the total nitric
acid digestion must be used.
The digestion procedure has been tested on various matrices using
EPA Methods 200.7, 200.8 and 200.9 and has been found comparable to
previously approved NPDES preparation procedures. Also, a joint EPA/
AOAC International study of Method 200.8 provided further
interlaboratory validation of the procedure.
b. Elements by ICP-MS
EPA proposes a multielement test procedure, Method 200.8
``Determination of Trace Elements in Waters and Wastes by Inductively
Coupled Plasma-Mass Spectrometry'' (Revision 5.4, 1994) for the
detection and quantification of 20 metals in aqueous wastewater
samples. Method 200.8 has been used in the NPDES program through ATP
approvals, and has been used in the NPDWR program for many years.
Method 200.8 determines elements using ICP-MS. Sample material in
solution is introduced by pneumatic nebulization into a radio-frequency
plasma where energy transfer processes cause desolvation, atomization,
and ionization. The ions are extracted from the plasma through a
differentially pumped vacuum interface and separated on the basis of
their mass-to-charge ratio by a quadrupole mass spectrometer having a
minimum resolution capability of 1 amu peak width at 5% peak height.
The ions transmitted through the quadrupole are registered by an
electron multiplier or Faraday detector, and the ion information is
processed by a data handling system. Interferences relating to the
technique are to be identified, and the results corrected accordingly.
Such corrections must compensate for isobaric elemental interferences
and interferences from polyatomic ions derived from the plasma gas,
reagents or sample matrix. Instrumental drift, as well as suppressions
or enhancements of instrument response caused by the sample matrix, are
to be corrected by using internal standards.
EPA developed ICP-MS Method 200.8 under a contract and in
cooperation with AOAC International, and
[[Page 18174]]
conducted a joint interlaboratory validation study of the method. The
method description includes a list of the elements to which the method
applies, sample collection practices, recommended analytical
conditions, quality control practices, instrumental and method
detection limits, and performance criteria based on the interlaboratory
study data.
EPA also is proposing to approve VCSB methods that are equivalent
to EPA Method 200.8: AOAC Method 993.14 [16th Edition], and ASTM Method
D5673-02. These methods should provide performance similar to that
obtained with Method 200.8.
c. Elements by STGFAA
EPA proposes a new multi-element test procedure, Method 200.9
``Determination of Trace Metals by Stabilized Temperature Graphite
Furnace Atomic Absorption'' (Revision 2.2, 1994) for the detection and
quantification of 16 metals in aqueous wastewater samples. Method 200.9
has been used in the NPDES program through ATP approvals, and it has
been used in the NPDWR program for many years.
Method 200.9 determines elements by stabilized temperature graphite
furnace atomic absorption spectroscopy (STGFAA). In STGFAA, the sample
and required matrix modifier are first pipetted onto the platform or a
device which provides delayed atomization. The sample is then dried at
a relatively low temperature (120 [deg]C) to avoid spattering. Once
dried, the sample is normally pretreated in a char or ashing step which
is designed to minimize the interference effects caused by the sample
matrix. After the char step, the furnace is allowed to cool prior to
atomization. The atomization cycle is characterized by rapid heating of
the furnace to a temperature where the metal (analyte) is atomized from
the pyrolytic graphite surface. The resulting atomic cloud absorbs the
element specific atomic emission produced by a hollow cathode lamp or a
electrodeless discharge lamp.
Because the resulting absorbance usually has a nonspecific
component (e.g., black body radiation) associated with the actual
analyte absorbance, an instrumental background correction device is
necessary to subtract from the nonspecific component from the total
signal. In the absence of interferences, the background corrected
absorbance is directly related to the concentration of the analyte.
Interferences relating to suppression or enhancement of instrument
response caused by the sample matrix, is to be corrected by the method
of standard addition.
The method description includes sample collection practices,
recommended analytical conditions, quality control practices, method
detection limits, and performance. Single laboratory studies show that
Method 200.9 achieves performance comparable to ICP-AES and ICP-MS
methods. In addition, Method 200.9 can achieve lower detection levels
than ICP-AES methods (for all analytes in common between the methods),
and ICP-MS methods (for certain analytes).
d. Hexavalent Chromium by Ion Chromatography
EPA proposes Method 218.6 ``Determination of Dissolved Hexavalent
Chromium in Drinking Water, Groundwater, and Industrial Wastewater
Effluent by Ion Chromatography'' (Revision 3.3, 1994) for determination
of hexavalent chromium. The NPDES program has used Method 218.6 through
interim approvals.
Method 218.6 uses ion chromatography (IC) to determine hexavalent
chromium (Cr(VI)) in samples. An aqueous sample is filtered through a
0.45 [mu]m filter, and the filtrate is adjusted to a pH of 9 to 9.5
with a buffer solution. A measured volume of sample (50-250 [mu]L) is
introduced into the ion chromatograph. A guard column is employed to
remove organics from the sample prior to separation of Cr(VI) as
CrO42-on an anion exchange separator column.
Cr(VI) is determined by post column derivatization with
diphenylcarbazide and passing through a low-volume flow-through cell
for detection of the colored complex with a visible lamp detector at
530 nm.
Cooperating with ASTM Committee D-19 on Water, EPA conducted an
interlaboratory validation study of EPA Method 218.6. The method
description includes sample collection practices, recommended
analytical conditions, quality control practices, method detection
limits for Cr(VI), and performance criteria. The Method MDL in reagent
water was 0.4 [mu]g/L, twenty-five times lower than the DL for
currently approved EPA Method 218.4, and performance was comparable to
the currently approved method. For example, according to regression
equations generated with data from the multilaboratory validation
study, analyses of a 50 [mu]g/L fortified reagent water sample would
produce an average recovery of 103% and a relative standard deviation
(RSD) of 5%.
ASTM, Standard Methods, and AOAC-International have approved this
method as a standard test method under their consensus systems and have
published it in their manuals of methods as follows: ASTM Method D5257-
97, Standard Methods Method 3500-Cr C [20th Edition] and 3500-Cr E
[18th, 19th], and AOAC Method 993.23 [16th Edition]. All three of these
methods were derived from EPA Method 218.6 and are being proposed for
approval.
e. Anions by Ion Chromatography
EPA proposes Method 300.0 ``The Determination of Inorganic Anions
in Water by Ion Chromatography,'' (Revision 2.1, August 1993) for
determination of common anions--bromide, chloride, fluoride, nitrate-N,
nitrite-N, ortho-phosphate, and sulfate--in wastewater. Method 300.0
has been used for many years in the NPDWR program and in the NPDES
program through interim approvals.
EPA Method 300.0 measures common anions using ion chromatography. A
water sample is injected into a stream of carbonate-bicarbonate eluent
and passed through a series of ion exchangers. Anions are separated on
the basis of their relative affinities for a low capacity, strongly
basic anion exchanger (guard and separator columns). The separated
anions are directed through a hollow fiber cation exchanger membrane
(fiber suppressor) or micromembrane suppressor bathed in continuously
flowing strong acid solution (regenerant solution). In the suppressor,
the separated anions are converted to their highly conductive acid
forms, and the carbonate-bicarbonate eluent is converted to weakly
conductive carbonic acid. The separated anions in their acid forms are
measured by conductivity. They are identified on the basis of retention
time as compared to reference standards. Quantitation is by measurement
of peak area or peak height.
Cooperating with ASTM Committee D-19 on Water, EPA conducted an
interlaboratory validation study of EPA method 300.0. The method
includes results of the study, sample collection practices, recommended
analytical conditions, quality control practices and estimated
detection limits for the applicable analytes, and performance criteria.
The method MDLs are lower than currently approved colorimetric methods,
and performance was comparable to currently approved methods, with
recovery falling within the 90-110% range and precision surpassing 10%
RSD for all analytes in the working range of the method (mid-point of
the calibrated range).
[[Page 18175]]
ASTM, Standard Methods, and AOAC-International approved and
published the method under their consensus systems. EPA proposes
approval of these following equivalents to EPA Method 300.0: ASTM
Method D4327-97 and -03, Standard Method 4110 B [18th, 19th and 20th
Ed.], and AOAC Method 993.30. EPA also is proposing EPA Method 300.1
``Determination of Inorganic Anions in Drinking Water by Ion
Chromatography,'' now approved for NPDWR compliance monitoring, and
which falls within the inherent flexibility (i.e., is equivalent to)
Method 300.0. This will further consistency among EPA monitoring
programs.
f. Nitrate and Nitrite by Colorimetry
EPA proposes the use of automated and manual cadmium reduction
methods for the determination of nitrate and nitrite, singly.
Specifically, EPA proposes that EPA Methods 353.2, Standard Methods
4500-NO3-E and F [18th, 19th, 20th] and 4500-NO3-
E and F (2000), ASTM Methods D3867-99(A) and (B), and I-4545-85 be used
to determine nitrate and nitrite singly, as well as in combination, in
NPDES compliance monitoring. Using these methods, ``nitrate+nitrite''
can be determined by passing the sample through a cadmium reduction
column (converting nitrate to nitrite for final analysis), and that the
column can be by-passed to determine nitrite singly. With both of these
values, nitrate can be determined by subtracting ``nitrite'' from
``nitrate+nitrite.'' This proposal is consistent with NPDWRs that allow
cadmium reduction-based methods for nitrate+nitrite to measure nitrate
and nitrite singly (see 40 CFR 141.23).
With regard to performance of automated methods, multi-laboratory
data for EPA Method 353.2 indicates that analysis of a 1 mg/L nitrate
sample will provide an average recovery of 100%, and a relative
standard deviation (RSD) of 5.4%. Manual methods provide similar
performance, with 4500-NO3-E demonstrating an average
recovery of 100% and RSD of 1% in single laboratory studies at
concentrations near 1 mg/L. The equivalent versions of these methods
published by other organizations should provide equivalent performance,
given that they employ the same chemistry and procedures.
g. Chlorine by Low Level Amperometry
EPA proposes Standard Method 4500-Cl E [18th Ed.] and proposes
4500-Cl E [19th and 20th Ed.] and 4500-Cl E (2000) for the detection
and quantification of low levels of chlorine in water (all editions are
essentially the same). Method 4500-Cl E is a minor modification of the
approved amperometric Method 4500-Cl D and can measure down to 10
[mu]g/L chlorine. Federal and state permitting authorities requested
such a method so they can assess compliance with effluent limits based
on EPA and state water quality criteria for chlorine. You can find
supporting performance data for the method at Journal of the Water
Pollution Control Federation, Vol. 51, pages 2636-2640 (1979), a copy
of which is included in the docket for this proposal.
h. Updated Versions of Currently Approved EPA Methods
In 1993 and 1994, EPA updated a number of methods from the
``Methods for the Chemical Analysis of Water and Wastes'' (MCAWW)
manual, and Method 200.7 (printed at 40 CFR part 136, Appendix A). For
the most part, these updates were technically equivalent to previously
approved versions, but offer the advantages of a consistent
Environmental Monitoring Management Council (EMMC--an EPA committee
consisting of EPA managers and scientists) format and explicit QC
requirements which should result in improved data quality. Many of the
versions are approved for NPDWR monitoring, so approval of these
methods will further the goal of consistency among EPA monitoring
programs. Finally many of these methods explicitly allow performance-
based modifications, thereby increasing method flexibility.
All these methods, listed in Table I, were included in the 10-18
proposal. EPA proposes the approval of these additions and withdrawal
of the old MCAWW versions.
Table I.--Updated Revisions Proposed in 10-18-95
----------------------------------------------------------------------------------------------------------------
Updated revisions Currently approved revision
--------------------------------------------- (to be withdrawn)
Parameter -------------------------------
Method Revision Method Revision
----------------------------------------------------------------------------------------------------------------
Turbidity.......................... 180.1 Revision 2.0, August 1993*. 180.1 1978
Multiple Metals.................... 200.7 Revision 4.4, 1994*........ 200.7 1990
Mercury............................ 245.1 Revision 3.0, 1994*........ 245.1 1974
Total Cyanide[dagger].............. 335.4 Revision 1.0 August 1993*.. 335.3 1978
Ammonia............................ 350.1 Revision 2.0, August 1993.. 350.1 1978
TKN................................ 351.2 Revision 2.0, August 1993.. 351.2 1978
Nitrate-Nitrite.................... 353.2 Revision 2.0, August 1993*. 353.2 1978
Phosphorus (all forms)............. 365.1 Revision 2.0, August 1993*. 365.1 1978
Sulfate............................ 375.2 Revision 2.0, August 1993*. 375.2 1978
COD................................ 410.4 Revision 2.0, August 1993.. 410.4 1978
Phenols............................ 420.4 Revision 1.0, August 1993.. 420.2 1974
----------------------------------------------------------------------------------------------------------------
* Currently approved for use in NPDWR or NSDWR monitoring
[dagger] Note: EPA Method 335.4 is technically equivalent to the currently approved version of Method 335.3 when
Method 335.3 is run in compliance 40 CFR 136.3, Table IB--Note 20 (specifically requiring the manual digestion
of cyanide samples; if compared method-to-method, the procedures are quite different). However, as currently
written, the sulfide removal procedure in Method 335.4 could lead to removal of particulate cyanide from the
sample prior to analysis. Therefore, EPA proposes to add a footnote to the table to clarify the proper
procedure for removing sulfide interferences. The footnote will require analysts to reconstitute samples
treated for sulfide so that particulates are distilled along with the liquid sample.
Because these new versions of methods contain QC requirements (not
previously included), and detection limits may have changed, EPA is
particularly interested in comments regarding the ability of
laboratories to achieve the specified QC requirements and detection
limits.
EPA also requests comments on any additional costs that
laboratories expect they might incur to comply with the QC requirements
specified in the methods. EPA believes that many laboratories are
already using thorough QC programs to ensure the reliability of the
results they
[[Page 18176]]
report, particularly for those methods already approved for NPDWR or
NSDWR monitoring. EPA expects that any additional costs will be at
least partially offset by the increased flexibility in these revisions
(which explicitly allow analysts to reduce costs by introducing cost-
effective innovations).
4. New EPA Methods
a. Mercury by CVAFS
EPA proposes Method 245.7, ``Mercury in Water by Cold Vapor Atomic
Fluorescence Spectrometry'' [December 2003] (EPA-821-D-03-001) for
measuring mercury (Hg) in wastewater. Method 245.7 provides reliable
measurements of mercury at EPA water quality criteria levels. The
method employs cold-vapor atomic fluorescence spectrometry (CVAFS), a
brominating digestion creating minimal interference, and ultra-pure
argon as the carrier gas. Samples are oxidized by a potassium bromate/
potassium bromide reagent, sequentially pre-reduced with
NH2OHCl to destroy excess bromine, and the ionic mercury
reduced with SnCl2 to convert Hg(II) to volatile Hg(0).
Hg(0) is then separated from solution by purging with high purity argon
gas through a semi-permeable dryer tube. Once the Hg(0) passes into the
inert argon gas stream, it is carried into the CVAFS detector cell to
determine mercury concentration.
Method 245.7 is similar to EPA Method 1631 ``Mercury in Water by
Oxidation, Purge and Trap, and CVAFS,'' originally promulgated on June
8, 1999 (64 FR 30434), for the NPDES program. Both methods use a CVAFS
detector to measure low levels of mercury. Method 245.7 uses a liquid-
gas separation and a dryer tube for analyte isolation, while Method
1631 uses a purge and gold trap isolation procedure. This difference
makes Method 245.7 a low cost alternative to Method 1631 for
measurement of trace-level mercury using CVAFS technology. For that
reason, the Association of Metropolitan Sewerage Agencies (AMSA)
petitioned the Agency to approve this alternative method. In response,
EPA conducted a multi-laboratory validation of this method in 2001 to
assess the method's performance.
During this validation study, the method was tested on a variety of
matrix types. In reagent water analyses performed in eight
laboratories, average recoveries range between 85% to 105%, and
relative standard deviations (RSDs) were below 15%. Percent recoveries
in matrix spike/matrix spike duplicate industrial and municipal
effluent samples ranged from 64% to 120%. The reported method detection
limit is 5.0 ng/L based on the data from the eight participating
laboratories. Following this study, Method 245.7 was updated to include
the resulting performance criteria and to conform with recent EPA
guidelines regarding contamination control.
Method 245.7 is available at http://www.epa.gov/waterscience/methods/. In addition, copies of the method and of the interlaboratory
validation study report are in the docket supporting this proposal.
In addition to proposing EPA Method 245.7, EPA is soliciting
comment on requirements for sample collection when using this method.
On October 29, 2002, EPA promulgated a footnote at 40 CFR part 136 that
includes sample preservation and storage requirements for samples
collected for the determination of mercury using EPA Method 1631. This
footnote states that: ``Samples collected for the determination of
trace level mercury (100 ng/L) using EPA Method 1631 must be collected
in tightly-capped fluoropolymer or glass bottles and preserved with
BrCl or HCl solution within 48 hours of sample collection. The time to
preservation may be extended to 28 days if a sample is oxidized in the
sample bottle. Samples collected for dissolved trace level mercury
should be filtered in the laboratory. However, if circumstances prevent
overnight shipment, samples should be filtered in a designated clean
area in the field in accordance with procedures given in Method 1669.
Samples that have been collected for determination of total or
dissolved trace level mercury must be analyzed within 90 days of sample
collection.'' EPA is requesting comments and data demonstrating whether
this footnote should or should not also be applied to Method 245.7.
5. New Voluntary Consensus Standard Bodies (VCSB) Methods
VCSB organizations asked EPA to approve several new VCSB methods
for NPDES monitoring. In response to these requests, EPA proposes
approval of the following VCSB methods. Some of the methods proposed
are used in EPA monitoring programs today and/or have been approved as
limited-use alternate test procedures.
a. Available Cyanide by Ligand Exchange-FIA
ASTM Method D6888-03 determines available cyanide (equivalent to
``cyanide amenable to chlorination'') using ligand exchange followed by
flow injection analysis using gas diffusion separation and amperometric
detection. It is very similar to the currently approved Method OIA-1677
(promulgated on December 30, 1999, 64 FR 73414).
Method D6888-03 was validated in an extensive intralaboratory study
using several natural and industrial water matrices, and a 10-
laboratory study using synthetic wastewater. Recoveries of potassium
nickel cyanide and mercury (II) cyanide, the two strongest available
cyanide complexes, ranged from 89.9 to 99.6% and 82.9 to 99.3%,
respectively (in samples fortified to 100 [mu]g/L as CN-).
Method D6888-03 states that either nickel cyanide or mercury (II)
cyanide may be used to prepare quality control samples. However, for
the purposes of NPDES compliance monitoring, EPA is proposing that only
mercury (II) cyanide be used. Mercury (II) cyanide is a stronger
complex than nickel cyanide (as evidenced by the slightly lower
recoveries cited above), and, therefore, provides the most rigorous
test for method performance. Currently approved Method OIA-1677 also
specifies use of mercury (II) cyanide for the same reason.
In addition, two issues have come to EPA's attention regarding the
use of ligand exchange-amperometric detection methods for available
cyanide. EPA seeks comment on both of these issues. First, EPA has
received information suggesting that sulfide at levels below those
detected with the lead acetate paper may produce false positive signals
on the amperometric detection systems used in D6888-03 and OIA-1677
(see Zheng et al. ``Evaluation and Testing of Analytical Methods for
Cyanide Species in Municipal and Industrial and Contaminated Waters,''
Environ. Sci. Technol. 2003, 37, 107-115). Lead acetate paper generally
recommended for screening for the presence of sulfide interferences in
cyanide methods, but the paper will not detect sulfides below
approximately 5 ppm. For this reason, analysts suspecting a sulfide
interference should test their sample with a more sensitive sulfide
procedure and treat the sample accordingly. Appropriate test procedures
for this purpose include the ion selective electrode (ISE) ASTM Method
D4658-92(1996) and Standard Method 4500-S2-G which are proposed for use
in today's rule.
Second, EPA's National Enforcement Investigation Center (NEIC)
laboratory has found that when samples that contain significant solids
are analyzed
[[Page 18177]]
by OIA-1677, particles in the sample can settle out in the sample
apparatus and also can clog the flow-injection system. As a result,
measurements of cyanide in samples containing particulates decrease as
the samples are allowed to stand in the sample tubes, and decrease as
the system clogs. This decrease could be due to a number of factors,
such as adsorption of released cyanide onto particulate or re-
complexation of released cyanide with metals. This settling and
clogging may be a problem in other similar cyanide-measurement systems
that contain a rack of sample tubes, because the particles can settle
during the time that the samples sit in these tubes. Suggested
solutions to the problem are to (1) limit methods that use a rack of
sample tubes to measurement of dissolved cyanide only; i.e., samples
that have been filtered through a 0.45-micron filter to remove
particles, (2) to limit these methods to analysis of one sample at a
time so that the settling cannot occur, (3) to limit the time between
addition of the ligand-exchange reagents and the time of analysis to
preclude settling, or (4) to require sample agitation during storage in
the sample rack. EPA solicits comment on the problem, on the proposed
solutions and on other possible solutions, and seeks data further
characterizing the conditions under which the problem occurs and any
solution(s) to the problem.
b. Cations by Ion Chromatography
ASTM International Standard Test Method D 6919-03, ``Determination
of Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water
and Wastewater by Ion Chromatography,'' applies to the simultaneous
determination of dissolved inorganic alkali and alkaline earth cations
and the ammonium cation in reagent water, drinking water, and
wastewaters by suppressed and non-suppressed ion chromatography. While
alkali and alkaline earth cations can be determined by alternative
techniques such as AAS or ICP, ammonium cation in the same sample must
be measured separately by a wet chemical technique such as colorimetry,
titrimetry, or ammonia-selective electrode. Ion chromatography in a
single automated run can determine ammonium plus all of the important
inorganic cations including lithium, sodium, potassium, magnesium and
calcium.
The cationic analytes are injected into a dilute acid eluent and
separated by differential retention as they flow through guard and
analytical columns packed with a low-capacity cation-exchange material.
The separated cations are detected using conductivity detection, which
is most sensitive when the background signal arising from the eluent
has the lowest possible noise. One means to achieve low background
noise is to combine the conductivity detector with a suppressor device
that reduces the conductance of the eluent (i.e., background noise) and
also transforms the separated cations into their more conductive
corresponding bases. Detection can also be achieved without chemical
suppression, whereby the difference between the ionic conductance of
the eluent and analyte cation is measured directly after the analytical
column. This test method includes both suppressed and non-suppressed
detection technologies.
A total of fourteen laboratories, employing one operator each,
contributed data to the test method interlaboratory collaborative
study. Three matrices were studied; reagent water, drinking water and
wastewater. Each participant prepared and analyzed four Youden pairs
for each of the six analytes in each of the three matrices. Analyte
recoveries using Method D 6919-03 were determined in the range of 0.5-
40 mg/L, with the specific concentration ranges tested for each cation
varying slightly within this overall range. Method Detection Limits
(MDLs) were confirmed in the 3-38 [mu]g/L range. MDLs obtained by
suppressed conductivity were approximately two times lower than the
MDLs obtained by non-suppressed conductivity. The precision and
recovery data for all analytes in all matrices tested are provided in
the method. For example, across all analytes at concentrations of
approximately 5 mg/L in drinking water, the range of multilaboratory
recovery was 89-103% with relative standard deviation ranging from 4-
15%. Quality control limits for the method and the data used to
generate them are available in the docket supporting today's proposal.
Standard Test Method D 6919-03 is available from ASTM
International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken,
PA 19428-2959, United States. Douglas Later, the ASTM Subcommittee
D19.05 Task Group Chairman for Method D 6919-03, can be reached at
Dionex Corporation, 500 Mercury Drive, Sunnyvale, CA 94086. Telephone:
(408) 481-4253, Fax: (408) 737-2470, e-mail: [email protected].
Copies of the method and the validation study report are in the docket
for today's proposed rule.
c. Chloride by Potentiometry
Standard Method 4500-Cl-D [18th, 19th, and 20th Ed.] and (2000) is
used to determine chloride in water by potentiometric titration, using
a silver nitrate/solution with a glass and silver-silver chloride
electrode system. During titration, an electronic voltmeter is used to
detect the change in potential between the two electrodes. The end
point of the titration is reached when the instrument reading at which
the greatest change in voltage has occurred for a small and constant
increment of silver nitrate added. The potentiometric method is a
useful alternative to other approved methods when measuring chloride in
colored or turbid samples that are not amenable to visual titration.
The method also is included in NSDWRs, so its approval for NPDES
program will further consistency between the wastewater and drinking
water programs.
d. Chloride by Ion Selective Electrode
Method D512-89 (1999) C is a method for determining chloride ion in
water by ion selective electrode (ISE). The stated range of the method
is 2 to 1000 mg/L. Precision and bias were determined in reagent water
and other matrices using a five-laboratory, seven-operator study.
Recovery ranged from roughly 93-103% with RSD that generally fell
within 5-10%. Additional data are available in the method.
e. Cyanide by Ion Selective Electrode
Standard Method 4500-CN-F [18th, 19th, and 20th Ed.] and (2000),
and ASTM Method D2036-98 A, allow for analysis of cyanides, following
distillation, using ion selective electrode (ISE) technology. These ISE
methods have been used for a number of years in the context of NPDWR
compliance monitoring, and have been approved in NPDES monitoring, on a
limited-use basis, through the ATP program. Given the common use of
these methods, and their ability to overcome certain interferences that
could affect approved colorimetric methods, their inclusion at 40 CFR
part 136 will be a useful addition to the suite of cyanide methods.
Furthermore, the approvals will improve consistency across EPA
programs.
ASTM conducted a six-operator, five-laboratory study of the ISE
method as applied to reagent water and selected matrices. The effective
range of the methods is 0.05-10 mg/L. Performance characteristics of
the method are summarized in regression equations reproduced by both
methods. As an example of performance, at 0.06 mg-
[[Page 18178]]
CN-/L reagent water, the interlaboratory percent recovery was 98% with
a relative standard deviation of 14%. The Standard Method is
technically identical and, therefore, should provide identical
performance.
f. Sulfide by Ion Selective Electrode
Standard Method 4500-S2-G [18th, 19th and 20th Ed.] and ASTM Method
D4658-92 (1996) determine sulfide in water using ion selective
electrode (ISE). The Standard Method cites an applicable range of
0.032-100 mg/L with a 5% RSD at a concentration of 0.182 mg/L. The ASTM
Method cites a range of 0.04-4000 mg/L, and a three-day, six-laboratory
study demonstrated concentration variations of 6.5% (for 0.05-1.0 mg/
L), 2.5% (1.0-100 mg/L), and 2.0% (100-4000 mg/L). Sulfide ISE methods
are unaffected by sample color and turbidity and, therefore, provide a
valuable substitute for approved colorimetric methods that may be
affected by these interferences.
g. Nitrate by Ion Selective Electrode
Method 4500-NO3-D [18th, 19th, 20th] and (2000)
determines nitrate in water. The method employs an ion selective
electrode (ISE) that develops a potential across a porous, inert
membrane that holds in place a water-immiscible liquid ion exchanger.
The method has a range of about 0.14 to 1400 mg nitrate-N/L, and a
precision over the range of 2.5%. Nitrate ISE methods are unaffected by
sample color and turbidity and therefore provide a valuable substitute
for approved colorimetric methods that may be effected by these
interferences. However, these ISE methods are susceptible to
interferences due to variations in ionic strength. Therefore, when
using these methods, analysts are to ensure that the sample and
standard ionic strength match, or the method is to be performed in a
way to prevent such interferences (e.g., standard additions).
6. Updated Versions of Currently Approved Analytical Methods
a. EPA WET Methods
This rule proposes, and seeks comment on, an errata sheet for the
following methods manuals:
USEPA. October 2002. Short-term Methods for
Estimating the Chronic Toxicity of Effluents and Receiving Waters to
Freshwater Organisms. Fourth Edition. U.S. Environmental Protection
Agency, Office of Water, Washington, DC EPA/821/R-02/013. (The
``freshwater chronic manual'').
USEPA. October 2002. Methods for Measuring the
Acute Toxicity of Effluents and Receiving Waters to Freshwater and
Marine Organisms. Fifth Edition. U.S. Environmental Protection Agency,
Office of Water, Washington DC EPA/821/R-02/012. (The ``freshwater
acute manual'').
The errata sheet contains revisions to correct the following
typographical errors:
1. Freshwater chronic manual page 274, section 1.10--
[GRAPHIC] [TIFF OMITTED] TP06AP04.000
The ``3'' before the square root symbol in the equation above
should be removed.
2. Freshwater chronic manual page 274, section 1.11--The value
0.087 should be changed to 0.162.
3. Freshwater chronic manual page 10, section 4.4.1--``* * * The
concentration of metals Al, As, Cr, Co, Cu, Fe, Pb, Ni, and Zn,
expressed as total metal, should not exceed 1 [mu]g/L each * * *''
4. Freshwater chronic manual page 11, section 4.8.3--``* * * The
concentration of total organochlorine pesticides should not exceed 0.15
[mu]g/g wet weight * * *''
5. Freshwater acute manual, section 7.2.3.1 Correct the
concentration of selenium from 2 mg/L to 2 ug/L.
b. ASTM Methods
This rule proposes to approve a number of updated ASTM methods in
NPDES compliance monitoring. Table II lists the most recently approved
versions of the ASTM and the proposed versions for NPDES monitoring, as
well as those proposed for NPDWR and NSDWR monitoring (proposed in
Section IV.C.2). Copies of all the proposed methods are in the paper
docket for review (they are not included in the e-docket due to
copyright issues).
All of the proposed methods, except D512-89 (1999) (which is
identical to the previous version), incorporate minor technical and/or
editorial revisions that improve the methods. Previously approved
versions of ASTM methods will remain approved.
Table II.--Proposed ASTM Methods
----------------------------------------------------------------------------------------------------------------
Proposed for Proposed for
Approved method wastewater drinking water New method number
----------------------------------------------------------------------------------------------------------------
D511-93(A)........................... X X D511-03(A)
D511-93(B)........................... X X D511-03(B)
D512-89(A)........................... X ................... D512-89(99)(A)
D512-89(B)........................... X X D512-89(99)(B)
D516-90.............................. X X D516-02
D858-95(A)........................... X ................... D858-02(A)
D858-95(B)........................... X ................... D858-02(B)
D858-95(C)........................... X ................... D858-02(C)
D859-94.............................. X X D850-00
D888-92(A)........................... X ................... D888-03(A)
D888-92(B)........................... X ................... D888-03(B)
D1067-92............................. X ................... D1067-02
D1067-92(B).......................... ................... X D1067-02(B)
D1068-96(A).......................... X ................... D1068-03(A)
D1068-96(B).......................... X ................... D1068-03(B)
D1068-96(C).......................... X ................... D1068-03(C)
D1068-96(D).......................... X ................... D1068-03(D)
D1125-95(A).......................... X X D1125-95(99)(A)
[[Page 18179]]
D1126-86(92)......................... X ................... D1126-02
D1179-93(A).......................... X ................... D1179-99(A)
D1179-93(B).......................... X X D1179-99(B)
D1246-95(C).......................... X ................... D1246-95(99)
D1252-95(A).......................... X ................... D1252-00(A)
D1252-95(B).......................... X ................... D1252-00(B)
D1253-86(92)......................... X X D1253-03
D1293-84(90)(A)...................... X ................... D1293-99(A)
D1293-84(90)(B)...................... X ................... D1293-99(B)
D1293-95............................. ................... X D1293-99
D1426-98(A).......................... X ................... D1426-03(A)
D1426-98(B).......................... X ................... D1426-03(B)
D1687-92(A).......................... X ................... D1687-02(A)
D1687-92(B).......................... X ................... D1687-02(B)
D1687-92(C).......................... X ................... D1687-02(C)
D1688-95(A).......................... X X D1688-02(A)
D1688-95(B).......................... X ................... D1688-02(B)
D1688-95(C).......................... X X D1688-02(C)
D1691-95(A).......................... X ................... D1691-02(A)
D1691-95(B).......................... X ................... D1691-02(B)
D1886-90(A).......................... X ................... D1886-94(98)(A)
D1886-90(B).......................... X ................... D1886-94(98)(B)
D1886-90(C).......................... X ................... D1886-94(98)(C)
D1889-94............................. X ................... D1889-00
D1890-90............................. X ................... D1890-96
D1943-90............................. X ................... D1943-96
D2330-88............................. X ................... D2330-02
D2460-90............................. X Already Approved D2460-97
D2972-97(A).......................... X ................... D2972-03(A)
D2972-97(B).......................... X X D2972-03(B)
D2972-97(C).......................... X X D2972-03(B)
D3086-90............................. X ................... D5812-96 (2002)
D3223-97............................. ................... X D3223-02
D3373-93............................. X ................... D3373-03
D3454-91............................. X Already Approved D3454-97
D3557-95(A).......................... X ................... D3557-02(A)
D3557-95(B).......................... X ................... D3557-02(B)
D3557-95(C).......................... X ................... D3557-02(C)
D3557-95(D).......................... X ................... D3557-02(D)
D3558-94(A).......................... X ................... D3558-03(A)
D3558-94(B).......................... X ................... D3558-03(B)
D3558-94(C).......................... X ................... D3558-03(C)
D3559-96(A).......................... X ................... D3559-03(A)
D3559-96(B).......................... X ................... D3559-03(B)
D3559-96(C).......................... X ................... D3559-03(C)
D3559-96(D).......................... X X D3559-03(D)
D3590-89(A).......................... X ................... D3590-02(A)
D3590-89(B).......................... X ................... D3590-02(B)
D3645-93(88)(A)...................... X ................... D3645-03(A)
D3645-93(88)(B)...................... X ................... D3645-03(B)
D3645-97(B).......................... ................... X D3645-03(B)
D3649-91............................. ................... X D3649-98a
D3697-92............................. ................... X D3697-02
D3859-98(A).......................... X X D3859-03(A)
D3859-98(B).......................... X X D3859-03(B)
D3867-90(B).......................... Already Approved X D3867-99(B)
D3972-97............................. ................... X D3972-02
D4107-91............................. ................... X D4107-98 (2002)
D4190-94............................. X ................... D4190-99
D4327-97............................. Proposed Today X D4327-03
D4382-95............................. X ................... D4382-02
D4657-92............................. X ................... D4657-92 (1999)
D4785-93............................. X X D4785-00a
D5174-97............................. X X D5174-02
D5317-93............................. ................... X D5317-98 (2003)
----------------------------------------------------------------------------------------------------------------
[[Page 18180]]
c. Standard Methods
This rule proposes to approve a number of updated Standard Methods
in NPDES compliance monitoring; methods previously approved will
continue to be applicable for compliance monitoring. Previously, USEPA
has referenced approved Standard Methods using the edition of Standard
Methods for the Examination of Water and Wastewater in which they were
published. However, Standard Methods will now distribute methods on-
line (likely in addition to printed volumes), so the option of only
referencing an edition will not be practical.
For this reason, EPA will use a new numbering system to track the
approved versions of Standard Methods. To indicate which version of the
method is approved, the date of approval of a section by the Standard
Method Committee will be used. For example, 2120 B-01 indicates the
version of 2120 B approved by the Standard Methods Committee in 2001.
The Committee Approval Date for a Standard Methods Section (e.g.,
Section 2120) is provided in a footnote at the beginning of the
Section.
Table III lists the most recently approved versions of the Standard
Methods and the proposed versions for NPDES monitoring, as well as
those proposed for NPDWR and NSDWR monitoring (proposed in Section
IV.C.3). While a number of methods contain no changes from previously
approved version, some incorporate minor technical and editorial
revisions to improve user-friendliness, update references, and correct
errors. Methods that were revised from previous versions are indicated
on the table. Previously approved versions of Standard Methods will
remain approved. Copies of all the proposed methods are in the paper
docket for review (they are not included in e-docket due to copyright
issues), see Section IV.C.2.
Table III.--Proposed Standard Methods
----------------------------------------------------------------------------------------------------------------
Revised from standard methods proposed for proposed for
[most recent approved version] revised wastewater drinking water New number
----------------------------------------------------------------------------------------------------------------
2120 B [20th]..................... X X X 2120 B-01
2130 B [20th]..................... .......... X ................. 2130 B-01
2150 B [20th]..................... .......... ................. X 2150 B-97
2310 B [20th]..................... .......... X ................. 2310 B-01
2320 B [20th]..................... .......... X X 2320 B-97
2340 B [20th]..................... X X ................. 2340 B-97
2510 B [20th]..................... X X X 2510 B-97
2540 B [20th]..................... .......... X ................. 2540 B-97
2540 C [20th]..................... .......... X X 2540 C-97
2540 D [20th]..................... .......... X ................. 2540 D-97
2540 F [20th]..................... .......... X ................. 2540 F-97
2550 B [20th] (listed as ``2550'' X X X 2550 B-00 (2550-00)
for drinking water regulations).
3111 B [19th]..................... X X X 3111 B-99
3111 C [19th]..................... .......... X ................. 3111 C-99
3111 D [19th]..................... .......... X ................. 3111 D-99
3112 B [19th]..................... .......... X X 3112 B-99
3113 B [19th]..................... .......... X X 3113 B-99
3114 B [19th]..................... X X X 3114 B-97
3120 B [20th]..................... X X X 3120 B-99
3500-Al B [20th].................. .......... X ................. 3500-Al B-01
3500-As B [20th].................. X X ................. 3500-As B-97
3500-Ca B [20th].................. .......... X X 3500-Ca B-97
3500-Cr B [20th].................. X X ................. 3500-Cr B-01
3500-Cu B [20th].................. X X ................. 3500-Cu B-99
3500-Cu C [20th].................. X X ................. ..........................
3500-Fe B [20th].................. X X ................. 3500-Fe B-97
3500-Pb B [20th].................. .......... X ................. 3500-Pb B-97
3500-Mg B [20th].................. .......... ................. X 3500-Mg B-97
3500-Mn B [20th].................. .......... X X 3500-Mn B-99
3500-K B [20th]................... .......... X ................. 3500-K B-99
3500-Na B [20th].................. X X ................. 3500-Na B-97
3500-V B [20th]................... .......... X ................. 3500-V B-97
3500-Zn B [20th].................. .......... X ................. 3500Zn B-97
4110 B [20th] (proposed for NPDES .......... X X 4110 B-00
in this rule).
4500-B B [20th]................... .......... X ................. 4500-B B-00
4500-CN-D [20th].................. .......... X ................. 4500-CN D-99
4500-CN-E [20th].................. .......... X X 4500-CN E-99
4500-CN-F [20th] (proposed for .......... X X 4500-CN F
NPDES in this rule).
4500-CN-G [20th].................. .......... X X 4500-CN G-99
4500-Cl B [20th].................. .......... X ................. 4500-Cl B-00
4500-Cl C [20th].................. .......... X ................. 4500-Cl C-00
4500-Cl D [20th].................. .......... X X 4500-Cl D-00
4500-Cl E [20th] (proposed for .......... X X 4500-Cl E-00
NPDES in this rule).
4500-Cl F [20th].................. .......... X X 4500-Cl F-00
4500-Cl G [20th].................. .......... X X 4500-Cl G-00
4500-Cl H [20th].................. .......... ................. X 4500-Cl H-00
4500-Cl I [20th].................. .......... ................. X 4500-Cl I-00
4500-Cl-B [20th].................. .......... X ................. 4500-Cl-B-97
4500-Cl-C [20th].................. .......... X X 4500-Cl-C-97
4500-Cl-D [20th].................. .......... ................. X 4500-Cl-D-97
4500-Cl-E [20th].................. .......... X ................. 4500-Cl-E-97
4500-ClO 2 C [20th]............... .......... ................. X 4500-ClO C-00
4500-ClO2 E [20th]................ .......... X X 4500-ClO2
4500-F-B [20th]................... .......... X X 4500-F-B-97
4500-F-C [20th]................... .......... X X 4500-F-C-97
4500-F-D [20th]................... .......... X X 4500-F-D-97
4500-F-E [20th]................... .......... X ................. 4500-F-E-97
4500-H+ B [20th].................. X X X 4500-H+ B-00
4500-NH3 B [20th]................. .......... X ................. 4500-NH3 B-97
4500-NH3 C [20th]................. .......... X ................. 4500-NH2-C-97
4500-NH3 D [20th]................. .......... X ................. 4500-NH3 D-97
4500-NH3 E [20th]................. .......... X ................. 4500-NH3 E-97
4500-NH3 G [20th]................. X X ................. 4500-NH3 G-97
4500-NO2 B [20th]................. .......... X X 4500-NO 2 B-00
4500-NO3-D [20th]................. .......... X ................. 4500-NO 3- D-00
4500-NO3- E [20th]................ X ................. X 4500-NO3- E-00
4500-NO3- F [20th]................ .......... X X 4500-NO3 F-00
4500-NO3- H [20th]................ .......... X ................. 4500-NO3- H-00
4500-Norg B [20th]................ .......... X ................. 4500-N org B-97
4500-Norg C [20th]................ .......... X ................. 4500-Norg C-97
4500-O C [20th]................... .......... X ................. 4500-O C-01
4500-O G [20th]................... .......... X ................. 4500-O G-01
4500-O 3 B [19th] (4500-O3 B X ................. X 4500-O3 B-97
[20th] is proposed in this rule).
4500-SiO2 C [20th] is proposed in X ................. X 4500-SiO2> C-97
this rule).
4500-SiO2 C [20th]................ X X ................. 4500-SiO2 C-97
4500-SiO2 D [20th]................ .......... ................. X 4500-SiO2 D-97
4500-SiO2 E [20th]................ .......... ................. X 4500-SiO2 E-97
4500-SiO2 F [20th]................ .......... ................. X 4500-SiO2- F-97
4500-S2- D [20th]................. .......... X ................. 4500-S2- D-00
4500-S2 F [20th].................. .......... X ................. 4500-S2- F-00
4500-S2- G [20th]................. .......... X ................. 4500-S2- G-00
4500-SO332- B [20th].............. .......... X ................. 4500-SO332- B-00
5210 B [20th]..................... X X ................. 5210 B-01
5220 C [20th]..................... .......... X ................. 5220 C-97
5220 D [20th]..................... .......... X ................. 5220 D-97
5310 B [20th]..................... .......... X ................. 5310 B-00
5310 C [20th]..................... .......... X ................. 5310 C-00
5310 D [20th]..................... .......... X ................. 5310 D-00
5520 B [20th]..................... X X ................. 5520 B-01
5540 C [20th]..................... X X X 5540 C-00
6200 B [20th]..................... X X ................. 6200 B-97
6200 C [20th]..................... .......... X ................. 6200 C-97
6410 B [20th]..................... .......... X ................. 6410 B-00
6420 B [20th]..................... X X ................. 6420 B-00
7110 B [20th]..................... X X X 7110 B-00
7110 C [20th]..................... .......... ................. X 7110 C-00
7120 [20th]....................... X ................. X 7120-97
7500-Cs B [20th].................. .......... ................. X 7500-Cs B-02
7500-I B [20th]................... .......... ................. X 7500-I B-00
7500-I C [20th]................... .......... ................. X 7500-I C-00
7500-I D [20th]................... .......... ................. X 7500-I D-00
7500-Ra B [20th].................. .......... X ................. 7500-Ra B-01
7500-Ra C [20th].................. .......... X X 7500-Ra C-01
7500-Ra D [20th].................. .......... ................. X 7500-Ra D-01
7500-Sr B......................... .......... ................. X 7500-Sr B-01
7500-3H B [20th].................. X ................. X 7500-3 H B-00
7500-U B [20th]................... .......... ................. X 7500-U B-00
7500-U C [20th]................... .......... ................. X 7500-U C-00
9215 B [20th]..................... .......... ................. X 9215 B-00
9221 A [20th]..................... .......... ................. X 9221 A-99
9221 B [20th]..................... .......... X X 9221 B-99
9221 C [20th]..................... X X X 9221 C-99
9221 D [20th]..................... .......... X X 9221 D-99
9221 E [20th]..................... .......... X X 9221 E-99
9222 A [20th]..................... X ................. X 9222A-97
9222 B [20th]..................... X X ................. 9222 B-97
9222 C [20th]..................... .......... ................. X 9222 C-97
9222 D [20th]..................... .......... X X 9222 D-97
9223 [20th]....................... .......... ................. X 9223-97
9230 B [20th]..................... X X ................. 9230 B-93
9230 C [20th]..................... .......... X ................. 9230 C-93
----------------------------------------------------------------------------------------------------------------
d. AOAC International
This rule proposes to update references to approved methods from
AOAC International to include the versions of those methods published
in the 16th edition of Official Methods of Analysis of AOAC
International, 1995, for use in NPDES compliance monitoring. Approved
AOAC methods from earlier editions of Official Methods of Analysis of
AOAC International will continue to be applicable for compliance
monitoring.
7. Method Modifications, Analytical Requirements, and Reporting
Requirements
a. Replacement of Mercury Catalyst in TKN Methods
Mercuric sulfate is used as a catalyst in some approved methods for
determining total Kjeldahl nitrogen (TKN). Mercuric sulfate is a toxic
hazard and the presence of mercury in used reagents increases waste
disposal costs. For these reasons, EPA proposes to explicitly require
the substitution of copper sulfate for mercuric sulfate in all TKN
methods. Copper sulfate exhibits significantly less toxicity than
mercuric sulfate. The European community has already eliminated
mercuric chloride from their total nitrogen methods in favor of less
toxic catalysts, and some approved methods (e.g., 19th and 20th Ed.
Standard Methods for TKN) have even included copper sulfate explicitly
as a catalyst (evidencing the technical acceptability of the
substitution).
b. Approval of Additional Standards for Turbidity
EPA is proposing to formally approve the use of styrene
divinylbenzene beads (AMCO-AEPA-1 Standard) and Hach StablCal as
alternatives to the presently approved formazin standard. Formazin is
prepared using hydrazine sulfate, a known carcinogen. The approval of
AMCO-AEPA-1 and Hach StablCal would eliminate the need to handle
hydrazine sulfate, and would, therefore, improve laboratory safety. The
NPDES ATP program has recognized AMCO-AEPA-1 Standard (listed in EPA
Method 180.1 as an approved primary standard for drinking water) and
Hach StablCal as acceptable alternatives to formazin for a number of
years. Inclusion at 40 CFR 136 would formalize this acceptance
nationwide.
c. Use of Capillary Columns
EPA proposes to allow the use of capillary (open tubular) GC
columns with EPA Methods 601-613, 624, 625, and 1624B provided that all
quality control (QC) tests in these methods are performed and all QC
acceptance criteria are met. This action would codify EPA's general
practice of allowing capillary GC columns in placed of the packed
columns described in the above methods. However, when employing
capillary columns, the retention times of analytes can change
substantially. Therefore, EPA proposes to require that analysts prepare
analyte retention time tables based on the capillary columns that they
used.
d. Analytical Requirements for Multi-analyte Methods (Target Analytes)
EPA proposes to clarify that analysts need only meet method
performance requirements for target analytes (those analytes being
measured for NPDES reporting). Some analysts interpreted performance
requirements in methods to mean that requirements for every analyte in
a method must be met. However, attempting to meet the performance
requirements of non-target analytes can add substantial cost (due to
extra analyses, extra preparation of standards, etc.) with little or no
benefit to the quality of target analyte data.
e. Requirements for Approval of Method Modifications
EPA also proposes codification of method flexibility provisions and
analytical requirements at 40 CFR 136.6. This new part describes
potentially allowable method modifications and requirements that
analysts would need to meet to use these modifications without prior
EPA approval. The part would also clarify the analytical requirements
for multi-analyte methods, and codify EPA's allowance of capillary
columns with gas chromatography methods that currently specify the use
of packed columns.
In order to evaluate method modifications, the analyst would be
required to assess performance by analyzing test samples and comparing
the results with performance benchmarks for the unmodified method. The
quality control (QC) tests and QC acceptance criteria provided in many
of the approved methods generally would serve this purpose. At a
minimum, the analyst would need to evaluate performance in wastewater
matrices and include both initial (start-up) and ongoing procedures to
evaluate performance. If the tests and criteria in a method meet these
minimum standards, they would be used to evaluate a modification. If
the tests and criteria in a method do not meet these minimum standards,
analysts would use QC tests and acceptance criteria specified in
Protocol for EPA Approval of Alternate Test Procedures for Organic and
Inorganic Analytes in Wastewater and Drinking Water (EPA-821-B-98-002;
March 1999) (ATP Protocol). The applicable tests, which are common to
the analytical community (e.g., calibration verification tests, matrix
spike-matrix spike duplicate tests), are described in Section 3.5 of
the ATP Protocol. QC acceptance criteria for these tests are found in
Table IF of the ATP Protocol.
When applying the ATP protocol, analysts would need to use the
tests and criteria in initial validation and ongoing verification. The
ongoing verification would include assessment of performance of the
modified method on the sample matrix (e.g., analysis of a matrix spike/
matrix spike duplicate pair for every twenty samples of a discharge
analyzed), and analysis of an ongoing precision and recovery sample and
a method blank with each batch of 20 or fewer samples.
The actions proposed would codify past EPA policy that has been
specified in certain approved methods and guidance. For example, with
regard to allowable method modifications, the proposed allowance of an
increase of sample volumes up to 25 mL for purge-and-trap methods,
recognizes the existing flexibility in EPA Method 524.2 (and places
reasonable limits on sample volumes based on the demonstrated
performance of that method) and the use of salt in sample extraction
recognizes recommendations from EPA's Guidance on Evaluation,
Resolution, and Documentation of Analytical Problems Associated with
Compliance Monitoring. Increasing the sample volume has been used as
one means to lower the detection limits of some
[[Page 18183]]
purge-and-trap procedures and EPA recognizes that the purging
efficiency of some of the analytes of interest may be adversely
affected by the increased sample volume and may lead to decreased
precision and recovery for those analytes. When using an increased
sample volume, EPA strongly recommends the use of one or more surrogate
analytes that are chemically similar to the analytes of interest. Use
of these surrogates should assist in the identification of analytical
errors that may result from the increased sample volume. EPA further
recognizes that increasing the sample volume may necessitate changes to
the configuration of the purge-and-trap device in order to provide a
water column height of at least 5 cm in the purge vessel. EPA requests
comments and data regarding whether the existing quality control
procedures and the use of calibration procedures in which the standards
that are also purged are sufficient to substantiate the performance of
these methods when the sample volume is increased beyond 5 mL. EPA also
requests comment as to whether the standards for evaluating
modifications are adequately defined, and whether the potentially
allowable modifications should be expanded, reduced, or changed.
Finally, EPA requests comment on the reference to the ATP protocol
in 40 CFR 136.6. The proposed 40 CFR 136.6 only references the ATP
protocol guidance to establish baseline QC tests and acceptance
criteria for modifications made under 40 CFR 136.6 where such criteria
are not available in methods. The reference to the ATP protocol would
not, however, bind EPA to apply the ATP protocol as written to ATPs
processed under 40 CFR 136.4 and 136.5. EPA may modify the ATP protocol
guidance or apply different requirements for validation of ATPs under
40 CFR 136.4 and 136.5, as appropriate, without notice and opportunity
for comment.
f. Clarification of Reporting Requirements
EPA proposes to add section 136.7 to clarify that a quality control
(QC) failure does not grant relief of timely reporting of results to a
regulated entity, and that results be reported to the level specified
in the method or required in the permit, whichever is lower. EPA
emphasizes that this clarification does not create any new or
additional reporting requirements. In fact, the methods in this part do
not create reporting requirements at all. Reporting requirements are
created when a regulatory or control authority requires reporting of
results upon use of a method at this part.
8. Withdrawal of Methods
a. Previous Versions of Updated Methods and Outdated Methods
EPA proposes to remove some older versions of EPA methods and
replace them with updated versions, (see Table I). The updated versions
include quality control procedures that should help improve data
reliability. In addition, EPA is proposing deletion of most methods
from EPA's Methods for the Chemical Analysis of Water and Wastes. In
many cases, these methods were replaced with newer versions of the EPA
methods, and in all cases approved alternatives (either published by
EPA or VCSBs like ASTM and Standard Methods) are available.
b. Liquid-Liquid Extraction Methods for Dichlorobenzenes
EPA proposes to delete liquid-liquid extraction (LLE) methods,
including EPA Methods 612 and 625 and Standard Methods Method 6410 B,
as approved procedures for 1,2-dichlorobenzene, 1,3-dichlorobenzene,
and 1,4-dichlorobenzene (originally included in the 10-18 proposal).
While these compounds can be determined by these LLE methods,
significant losses of these volatiles can occur using the prescribed
sample collection procedures in the LLE methods, resulting in
relatively low recovery of these compounds. These compounds are more
accurately and precisely analyzed by EPA Method 624 or 1625B (an
isotope-dilution method that compensates for evaporation losses).
c. CFC-based Oil and Grease Methods
EPA proposes to withdraw approval for all oil and grease methods
that use chlorofluorocarbon-113 (CFC-113; Freon-113) as an extraction
solvent because CFC-113 is a Class I ozone-depleting substance (ODS).
On May 14, 1999 (64 FR 26315), EPA approved EPA Method 1664A as a
replacement for Freon-based oil and grease methods to reduce dependency
on CFC-113 (Method 1664A uses n-hexane as an extraction solvent). On
March 13, 2001 (66 FR 14759), EPA published rules that would eliminate
the global laboratory use exemption for ODSs produced or imported after
December 31, 2001, for testing oil and grease and petroleum
hydrocarbons in water; on November 1, 2001 (66 FR 55145), EPA proposed
to codify this elimination. To further reduce reliance on ODSs, EPA
proposes to withdraw EPA Method 413.1 and USGS Method I-4540-85 from
use, and to specify that only n-hexane extraction solvent (as used in
EPA Method 1664A) is approved with the remaining methods. The
withdrawal and replacement would take effect on December 31, 2005,
consistent with the November 1, 2001, proposal. This would allow those
remaining dischargers and permittees who have not switched to n-hexane
methods (e.g., 1664A) time to become completely familiar with the
alternative n-hexane methods.
B. Sample Collection, Preservation, and Holding Time Requirements for
NPDES Compliance Monitoring and Pretreatment
1. Updates to Sampling Requirements at 40 CFR Parts 122, 136, and 403
This rule proposes to correct inconsistencies in sampling
requirements at 40 CFR parts 122, 136, and 403. These inconsistencies
were inadvertently created by past rulemakings. In addition to
correcting the current language, references back to 40 CFR part 136
would be added to Sections 122 and 403 because the analytical methods
and sampling requirements promulgated at 40 CFR part 136 often give
detailed and up-to-date instructions on sample collection. Also
recognizing that a single section of the CFR is the primary source for
sample collection requirements will prevent future inconsistencies.
2. Revisions to 40 CFR Part 136, Table II
40 CFR part 136, Table II specifies sampling, preservation, and
holding time requirements. This proposal would make a number of
additions and modifications to these tables to reduce confusion and
reflect current understanding of sample preservation requirements. The
proposed changes are:
Changes to General Requirements
EPA proposes to clarify the abbreviation ``do.'' (used extensively
in Table II), and to change the general sample preservation temperature
from 4 [deg]C to <=6.00 [deg]C (unfrozen).
``Do.'' means ``ditto''; i.e., that the entry immediately above the
``do.'' applies. This definition has always been the meaning of
``do.,'' but EPA would add language to Table II to clarify this point.
EPA has received requests to make temperature requirements
consistent with those of the National Environmental Laboratory
Accreditation Committee (NELAC). NELAC has adopted a standard of 4
2 [deg]C for sample preservation temperature and
has asked
[[Page 18184]]
EPA to adopt this definition. EPA has proposed a <=6.00 [deg]C
(unfrozen) sample perservation temperature because maintenance of a 4
2 [deg]C temperature requires an active
refrigeration system (which will raise sample shipping costs), and
because EPA is not aware of any evidence to suggest that allowing
refrigeration below 2 [deg]C (the lower limit of NELAC standard) will
adversely effect samples.
Because many approved methods list preservation temperatures,
adopting the <=6.00 [deg]C (unfrozen) sample preservation temperature
would cause inconsistencies between Table II and methods that list a 4
[deg]C sample preservation temperature. Therefore, EPA proposes to add
a note to Table II specifying that preservation temperatures in Table
II supersede all temperature requirements listed in approved methods or
other sources.
Requirements for Inorganic Parameters
EPA is proposing changes to parameter 10 (boron), 18 (hexavalent
chromium), and 23-24 (cyanides), 25 (fluoride), 35 (mercury), and
metals. Changes to boron and fluoride are proposed because of proposed
changes in footnote 1 of Table II described later in this section, and
make no substantive changes. For boron, EPA proposes to remove ``PTFE''
because this information duplicates the allowed use of fluoropolymer in
proposed footnote 1. Similarly, the entry for fluoride will explicitly
limit sample collection to polyethylene containers.
For cyanides, EPA proposes to re-draft listings in Table II to
include total cyanide, cyanide amenable to chlorination, and available
cyanide (to be consistent with 40 CFR part 136, Table IB). This, too,
does not pose a substantive change.
The other proposed changes are substantive. For hexavalent
chromium, EPA proposes to increase the holding time for chromium 6
(CrVI) from 24 hr to 28 days when the sample is preserved to pH 9.3 to
9.7 using sodium hydroxide and the ammonium sulfate buffer solution
specified in EPA Method 218.6. (Method 218.6 is also being proposed
today.) EPA has received a presentation and spreadsheet from
Montgomery-Watson Laboratories and East Bay MUD supporting the increase
in holding time and has placed the presentation and spreadsheet in the
Docket for today's proposal. EPA solicits further data supporting,
refuting, or causing modification of the proposed increase in holding
time.
For mercury, requirements would be divided by methodology (as each
requires different sample handling and preservation techniques) and
sample type, and tissue samples frozen to <-10 [deg]C could be held for
10 years under certain conditions. Finally, for metals (elements) other
than boron, hexavalent chromium, and mercury, EPA proposes to allow
sample preservation (in the original sample) with nitric acid 24 hours
prior to analysis. In other words, acid preservation in the field for
elements would not be required except for boron, hexavalent chromium,
and mercury. This proposal reflects current EPA policy, prevents the
shipment of dangerous acidic materials, and is supported by data
showing that metals adsorbed to a sample container will resolubilize
with 24 hours of acidification.
Requirements for Organics in Table IC
EPA proposes to split the entry for field preservation into
separate entries for tissue and for solid and mixed phase samples,
allowing a seven-day holding time for mixed phase samples, a 24-hour
holding time for tissues in the field, and one-year holding time for
all samples frozen to <-10 [deg]C. These changes reflect that tissue
samples must be frozen within 24 hours to maintain sample integrity.
Footnotes In Table II
This rule proposes modifications to footnotes 1, 2, 4, 5, 6, 7, 11,
and 13 to 40 CFR 136.3, Table II. By editing footnote 1, EPA would
allow fluoropolymer sample containers for all tests that presently
allow use of polyethylene, except fluoride (for which this container is
not appropriate). This change reflects the common use of fluoropolymers
(like PTFE) in the laboratory, and their value in making unreactive
sample containers.
EPA proposes to revise footnote 2 to clarify current sampling
requirements. Similarly, EPA proposes to revise footnote 4 to clarify
that the start of holding times. The holding time for a grab sample
starts at the time of sample collection. The holding time for a
composite sample starts at the time the last grab sample component is
collected.
EPA proposes to revise footnote 4 to clarify that for
bacteriolgical samples, the holding time of six hours may followed by
two hours to analyze the sample. EPA has received questions about
whether the holding time of six hours includes sample analysis time or
not.
EPA proposes to update footnotes 5 and 6 as part of revisions to
the preservation requirements at 40 CFR 136.3, Table II to reflect the
options included in certain proposed and currently approved methods.
EPA has received complaints about current sample preservation
techniques (such as the addition of ascorbic acid as an anti-
chlorinating agent) and believes the procedures that EPA proposes would
prove more successful at providing high quality data. By citing all the
recommended preservation options in approved methods, EPA expects
analysts to chose those that provide the most accurate results.
EPA also is considering alternative preservation and interference
removal procedures for cyanide samples. In particular, for samples
containing sulfides, EPA is proposing to allow use of bismuth (as
opposed to cadmium or lead) or lowering the sample pH and stripping out
hydrogen sulfide with air prior to addition of sodium hydroxide. Lead
and cadmium may inadvertently promote the precipitation of metal-
cyanide complexes, leading to the under-reporting of total cyanide. EPA
requests comment on all the preservation procedures proposed and under
consideration, as well as alternatives which could improve total
cyanide recoveries. EPA further requests that pertinent data and
references to relevant articles be included with such comments.
Footnote 7 would be revised to clarify that samples analyzed for
dissolved metals should be filtered within 15 minutes of collection
(currently the footnotes specifies that samples should be filtered
``immediately''). Footnote 11 would be revised to reflect the proposed
change in sample preservation temperature to <=6.00 [deg]C, described
above. Also, footnote 13 would be revised to allow the storage of
sample extracts for 30 days if stored at <0 [deg]C (based on results of
studies with EPA Method 553).
C. Editorial Revisions and Clarifications to 40 CFR Parts 122, 136,
455, and 465
This proposal would make many other minor changes to 40 CFR part
136. These changes are intended to clarify existing regulations, or
increase method flexibility.
40 CFR Part 122
EPA is considering two options to clarify regulations regarding the
use of analytical methods specific to Title 40 of the CFR, Chapter I,
Subchapters N and O (effluent guidelines and sewage sludge,
respectively). Currently, regulations at 40 CFR part 122 (that
implement the general provisions of the NPDES regulations), state that
NPDES monitoring must be conducted with methods specified at 40 CFR
part 136. As a result, 40 CFR part 122 may
[[Page 18185]]
confuse the reading of effluent guidelines regulations at 40 CFR parts
400-471 (Chapter I, Subchapter N), and with sewage sludge regulations
at 40 CFR part 501-503 (Chapter I, Subchapter O), because methods are
included in those regulations that are not specified at 40 CFR part
136. For example, the pulp, paper, and paperboard point source category
(40 CFR part 430) provides two methods specifically for use in that
category at 40 CFR part 430, Appendix A (EPA Methods 1650 and 1653).
The intent of including these methods at 40 CFR part 430 was that
permit writers would specify their use in permits covering the pulp,
paper and paperboard effluent. However, the language at 40 CFR part 122
could be read to defeat this intent.
To harmonize the existing regulations, EPA is considering two
options. Under Option 1, EPA may modify language at 40 CFR part 122 to
explicitly allow use of methods at 40 CFR part 136 or that are
specifically included in regulations that cover the discharge. For
example, the following language in [brackets] would be added to 40 CFR
122.21(g)(7)(i):
(7) Effluent characteristics. (i) Information on the discharge of
pollutants specified in this paragraph (g)(7) (except information on
storm water discharges which is to be provided as specified in Sec.
122.26). When ``quantitative data'' for a pollutant are required,
the applicant must collect a sample of effluent and analyze it for
the pollutant in accordance with analytical methods approved under
part 136 of this chapter [unless a method is specified for an
industry-specific waste stream at 40 CFR subchapters N or O]. When
no analytical method is approved [under part 136 or specified under
subchapters N or O,] the applicant may use any suitable method but
must provide a description of the method.
Similar changes would be made to 40 CFR 122.1(a)(4), 122.41(j)(4),
122.41(l)(4)(ii), and 122.44(i)(1)(iv), as described in the regulatory
text of this rule.
Under Option 2, EPA would add a table or tables to 40 CFR part 136
listing methods that are included in other parts of the CFR and the
regulations to which they are applicable. This approach has been taken
in the past with certain industry-specific effluent guidelines. For
example, 40 CFR part 136, Table IF specifies methods that may be used
at 40 CFR part 439 (pharmaceutical manufacturing point source
category), and today's rule proposes the addition of Table IG to 40 CFR
136 to list methods for use at 40 CFR 455 (pesticide chemical point
source category). EPA solicits comments on both approaches, or other
options that may be preferable for resolving the current confusion.
40 CFR 136.3, 136.4 and 136.5
EPA proposes to revise all occurrences of ``Director of the
Environmental Monitoring Systems Laboratory'' and ``Director,
Analytical Methods Staff'' to ``Alternate Test Procedure Program
Coordinator, Washington, DC'' to reflect EPA's current ATP Program
management. In addition, addresses for submission of ATPs will be
updated to reflect the current location of the Alternate Test Procedure
Program Coordinator.
40 CFR Part 136, Table IA
EPA proposes to delete footnote 4, which provides reference
information for Standard Methods. Footnote 4 is not needed because the
reference is recognized by the laboratory and regulated community, and
reference information is provided at 40 CFR 136.3(b).
40 CFR Part 136, Table IB
EPA proposes minor edits to footnotes 1, 4, and 6. EPA proposes to
add an NTIS order number to footnote 1, revise metals digestion
requirements to footnote 4 (in light of changes previously in this
Section), and to remove the word ``company'' from footnote 6 (because
entities that conduct testing are not always companies). Also, EPA
proposes to revise the format of references to footnote 10 to be
consistent with other sections of the CFR.
40 CFR Part 136, Table IC and ID
EPA proposes to remove the ``Note'' regarding warning limits
``interim'' status from footnote 7 to both tables, because these limits
have been in use for more than 15 years without difficulties (beyond
those always encountered when first starting to use a method).
40 CFR Part 136, Table IE
EPA proposes to add an NTIS reference number to footnote 1.
40 CFR Part 136, Table IG and 40 CFR 455
EPA proposes to move Table 7 from 40 CFR part 455, to 40 CFR part
136, Table IG. EPA proposes this change to further consolidate lists of
analytical methods in a single section of the CFR.
Addition of 40 CFR 136.6
EPA proposes to add the additional method flexibility and
analytical requirements discussed in Section III.A.7.
Addition of 40 CFR 136.7
EPA proposes to add the clarified reporting requirements discussed
in Section III.A.7.
Changes to 40 CFR Part 465
This rule proposes to remove the exemption for Freon-based oil and
grease methods (described supra). The Coil Coating Point Source
Category at 465.03 contains a method for determination of petroleum
hydrocarbons using a freon extraction method. EPA proposes to remove
this method and to replace it with a reference to EPA Method 1664A for
determination of non-polar materials (NPM), which is generally
equivalent to total petroleum hydrocarbons. EPA has received many
requests to allow the use of Method 1664A for this industrial category.
This change will further the goal of reducing the use of ozone
depleting substances.
IV. Summary of Proposed Revisions to Drinking Water Regulations
A. Vendor Developed Methods
1. Anions by CIE-UV
Waters Corporation CIE/UV Method (D6508, Rev. 2), described in
Section III.A.1.a above, is a new method that employs capillary ion
electrophoresis to determine common anions in wastewater and drinking
water. This method is being proposed today for use in NPDWR and NSDWR
compliance monitoring for determination of the common anions.
2. Free Chlorine by Color Comparison Test Strip
This rule proposes to allow States the option of approving ITS free
chlorine test strips as a test kit for the measurement of free
chlorine. The ITS test strip is configured with a ``color pad''
attached to a plastic holder. The color pad contains 3,3,5',5'-
tetramethylbenzidine (TMB) which reacts with chlorine to produce a
color change that is proportional to the amount of free chlorine in the
sample. The chlorine concentration is quantified by comparison of this
color with an ITS color chart.
The use of ITS free chlorine test strips has been discussed in
literature and has been validated in drinking water using two
interlaboratory validation studies. The studies were performed to
characterize the false negative and false positive rates of the strips,
the precision and recovery using the strips, the sensitivity of the
strips, and the variability of test strips between lots. To eliminate
potential analyst bias, all studies were double-blind and random.
[[Page 18186]]
The false positive and false negative rates were 0-1%. Method precision
and recovery was characterized in multiple matrices at multiple
concentrations. For example, free chlorine recovery was approximately
100%, and relative standard deviation (RSD) was generally below 20% for
analysis of drinking water samples fortified with 0.1 ppm of free
chlorine. Method sensitivity was demonstrated to be sufficient for
monitoring chlorination levels at 0.1 ppm or above; chlorination levels
required by NPDWRs is 0.2 ppm. Finally, results did not appear to vary
across different lots of ITS strips.
The use of the test strips is described in Method D99-003, ``Free
Chlorine Species'' (HOCl- and OCl-) by Test Strip'' [Revision 3.0,
November 21, 2003]. A copy of Method D99-003 and the method validation
study report are in the docket supporting this rule. In addition,
copies of Method D99-003 and test strips are available from Industrial
Test Systems, Inc., 1875 Langston St., Rock Hill, SC 29730.
3. Available Cyanide by Ligand Exchange--FIA
This rule proposes approval of two similar methods for the
determination of available cyanide: Method OIA-1677, DW and ASTM D6888-
03. Studies have shown that available cyanide is equivalent to cyanide
amenable to chlorination (CATC), and, therefore, that available cyanide
methods can be used in place of approved procedures for the
determination of CATC. Under NPDWR regulations, CATC is generally
measured when the total cyanide level provides a value higher than the
cyanide MCL (See 57 FR 31800; July 17, 1992).
EPA-821-R-99-013, August 1999 Method OIA-1677, DW ``Available
Cyanide by Flow Injection, Ligand Exchange, and Amperometry,'' January
2004 is technically equivalent to Method OIA-1677, which is currently
approved for determination of available cyanide in the NPDES program
(64 FR 73414; December 30, 1999). Method OIA-1677, DW only differs from
OIA-1677 in having (a) updated contact information, and (b) less method
modification flexibility (references to performance-based modifications
have been removed). Therefore the validation data on OIA-1677 is
applicable to OIA-1677, DW.
Method OIA-1677 was validated by an intralaboratory validation
study and a nine-laboratory validation study. The intralaboratory study
was performed to establish (1) the ability of OIA-1677 to detect and
quantify 11 specific metallocyanide complexes as compared to CATC and
Weak Acid Dissociable (WAD) cyanide methods, (2) the ability of OIA-
1677 to identify and overcome analytical interferences, and (3) compare
the precision and recovery of OIA-1677 to CATC and WAD cyanide methods.
These studies showed that OIA-1677 could (1) recover up to 100% of the
cyanide compounds that were detected by the CATC and WAD cyanide
methods, (2) overcome most analytical interferences, and (3) provide
comparable or better precision and recovery than CATC and WAD cyanide
methods.
The interlaboratory study was conducted to (1) confirm the
performance of OIA-1677 across multiple laboratories, (2) assess
interlaboratory and matrix variability, and (3) develop QC acceptance
criteria. Nine laboratories participated in the study, each analyzing
an identical set of six field samples (effluents) using OIA-1677. Along
with these effluent analyses, laboratories performed all the required
QC analyses in OIA-1677 and an MDL study. The relative standard
deviation (RSD) of results across all laboratories and all samples was
12%. The mean recoveries across all effluents tested was 96%.
ASTM Method D6888-03, which also is being proposed for use in NPDES
compliance monitoring in this rule, uses a similar technology to Method
OIA-1677, and is described above.
While these methods generally provide dependable results, sulfide
at levels below those detected with the lead acetate paper may produce
false positive signals on the amperometric detection systems used in
D6888-03 and OIA-1677 (see Zheng et al. ``Evaluation and Testing of
Analytical Methods for Cyanide Species in Municipal and Industrial and
Contaminated Waters,'' Environ. Sci. Technol. 2003, 37, 107-115). Lead
acetate paper is generally recommended means for screening for the
presence of sulfide interferences in cyanide methods, but the paper
will not detect sulfides below approximately 5 ppm. For this reason,
analysts suspecting a sulfide interference should test their sample
with a more sensitive sulfide procedure and treat the sample
accordingly.
4. Radium-226 and 228 by Gamma Spectrometry
The Environmental Resources Center (ERC) at the Georgia Institute
of Technology has developed a method, ``The Determination of Radium-226
and Radium-228 in Drinking Water by Gamma-ray Spectrometry Using HPGE
or Ge(Li) Detectors.'' The method simultaneously determines the
concentration of both Radium-226 and Radium-228 from a single sample
aliquot. This method can significantly reduce the isolation and
purification steps currently required in EPA-approved sequential
methods for the measurement of these radioisotopes, potentially
reducing both the labor and waste disposal costs by greater than 50
percent.
A sample has its radium isotope content preconcentrated using a
sulfate coprecipitation. It is then placed into a sample container
appropriate for the laboratory's gamma detection system. The prepared
sample is then measured in a reproducible counting geometry for a
suitable amount of time so that the collected gamma spectra
demonstrates the required sensitivity, defined as a Minimum Detectable
Concentration (MDC), of 1 picoCurie per liter (pCi/L) for both of the
regulated contaminant radioisotopes.
Method performance was characterized using a 3-laboratory study to
test the method's recovery, precision, sensitivity, and ruggedness
using diverse matrices found in finished drinking waters. The results
of these studies demonstrate this method has the required sensitivity,
and can be expected to provide results that are at least equivalent to,
or have a higher degree of recovery and precision than the current EPA-
approved methods for producing these measurements.
ERC's method and a copy of the method validation study report are
in the docket supporting this rule. In addition, copies of ERC's method
are available from The Environmental Resources Center, Georgia
Institute of Technology, 620 Cherry Street, Atlanta, GA 30332-0335,
USA, Phone: 404-894-3776.
B. EPA Method for Chlorine Dioxide by Colorimetry
EPA is proposing to add a new method to 40 CFR 141.74 for the
measurement of chlorine dioxide residuals. EPA Method 327.0 (USEPA
2003), which has been proposed for addition to 40 CFR 141.131 in a
previous rulemaking (68 FR 49548, August 18, 2003) is an enzymatic /
spectrophotometric method in which a total chlorine dioxide plus
chlorite concentration is determined in an unsparged sample and the
chlorite concentration is determined in a sparged sample. The chlorine
dioxide concentration is then calculated by subtracting the chlorite
concentration from the total.
EPA proposes to approve EPA Method 327.0 as an additional method
for CT
[[Page 18187]]
determinations when chlorine dioxide is the disinfectant residual in
use. It would provide water systems with additional flexibility in
monitoring the application of chlorine dioxide. EPA believes that many
water plant operators will prefer the new method over the currently
approved methods due to its ease of use.
The pH of the samples (sparged and unsparged) and blank are
adjusted to 6.0 with a citric acid/glycine buffer. The chromophore
Lissamine Green B (LGB) and the enzyme horseradish peroxidase are
added. The enzyme reacts with the chlorite in the sample to form
chlorine dioxide which then reacts with the chromophore LGB to reduce
the absorbance of the sample at 633 nm. The absorbance of the samples
and blank are determined spectrophotometrically. The difference in
absorbance between the samples and the blank is proportional to the
chlorite and total chlorine dioxide/chlorite concentrations in the
samples.
EPA Method 327.0 offers advantages over the currently approved
chlorine dioxide methods in that it is not subject to positive
interferences from other chlorine species and it is easier to use.
The single laboratory detection limits presented in the method are
0.04-0.16 mg/L for chlorine dioxide. The detection limits are based on
the analyses of sets of seven replicates of reagent water that were
fortified with low concentrations of chlorine dioxide with and without
the presence of chlorite. The standard deviation of the mean
concentration for each set of samples was calculated and multiplied by
the student's t-value at 99% confidence and n-1 degrees of freedom
(3.143 for 7 replicates) to determine the detection limit. The recovery
reported in the method for laboratory fortified blanks at
concentrations of 0.2-1.0 mg/L is 102-124% for chlorine dioxide with
relative standard deviations between 3.6 and 16%. Replicate analyses of
drinking water samples from surface and ground water sources fortified
at concentrations of approximately 1 and 2 mg/L chlorite and chlorine
dioxide showed average recoveries of 91-110% with relative standard
deviations of 1-9%.
Method 327.0 (EPA 815-B-03-001) is available from the Office of
Ground Water and Drinking Water Technical Support Center, U.S.
Environmental Protection Agency, 26 W. Martin Luther King Dr.,
Cincinnati, OH 45268. The method also may be viewed and downloaded from
http://www.epa.gov/ogwdw/methods/sourcalt.html.
C. New and Updated VCSB Methods
1. ASTM
This rule proposes to approve a number of updated ASTM methods in
NPDWR, and NSDWR compliance monitoring. Previously approved versions of
ASTM methods will remain approved. Consult Table II in Section
III.A.6.b for a list of proposed methods.
Today's rule also proposes ASTM Method D 6919-03, ``Determination
of Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water
and Wastewater by Ion Chromatography,'' for use in drinking water
compliance monitoring. Consult Section III.A.5.b for more information.
2. Standard Methods
EPA proposes to approve a number of updated Standard Methods in
NPDWR, and NSDWR compliance monitoring. Copies of all the proposed
methods are in the paper docket for review (they are not included in e-
docket due to copyright issues). Copies of Standard Methods are
available at a nominal cost from the web site www.standardmethods.org
or from the Standard Methods Manager, American Water Works Association,
6666 West Quincy Avenue, Denver, CO 80235, 303-347-6175,
[email protected]. Previously approved versions of Standard Methods
will remain approved.
Consult Section III.A.6.c for a discussion of EPA's proposed
numbering scheme for standard methods, and Table III of that section
for a list of proposed methods. While a number of methods contain no
changes from previously approved version, some incorporate technical
and editorial revisions to improve user-friendliness, update
references, and correct errors (methods that were revised from previous
versions are indicated in Table III).
D. Withdrawal of Immunoassay Method for Atrazine
A final rule was published by EPA in the Federal Register on
October 29, 2002 (67 FR 65888), that approved Syngenta Method AG-625
for monitoring atrazine in finished drinking water. EPA proposes to
withdraw this method. The proposed withdrawal is motivated by recent
reports that show interferences due to chlorine and chlorine dioxide
that result in false positive detection and elevated concentrations of
atrazine. This has been demonstrated when measuring the concentrations
of atrazine in drinking water matrices when compared to values obtained
using currently approved methods. EPA seeks comments and information
regarding modifications to Syngenta Method AG-625 that would eliminate
or substantially mitigate the interferences described above, or
regarding conditions under which the method would be suitable for use
in drinking water compliance monitoring. If EPA receives such
information, the Agency may, in a subsequent notice, propose to modify
this method rather than withdraw approval.
V. Request for Comment on Microbiological ATP Protocol
EPA is soliciting comments on ``EPA Microbiological Alternate Test
Procedure (ATP) Protocol for Drinking Water, Ambient Water, and
Wastewater Monitoring Methods--Guidance'' (July 2003; EPA-821-B-03-004)
(Protocol). The Protocol is a guidance document for evaluating
microbiological ATPs, and was referenced in the July 21, 2003, rule
promulgating methods for the analysis of microbiological contaminants
in ambient waters (July 21, 2003; 68 FR 43272). EPA does not plan to
codify the protocol, but is interested in receiving comments that it
may consider in future revisions to the protocol.
VI. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review
Under Executive Order 12866 (58 FR 51735 (October 4, 1993)), the
Agency must determine whether the regulatory action is ``significant''
and therefore subject to OMB review and the requirements of the
Executive Order. The Executive Order defines ``significant regulatory
action'' as one that is likely to result in a rule that may:
(1) Have an annual effect on the economy of $100 million or more,
or adversely affect in a material way the economy, a sector of the
economy, productivity, competition, jobs, the environment, public
health or safety, or State, local, or Tribal governments or
communities;
(2) Create a serious inconsistency or otherwise interfere with an
action taken or planned by another agency;
(3) Materially alter the budgetary impact of entitlements, grants,
user fees, or loan programs or the rights and obligations of recipients
thereof; or
(4) Raise novel legal or policy issues arising out of legal
mandates, the President's priorities, or the principles set forth in
the Executive Order.
It has been determined that this rule is not a ``significant
regulatory action'' under the terms of Executive Order
[[Page 18188]]
12866 and is therefore not subject to E.O. 12866 review.
B. Paperwork Reduction Act
This action does not impose an information collection burden under
the provisions of the Paperwork Reduction Act, 44 U.S.C. 3501 et. seq.
This rule does not impose any information collection, reporting, or
recordkeeping requirements. This rule merely proposes new and updated
versions of testing procedures, withdraws some older testing
procedures, and proposes new sample collection, preservation, and
holding time requirements.
Burden means the total time, effort, or financial resources
expended by persons to generate, maintain, retain, or disclose or
provide information to or for a Federal agency. This includes the time
needed to review instructions; develop, acquire, install, and utilize
technology and systems for the purpose of collecting, validating, and
verifying information, processing and maintaining information, and
disclosing and providing information; adjust the existing ways to
comply with any previously applicable instructions and requirements;
train personnel to be able to respond to a collection of information;
search data sources; complete and review the collection of information;
and transmit or otherwise disclose the information.
An Agency may not conduct or sponsor, and a person is not required
to respond to a collection of information unless it displays a
currently valid OMB control number. The OMB control numbers for EPA's
regulations in 40 CFR are listed in 40 CFR part 9.
C. Regulatory Flexibility Act
The RFA generally requires an agency to prepare a regulatory
flexibility analysis of any rule subject to notice and comment
rulemaking requirements under the Administrative Procedure Act or any
other statute unless the agency certifies that the rule will not have a
significant economic impact on a substantial number of small entities.
Small entities include small businesses, small organizations, and small
governmental jurisdictions.
The RFA provides default definitions for each type of small entity.
It also authorizes an agency to use alternative definitions for each
category of small entity, ``which are appropriate to the activities of
the agency'' after proposing the alternative definition(s) in the
Federal Register and taking comment. 5 U.S.C. secs. 601(3)-(5). In
addition to the above, to establish an alternative small business
definition, agencies must consult with SBA's Chief Counsel for
Advocacy.
For purposes of assessing the impacts of this rule on small
entities for methods under the Clean Water Act, small entity is defined
as: (1) A small business that meets RFA default definitions (based on
SBA size standards) found in 13 CFR 121.201; (2) a small governmental
jurisdiction that is a government of a city, county, town, school
district or special district with a population less than 50,000; and
(3) a small organization that is any not-for-profit enterprise which is
independently owned and operated and is not dominant in its field.
For purposes of assessing the impacts of this rule on small
entities for methods under the Safe Drinking Water Act, EPA considered
small entities to be public water systems serving 10,000 or fewer
persons. This is the cut-off level specified by Congress in the 1996
Amendments to the Safe Drinking Water Act for small system flexibility
provisions. In accordance with the RFA requirements, EPA proposed using
this alternative definition in the Federal Register (63 FR 7620,
February 13, 1998), requested public comment, consulted with the Small
Business Administration, and expressed its intention to use the
alternative definition for all future drinking water regulations in the
Consumer Confidence Reports regulation (63 FR 44511, August 19, 1998).
As stated in that final rule, the alternative definition would be
applied to this regulation as well.
After considering the economic impacts of today's proposed rule on
small entities, I certify that this action will not have a significant
economic impact on a substantial number of small entities. This action
proposes new and updated versions of testing procedures, withdraws some
older testing procedures, and proposes new sample collection,
preservation, and holding time requirements. Generally, these changes
will have a positive impact on small entities by increasing method
flexibility, thereby allowing entities to reduce costs by choosing more
cost effective methods. In some cases, analytical costs may increase
slightly due to the additional QC requirements included in the methods
that have been proposed to replace older EPA methods. However, most
laboratories that analyze samples for EPA compliance monitoring have
already instituted QC requirements as part of their laboratory
practices. We have determined that a small number of small entities
that are still using the CFC-113 based oil and grease methods may need
to devote resources to analyst training when they switch to hexane-
based methods. However, due to the decreased availability of CFC-113 in
the marketplace, we anticipate that the cost differential, if any, will
soon favor the use of the hexane-based methods. The phaseout of CFC-113
based methods is required to comply with the Montreal Protocol which
prohibits the use of CFC-113 based methods after December 31, 2005.
Although this proposed rule will not have a significant economic
impact on a substantial number of small entities, EPA nonetheless has
tried to reduce the impact of this rule on small entities. Anticipating
the prohibition of CFC-113 based methods, EPA promulgated hexane-based
methods in May 1999. EPA has determined that most laboratories have now
switched to hexane-based oil and grease methods, making the analysis
costs competitive with the CFC-113 based methods. We continue to be
interested in the potential impacts of the proposed rule on small
entities and welcome comments on issues related to such impacts.
D. Unfunded Mandates Reform Act
Title II of the Unfunded Mandates Reform Act of 1995 (UMRA), Public
Law 104-4, establishes requirements for Federal agencies to assess the
effects of their regulatory actions on State, Tribal, and local
governments and the private sector. Under section 202 of the UMRA, EPA
generally must prepare a written statement, including a cost-benefit
analysis, for proposed and final rules with ``Federal mandates'' that
may result in expenditures to State, local, and Tribal governments, in
the aggregate, or to the private sector, of $100 million or more in any
one year. Before promulgating an EPA rule for which a written statement
is needed, section 205 of the UMRA generally requires EPA to identify
and consider a reasonable number of regulatory alternatives and adopt
the least costly, most cost-effective or least burdensome alternative
that achieves the objectives of the rule. The provisions of section 205
do not apply when they are inconsistent with applicable law. Moreover,
section 205 allows EPA to adopt an alternative other than the least
costly, most cost-effective or least burdensome alternative if the
Administrator publishes with the final rule an explanation of why that
alternative was not adopted.
Before EPA establishes any regulatory requirements that may
significantly or uniquely affect small governments, including Tribal
governments, it must have developed under section 203 of the UMRA a
small government agency plan. The plan must provide for the
[[Page 18189]]
notification of potentially affected small governments, enabling
officials of affected small governments to have meaningful and timely
input in the development of EPA regulatory proposals with significant
Federal intergovernmental mandates, and informing, educating, and
advising small governments on compliance with the regulatory
requirements.
This rule contains no Federal mandates (under the regulatory
provisions of Title II of UMRA) for State, local, or Tribal governments
or the private sector. The rule imposes no enforceable duty on any
State, local, or Tribal governments or the private sector. In fact,
this rule should (on the whole) save money for governments and the
private sector by increasing method flexibility, and allowing these
entities to reduce monitoring costs by taking advantage of innovations.
Thus, today's rule is not subject to the requirements of Sections 202
and 205 of the UMRA.
EPA has determined that this rule contains no regulatory
requirements that might significantly or uniquely affect small
governments. Generally, this action will have a positive impact by
increasing method flexibility, thereby allowing method users to reduce
costs by choosing more cost effective methods. In some cases,
analytical costs may increase slightly due to changes in methods, but
these increases are neither significant nor unique to small
governments. This rule merely proposes new and updated versions of
testing procedures, withdraws some older testing procedures, and
proposes new sample collection, preservation, and holding time
requirements. Thus, today's rule is not subject to the requirements of
Section 203 of UMRA.
E. Executive Order 13132: Federalism
Executive Order 13132, entitled ``Federalism'' (64 FR 43255, August
10, 1999), requires EPA to develop an accountable process to ensure
``meaningful and timely input by State and local officials in the
development of regulatory policies that have federalism implications.''
``Policies that have federalism implications'' is defined in the
Executive Order to include regulations that have ``substantial direct
effects on the States, on the relationship between the national
government and the States, or on the distribution of power and
responsibilities among the various levels of government.''
This proposed rule does not have federalism implications. It will
not have substantial direct effects on the States, on the relationship
between the national government and the States, or on the distribution
of power and responsibilities among the various levels of government,
as specified in Executive Order 13132. This rule merely proposes new
and updated versions of testing procedures, withdraws some older
testing procedures, and proposes new sample collection, preservation,
and holding time requirements. The costs to State and local governments
will be minimal (in fact, governments may see a cost savings), and the
rule does not preempt State law. Thus, Executive Order 13132 does not
apply to this rule.
In the spirit of Executive Order 13132, and consistent with EPA
policy to promote communications between EPA and State and local
governments, EPA specifically solicits comment on this proposed rule
from State and local officials.
F. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments
Executive Order 13175, entitled ``Consultation and Coordination
with Indian Tribal Governments'' (65 FR 67249, November 9, 2000),
requires EPA to develop an accountable process to ensure ``meaningful
and timely input by tribal officials in the development of regulatory
policies that have tribal implications.''
``Policies that have tribal implications'' is defined in the
Executive Order to include regulations that have ``substantial direct
effects on one or more Indian tribes, on the relationship between the
Federal government and the Indian tribes, or on the distribution of
power and responsibilities between the Federal government and the
Indian tribes.''
This proposed rule does not have tribal implications. It will not
have substantial direct effects on Tribal governments, on the
relationship between the Federal government and Indian tribes, or on
the distribution of power and responsibilities between the Federal
government and Indian tribes, as specified in Executive Order 13175.
This rule merely proposes new and updated versions of testing
procedures, withdraws some older testing procedures, and proposes new
sample collection, preservation, and holding time requirements. The
costs to Tribal governments will be minimal (in fact, governments may
see a cost savings), and the rule does not preempt State law. Thus,
Executive Order 13175 does not apply to this rule.
In the spirit of Executive Order 13175, and consistent with EPA
policy to promote communications between EPA and Tribal governments,
EPA specifically solicits comment on this proposed rule from Tribal
officials.
G. Executive Order 13045: Protection of Children From Environmental
Health Risks and Safety Risks
Executive Order 13045: ``Protection of Children from Environmental
Health Risks and Safety Risks'' (62 FR 19885, April 23, 1997) applies
to any rule that: (1) Is determined to be ``economically significant''
as defined under Executive Order 12866, and (2) concerns an
environmental health or safety risk that EPA has reason to believe may
have a disproportionate effect on children. If the regulatory action
meets both criteria, the Agency must evaluate the environmental health
or safety effects of the planned rule on children, and explain why the
planned regulation is preferable to other potentially effective and
reasonably feasible alternatives considered by the Agency. This
proposed rule is not subject to the Executive Order 13045 because it is
not economically significant as defined in Executive Order 12866.
Further it does not concern an environmental health or safety risk that
EPA has reason to believe may have a disproportionate effect on
children. This action proposes new and updated versions of testing
procedures, withdraws some older testing procedures, and proposes new
sample collection, preservation, and holding time requirements.
H. Executive Order 13211: Actions That Significantly Affect Energy
Supply, Distribution, or Use
This rule is not subject to Executive Order 13211, ``Actions
Concerning Regulations That Significantly Affect Energy Supply,
Distribution, or Use'' (66 FR 28355 (May 22, 2001)) because it is not a
significant regulatory action under Executive Order 12866.
I. National Technology Transfer and Advancement Act
Section 12(d) of the National Technology Transfer and Advancement
Act of 1995, (NTTAA), Public Law 104-113, section 12(d) (15 U.S.C. 272
note), directs EPA to use voluntary consensus standards in its
regulatory activities unless to do so would be inconsistent with
applicable law or otherwise impractical. Voluntary consensus standards
are technical standards (e.g., material specifications, test methods,
sampling procedures, and business practices) that are developed or
adopted by voluntary consensus standard bodies. The NTTAA directs EPA
to provide Congress, through the OMB, explanations when the Agency
decides
[[Page 18190]]
not to use available and applicable voluntary consensus standards.
This proposed rulemaking involves technical standards. As described
throughout this document, EPA proposes to use over 150 standards
developed by Standard Methods and ASTM International. Paragraphs
III.A.3, III.A.5, III.A.6.b, and III.A.6.c specify the methods from
these two voluntary consensus standards bodies (including version
numbers and dates), provide information on how to obtain copies of
these standards, and describe EPA's rationale for employing these
standards.
List of Subjects
40 CFR Part 122
Administrative practice and procedure, Confidential business
information, Environmental protection, Hazardous substances, Reporting
and recordkeeping requirements, Water pollution control.
40 CFR Part 136
Environmental protection, Incorporation by reference, Reporting and
recordkeeping requirements, Water pollution control.
40 CFR Part 141
Chemicals, Environmental protection, Incorporation by reference,
Indians-lands, Intergovernmental relations, Radiation protection,
Reporting and recordkeeping requirements, Water supply.
40 CFR Part 143
Chemicals, Environmental protection, Incorporation by reference,
Indians-lands, Water supply.
40 CFR Part 403
Confidential business information, Environmental protection,
Reporting and recordkeeping requirements, Waste treatment and disposal,
Water pollution control.
40 CFR Part 430
Environmental protection, Paper and paper products industry,
Reporting and recordkeeping requirements, Waste treatment and disposal,
Water pollution control.
40 CFR Part 455
Chemicals, Environmental protection, Packaging and containers,
Pesticides and pests, Waste treatment and disposal, Water pollution
control.
40 CFR Part 465
Coil coating industry, Environmental protection, Reporting and
recordkeeping requirements, Waste treatment and disposal,Water
pollution control.
Dated: March 16, 2004.
Michael O. Leavitt,
Administrator.
For the reasons set out in the preamble, title 40, chapter I of the
Code of Federal Regulations, is proposed to be amended as follows:
PART 122--EPA ADMINISTERED PERMIT PROGRAMS: THE NATIONAL POLLUTANT
DISCHARGE ELIMINATION SYSTEM
1. The authority citation for Part 122 continues to read as
follows:
Authority: The Clean Water Act, 33 U.S.C. 1251 et seq.
2. Section 122.1 is amended by revising paragraph (a)(4).
Sec. 122.1 Purpose and Scope.
(a) * * *
(4) The NPDES permit program has separate additional provisions
that are used by permit issuing authorities to determine what
requirements must be placed in permits if issued. These provisions are
located at parts 125, 129, 133, 136 of this chapter and 40 CFR
subchapter N and subchapter O of this chapter.
* * * * *
3. Section 122.21 is amended:
a. By revising paragraph (g)(7)(i).
b. In paragraph (h)(4)(i) by revising the fourth and fifth
sentences with two revised sentences.
Sec. 122.21 Application for a permit (applicable to State programs,
see Sec. 123.25).
* * * * *
(g) * * *
(7) Effluent Characteristics. (i) Information on the discharge of
pollutants specified in this paragraph (g)(7) (except information on
storm water discharges which is to be provided as specified in Sec.
122.26). When ``quantitative data'' for a pollutant are required, the
applicant must collect a sample of effluent and analyze it for the
pollutant in accordance with analytical methods approved under part 136
of this chapter unless a method is specified for an industry-specific
waste stream at 40 CFR subchapters N or O. When no analytical method is
approved under part 136 or specified under subchapters N or O, the
applicant may use any suitable method but must provide a description of
the method. When an applicant has two or more outfalls with
substantially identical effluents, the Director may allow the applicant
to test only one outfall and report that the quantitative data also
apply to the substantially identical outfall. The requirements in
paragraphs (g)(7) (vi) and (vii) of this section that an applicant must
provide quantitative data for certain pollutants known or believed to
be present do not apply to pollutants present in a discharge solely as
the result of their presence in intake water; however, an applicant
must report such pollutants as present. Grab samples must be used for
pH, temperature, cyanide, total phenols, residual chlorine, oil and
grease, sulfide, fecal coliform, fecal streptococcus, and volatile
organics, unless specified otherwise at 40 CFR part 136. For all other
pollutants, a 24-hour composite sample, using a minimum of four (4)
grab samples, must be used unless specified otherwise at 40 CFR part
136. Results of analyses of individual grab samples for any parameter
may be averaged to form the daily average. Grab samples that are not
required to be analyzed immediately (see Table II at 40 CFR part 136)
may be composited in the laboratory, provided that container,
preservation, and holding time requirements are met (see Table II at 40
CFR part 136) and that sample integrity is not compromised by
compositing. However, a minimum of one grab sample may be taken for
effluents from holding ponds or other impoundments with a retention
period greater than 24 hours. In addition, for discharges other than
storm water discharges, the Director may waive composite sampling for
any outfall for which the applicant demonstrates that the use of an
automatic sampler is infeasible and that the minimum of four (4) grab
samples will be a representative sample of the effluent being
discharged.
* * * * *
(h) * * *
(4) * * *
(i) * * * Grab samples must be used for pH, temperature, cyanide,
total phenols, residual chlorine, oil and grease, sulfide, fecal
coliform, fecal streptococcus, and volatile organics, unless specified
otherwise at 40 CFR part 136. For all other pollutants, a 24-hour
composite sample, using a minimum of four (4) grab samples, must be
used unless specified otherwise at 40 CFR part 136. * * *
* * * * *
4. Section 122.41 is amended by revising paragraphs (j)(4) and
(l)(4)(ii).
Sec. 122.41 Conditions applicable to all permits (applicable to State
programs, see Sec. 123.25).
* * * * *
(j) * * *
(4) Monitoring must be conducted according to test procedures
approved under 40 CFR part 136 or unless a method is specified for an
industry-
[[Page 18191]]
specific waste stream at 40 CFR subchapters N or O.
* * * * *
(l) * * *
(4) * * *
(ii) If the permittee monitors any pollutant more frequently than
required by the permit using test procedures approved under 40 CFR part
136, or a method specified for an industry-specific waste stream at 40
CFR subchapters N or O, the results of such monitoring shall be
included in the calculation and reporting of the data submitted in the
DMR or sludge reporting form specified by the Director.
* * * * *
5. Section 122.44 is amended by revising paragraph (i)(1)(iv).
Sec. 122.44 Establishing limitations, standards, and other permit
conditions (applicable to State NPDES programs; see Sec. 123.25) .
* * * * *
(i) * * *
(1) * * *
(iv) According to test procedures approved under 40 CFR part 136
for the analyses of pollutants having approved methods under that part,
unless a method is specified for an industry-specific waste stream at
40 CFR subchapters N or O; otherwise, monitoring must be conducted
according to a test procedure specified in the permit for pollutants
with no methods approved under 40 CFR part 136 or specified at 40 CFR
subchapters N or O.
* * * * *
PART 136--GUIDELINES ESTABLISHING TEST PROCEDURES FOR THE ANALYSIS
OF POLLUTANTS
1. The authority citation for Part 136 continues to read as
follows:
Authority: Secs. 301, 304(h), 307, and 501(a) Pub. L. 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 amended:
a. In paragraph (a) by revising the introductory text and Tables
IA, IB, IC, ID, and IE.
b. In paragraph (a) by adding Table IG after the notes of Table IF.
c. In paragraph (b) by revising references 6, 10, and 17, and
adding references 63 through 69.
d. By revising paragraphs (c), (d), and (e).
The revisions and additions read as follows:
Sec. 136.3 Identification of test procedures.
(a) Parameters or pollutants, for which methods are approved, are
listed together with test procedure descriptions and references in
Tables IA, IB, IC, ID, IE, IF, and IG. The full text of the referenced
test procedures are incorporated by reference into Tables IA, IB, IC,
ID, IE, IF, IG. The incorporation by reference of these documents, as
specified in paragraph (b) of this section, was approved by the
Director of the Federal Register in accordance with 5 U.S.C. 552(a) and
1 CFR part 51. Copies of the documents may be obtained from the sources
listed in paragraph (b) of this section. You can get information about
obtaining these documents from the EPA Office of Water Statistics and
Analytical Support Branch at 202-566-1000. Documents may be inspected
at EPA's Water Docket, EPA West, 1301 Constitution Avenue, NW., Room
B135, Washington, DC (Telephone: 202-566-2426); or at the Office of the
Federal Register, 800 North Capitol Street, NW., Suite 700, Washington,
DC. These test procedures are incorporated as they exist on the day of
approval and a notice of any change in these test procedures will be
published in the Federal Register. The discharge parameter values for
which reports are required must be determined by one of the standard
analytical test procedures incorporated by reference and described in
Tables IA, IB, IC, IE, IF, and IG or by any alternate test procedure
which has been approved by the Administrator under the provisions of
paragraph (d) of this section and Sec. Sec. 136.4 and 136.5. Under
certain circumstances (paragraph (b) or (c) of this section or 40 CFR
401.13) other test procedures may be more advantageous when such other
test procedures have been previously approved by the Regional
Administrator of the Region in which the discharge will occur, and
providing the Director of the State in which such discharge will occur
does not object to the use of such alternate test procedure.
Table IA.--List of Approved Biological Methods
--------------------------------------------------------------------------------------------------------------------------------------------------------
Standard methods Standard methods on- AOAC, ASTM,
Parameter and units Method \1\ EPA 18th, 19th, 20th Ed. line USGS Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Bacteria:
1. Coliform (fecal) Most Probable p. 132 \3\ 9221C E 9221C E-99
number per 100 mL. Number (MPN),
5 tube 3
dilution, or.
Membrane filter p. 124 \3\ 9222D 9222D-97 B-0050-85 \5\
(MF) \2\
single step.
2. Coloform (fecal) in MPN, 5 tube, 3 p. 132 \3\ 9221C E 9221C E-99
presence of chlorine, dilution, or.
number per 100 mL.
MF, single step p. 124 \3\ 9222D 9222D-97
\6\.
3. Coliform (total), MPN, 5 tube, 3 p. 114 \3\ 9221B 9221B-99
number per. 100 mL. dilution, or.
MF \2\, single p. 108 \3\ 9222B 9222B-97 B-0025-85 \5\
step or two
step.
4. Colofirm (total), in MPN, 5 tube, 3 p. 114 \3\ 9221B 9221B-99
presence of chlorine, dilution.
number per 100 mL.
or MF \2\ with p. 111 \3\ 9222 (B+B.5 c) 9222 (B+B.5c)--97
enrichment.
5. E. coli, number per MPN\7,\ \9,\ .................... 9221B.1/9221F \12,\ 9221B.1/9221F-99
100 mL \28\. \15\, multiple \14\ \12,\ \14\
tube.
[[Page 18192]]
multiple tube/ .................... 9223B \13\ 9223B-97 \13\ 991.15 \11\ Coliert[reg] \13,\
multiple well. \17,\ Colilert-
18[reg] \13\ \16\
\17\
MF \2,\ \6,\ 1103.1 \20\ 9222B/9222G \19\, 9222B/9222G-97 \19\ D5392-93 \10\
\7,\ \8,\ \9\, 9213D
two step, or.
single step.... 1603 \21\, 1604 \22\ .................... ..................... .............. mColiBlue-24 \18\
6. Fecal streptococci, MPN, 5 tube, 3 p. 139 \3\ 9230B 9230B-93
number per 100 mL. dilution.
MF \2\, or..... p. 136 \3\ 9230C 9230C-93 B-0055-85 \5\
Plate count.... p. 143 \3\ .................... ..................... ..............
7. Enterococci, number MPN \7,\ \9\ .................... 9230B 9230B-93
per 100 mL \28\. multiple tube.
multiple tube/ .................... .................... D6503-99 \10\ Entero-
multiple well. lert[reg]
\13,\ \23\
MF \2\ \6\ \7\ 1106.1 \24\ 9230C 9230C-93 5259-92 \10\
\8\ \9\ two
step.
single step, or 1600 \25\, p. 143
Plate count. \3\
Protozoa:
8. Cryptosporidium \28\.. Filtration/IMS/ 1622 \26\, 1623 \27\
FA.
9. Giardia \28\.......... Filtration/IMS/ 1623 \27\ .................... ..................... ..............
FA.
Aquatic Toxicity:
10. Toxicity, acute, Ceriodaphnia 2002.0 \29\
fresh water organisms, dubia acute.
LC50 percent effluent..
Daphnia puplex 2021.0 \29\
and Daphnia
magna acute.
Fathead Minnow, 2000.0 \29\
Pimephales
promelas, and
Bannerfin
shiner,
Cyprinella
leedsi, acute.
Rainbow Trout, 2019.0 \29\
Oncorhynchus
mykiss, and
brook trout,
Salvelinus
fontinalis,
acute.
Bioluminescent Microtox[supreg]
bacteria, \32\
Vibrio
Fischeri.
11. Toxicity, acute, Mysid, 2007.0 \29\
estuarine and marine Mysidopsis
organisms of the bahia, acute.
Atlantic Ocean and Gulf
of Mexico, LC50, percent
effluent..
Sheepshead 2004.0 \29\
Minnow,
Cyprinodon
variegatus,
acute.
Silverside, 2006.0 \29\
Menidia
beryllina,
Menidia
menidia, and
Menidia
peninsulae,
actue.
Bioluminescent Microtox[supreg]
bacteria, \33\
Vibrio
Fischeri.
12. Toxicity, chronic, Fathead minnow, 1000.0 \30\
fresh water organisms, Pimephales
NOEC or IC25, percent promelas,
effluent.. larval
survival and
growth.
Fathead minnow, 1001.0 \30\
Pimephales
promelas,
embryo-larval
survival and
teratogenicity.
[[Page 18193]]
Daphnia, 1002.0 \30\
Ceriodaphnia
dubia,
survival and
reproduction.
Green alga, 1003.0 \30\
Selenastrum
capricomutum,
growth.
13. Toxicity, chronic, Sheepshead 1004.0 \31\
estuarine and marine minnow,
organisms of the Cyprinodon
Atlantic Ocean and Gulf variegatus,
of Mexico, NOEC or IC25, larval
percent effluent.. survival and
growth.
Sheepshead 1005.0 \31\
minnow,
Cyprinodon
variegatus,
embryo-larval
survival and
teratogenicity.
Inland 1006.0 \31\
silverside,
Menidia
beryllina,
larval
survival and
growth.
Mysid, 1007.0 \31\
Mysidopsis
bahia,
survival,
growth, and
fecundity.
Sea urchin, 1008.0 \31\
Arbacia
punctulata,
fertilization.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Notes to Table IA:
\1\ The method must be specified when results are reported.
\2\ A 0.45-[mu]m membrane filter (MF) or other pore size certified by the manufacturer to fully retain organisms to be cultivated and to be free of
extractables which could interfere with their growth.
\3\ USEPA. 1978. Microbiological Methods for Monitoring the Environment, Water, and Wastes. Environmental Monitoring and Support Laboratory, U.S.
Environmental Protection Agency, Cincinnati, OH. EPA/600/8-78/017.
\4\ [Reserved]
\5\ USGS. 1989. U.S. Geological Survey Techniques of Water-Resource Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and
Analysis of Aquatic Biological and microbiological Samples, U.S. Geological Survey, U.S. Department of Interior, Reston, VA.
\6\ Because the MF technique usually yields low and variable recovery from chlorinated wastewaters, the Most Probable Number method will be required to
resolve any controversies.
\7\ Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes
to account for the quality, character, consistency, and anticipated organism density of the water sample.
\8\ When the MF method has not be used previously to test ambient waters with high tubidity, large number of noncoliform bacteria, or samples that may
contain organisms stressed by chlorine, a parallel test should be conducted with a multiple-tube technique to demonstrate applicability and
comparability of results.
\9\ To assess the comparability of results obtained with individual methods, it is suggested that side-by-side tests be conducted across seasons of the
year with the water samples routinely tested in accordance with the most current Standard Methods for the Examination of Water and Wastewater or EPA
alternate test procedure (ATP) guidelines.
\10\ ASTM. 2000, 1999, 1996. Annual Book of ASTM Standards--Water and Environmental Technology. Section 11.02. American Society for Testing and
Materials. 100 Barr Harbor Drive, West Conshohocken, PA 19428.
\11\ AOAC. 1995. Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. Association of Official Analytical Chemists
International. 481 North Frederick Avenue, Suite 500, Gaithersburg, MD 20877-2417.
\12\ The multiple-tube fermentation test is used in 9221B.1. Lactose broth may be used in lieu of lauryl tryptose broth (LTB), if at least 25 parallel
tests are conducted between this broth and LTB using the water samples normally tested, and this comparison demonstrates that the false-positive rate
and false-negative rate for total coliform using lactose broth is less than 10 percent. No requirement exists to run the completed phase on 10 percent
of all total coliform-positive tubes on a seasonal basis.
\13\ These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is used to detect the enzyme [beta]-
glucuronidase produced by E. coli.
\14\ After prior enrichment in a presumptive medium for total coliform using 9221B.1, all presumptive tubes or bottles showing any amount of gas, growth
or acidity within 48 h 3 h of incubation shall be submitted to 9221F. Commercially available EC-MUG media or EC media
supplemented in the laboratory with 50 [mu]g/mL of MUG may be used.
\15\ Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube and
dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert[reg] may be enumerated with the
multiple-well procedures, Quanti-Tray[reg] or Quanti-Tray[reg] 2000, and the MPN calculated from the table provided by the manufacturer.
\16\ Colilert-18[reg] is an optimized formulation of the Colilert[reg] for the determination of total coliforms and E. coli that provides results within
18 h of incubation at 35[deg]C rather than the 24 h required for the Colilert[reg] test and is recommended for marine water samples.
\17\ Descriptions of the Colilert[reg], Colilert-18[reg], Quanta-Tray[reg], and Quanta-Tray[reg]/2000 may be obtained from IDEXX Laboratories, Inc., One
IDEXX Drive, West Brook, ME 04092.
\18\ A description of the mColiBlue24[reg] test, Total Coliforms and E. coil, is available from Hach Company, 100 Dayton Ave., Ames, IA 50010.
\19\ Subject total coliform positive samples determined by 9222B or other membrane filter procedure to 9222G using NAN-MUG media.
\20\ USEPA. 2002. Method 1103.1: Eschericia coil (E. coil) In Water By Membrane Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC).
U.S. Environmental Protection Agency, Office of Water, Washington, DC EPA-821-R-02-02.
\21\ USEPA. 2002. Method 1603: Escherichia coil (E. coil) In Water By Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar
(modified mTEC). U.S. Environmental Protection Agency, Office of Water, Washington, DC EPA-821-R-02-023.
[[Page 18194]]
\22\ Preparation and use of MIT agar with a standard membrane filter procedure is set forth in the article, Brenner et al. 1993. ``New Medium for the
Simultaneous Detection of Total Coliform and Escherichia coli in Water.'' Appl. Environ. Microbial. 59:3534-3544 and in USEPA. 2002. Method 1604:
Total Coliforms and Escherichia coil (E. coil) in Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI Medium). U.S.
Environmental Protection Agency, Office of Water, Washington, DC EPA 821-R-02-024.
\23\ A description of the Enterolert[reg] test may be obtained from IDEXX Laboratories, Inc., One IDEXX Drive, Westbrook, ME 04092.
\24\ USEPA. 2002. Method 1106.1: Enterococci In Water By Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA). U.S. Environmental
Protection Agency, Office of Water, Washington, DC EPA-821-R-02-021.
\25\ USEPA. 2002. Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI). U.S.
Environmental Protection Agency, Office of Water, Washington, DC EPA-821-R-02-022.
\26\ Method 1622 uses filtration, concentration, immunomagnetic separation of oocysts from captured material, immunofluorescence assay to determine
concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the detection of Cryptosporidium.
USEPA. 2001. Method 1622: Cryptosporidium in Water by Filtration/IMS/FA. U.S. Environmental Protection Agency, Office of Water, Washington, DC EPA-821-
R-01-026.
\27\ Method 1623 uses filtration, concentration, immunomagnetic separation of oocysts and cysts from captured material, immunofluorescence assay to
determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the simultaneous detection
of Cryptosporidium and Giardia oocysts and cysts. USEPA. 2001. Method 1623. Cryptosporidium and Giardia in Water by Filtration/IMS/FA. U.S.
Environmental Protection Agency, Office of Water, Washington, DC EPA-821-R-01-025.
\28\ Recommended for enumeration of target organism in ambient water only.
\29\ USEPA. October 2002. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms. Fifth Edition.
U.S. Environmental Protection Agency, Office of Water, Washington, DC EPA-821-R-02-012.
\30\ USEPA. October 2002. Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater and Organisms. Fourth
Edition. U.S. Environmental Protection Agency, Office of Water, Washington, DC EPA-821-R-02-013.
\31\ USEPA. October 2002. Methods for Measuring the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms. Third Edition.
U.S. Environmental Protection Agency, Office of Water, Washington, DC EPA-821-R-02-014.
\32\ EPA has determined that Microtox[reg] is appropriate for use as a screening level test in a tiered testing system when used in conjunction with
current EPA approved WET test methods. Microtox[reg] may not be used by itself to monitor compliance with WET permit limits established for discharges
to freshwater.
\33\ Prior to using Microtox[reg] to monitor compliance with a WET permit limit, the effluent must be tested using three different species (one test
being Microtox[reg]), and Microtox[reg] must be determined to be the method with the most sensitive test species. This requirement strengthens the
recommedation from EPA's Technical Support Document (1991 Technical Support Document for Water Quality-based Toxics Control, Second Printing, pg. 16)
which states: ``To provide sufficient information for making permitting decisions, EPA recommends a minimum number of three species, representing
three different phyla (e.g., a fish, an invertebrate, and a plant) be used to test an effluent for toxicity.'' In addition, EPA's NPDES regulations at
40 CFR 122.44(d)(1)(ii) require that when a permitting authority is determining WET reasonable potential for exceeding a narrative or numeric criteria
within a State water quality standard, the permitting authority shall use procedures which account for (in addition to other requirements listed in
the regulatory cite) the sensitivity of the species to toxicity testing (when evaluating WET).
[[Page 18195]]
Table 1B.--List of Approved Inorganic Test Procedures
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method number or page)
----------------------------------------------------------------------------------------------------------------------------------------------
Parameter Methodology \57\ Standard methods Standard methods Standard methods on-
EPA \52\ (18th, 19th) (20th) line ASTM USGS/AOAC/other
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acidity, as CaCO3, mg/L.... Electrometric, ...................... 2310 B(4a) 2310 B(4a) 2310 B(4a)-01 D1067-92, 02 I-1020-85 2
endpoint or
phenolphthalein
endpoint.
2. Alkalinity, as CaCO3, mg/L. Electrometric or ...................... 2320 B 2320 B 2320 B-97 D1067-92, 02 973.433, I-1020-85 2
Colorimetric
titration to pH
4.5, manual, or
automatic........ 310.2 (Rev. 1974) 1 ...................... ...................... ....................... ..................... I-2030-85 2
3. Aluminum--Total,4 mg/L..... Digestion 4 ...................... ...................... ...................... ....................... ..................... .....................
followed by:
AA direct ...................... 3111 D ...................... 3111 D-99 ..................... I-3051-85 2
aspiration 36.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 ..................... .....................
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... .....................
ICP/AES 36..... 200.7, Rev. 4.4(1994) 3120 B 3120 B 3120 B-99 ..................... I-4471-97 50
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 3
Direct Current ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Plasma (DCP)
36.
Colorimetric ...................... 3500-AI D 3500-AI-B 3500-AI-B-01 ..................... .....................
(Eriochrome
cyanine R).
4. Ammonia (as N), mg/L....... Manual, 350.1, Rev. 2.0 (1993) 4500-NH3 B 4500-NH3 B 4500-NH3 B-97 ..................... 973.49 3
distillation (at
pH 9.5) 6
followed by:
Nessleri- ...................... 4500-NH3 C (18th only) ...................... ....................... D1426-98, 03 (A) 973.49 3, I-3520-85 2
zation.
Titration...... ...................... 4500-NH3 C (19th) and 4500-NH3 C 4500-NH3 C-97 ..................... .....................
4500-NH3 E (18th)
Electrode...... ...................... 4500-NH3 D or E (19th) 4500-NH3 D or E 4500-NH3 D or E-97 D1426-98, 03 (B) .....................
and 4500-NH3 F or G
(18th)
Automated 350.1, Rev. 2.0 (1993) 4500-NH3 G (19th) and 4500-NH3 G 4500-NH3 G-97 ..................... I-4523-85 2
phenate, or. 4500-NH3 H (18th)
Automated ...................... ...................... ...................... ....................... ..................... Note 7
electrode.
5. Antimony--Total,4 mg/L..... Digestion 4 ...................... ...................... ...................... ....................... ..................... .....................
followed by:
AA direct ...................... 3111 B ...................... 3111 B-99 ..................... .....................
aspiration 36.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 ..................... .....................
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES 36..... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... .....................
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 3
6. Arsenic--Total,4 mg/L...... Digestion 4 206.5 (Issued 1978) 1 ...................... ...................... ....................... ..................... .....................
followed by:
AA gaseous ...................... 3114 B 4.d ...................... 3114 B 4.d-97 2972-97, 03 (B) I-3062-85 2
hydride.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D2972-97, 03 (C) I-4063-98 49
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES \36\.. 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... .....................
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
Colorimetric ...................... 3500-As C 3500-As B 3500-As B-97 2972-97, 03(A) I-3060-85
(SDDC).
7. Barium--Total,\4\ mg/L..... Digestion \4\
followed by:
AA direct ...................... 3111 D ...................... 3111 D-99 ..................... I-3084-85 \2\
aspiration
\36\.
AA direct ...................... 3113 B ...................... 3113 B-99 D4382-95, 03 .....................
furnace \36\.
[[Page 18196]]
ICP/AES \36\... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... .....................
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP \36\....... ...................... ...................... ...................... ....................... ..................... Note 34
8. Beryllium--Total,\4\ mg/L Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:
AA direct ...................... 3111 D ...................... 3111 D-99 3645-98(88), 03(A) I-3095-85 \2\
aspiration.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D3645-98(88), 03(B) .....................
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... .....................
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP, or........ ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Colorimetric ...................... 3500-Be D ...................... ....................... ..................... .....................
(aluminon).
9. Biochemical oxygen demand Dissolved Oxygen ...................... 5210 B 5210 B 5210 B-01 ..................... 973.44,\3\ p. 17.\9\,
(BOD 5), mg/L: Depletion. I-1578-78 \8\, I-
3112-85 \2\, I-4471-
97 \50\
10. Boron \37\--Total, mg/L:.. Colorimetric ...................... 4500-B 4500-B 4500-B B-00 ..................... .....................
(curcumin).
ICP/AES.......... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... .....................
DCP.............. ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
11. Bromide, mg/L: Titrimetric...... ...................... ...................... ...................... ....................... D1246-95(99)(C) p. S44.\10\, I-1125-
85 \2\
Ion 300.0, Rev 2.1 (1993) 4110 B 4110 B 4110 B-00 D4327-97, 03 993.30 \3\
Chromatography. and 300.1, Rev 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters \54\
12. Cadmium--Total,\4\ mg/L... Digestion \4\
followed by:
AA direct ...................... 3111 B or C ...................... 3111 B or C-99 D3556-97, 02 (A or B) 974.27,\3\ p. 37.\9\,
aspiration I-3135-85 \2\ or I-
\36\. 3136-85 \2\
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D3557-95, 02 (D) I-4138-89 \51\
STGFAA......... 200.9, Rev. 2.2 (1994)
ICP/AES \36\... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... I-1472-85 \2\
or
I-4471-97 \50\
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP \36\....... ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Voltametry \11\, ...................... ...................... ...................... ....................... D3557-95, 02 (C)
or
Colorimetric ...................... 3500-Cd D ...................... 3500-Cd D-90
(Dithizone).
13. Calcium--Total,\4\ mg/L... Digestion \4\
followed by:
AA direct ...................... 3111 B ...................... 3111 B-99 D511-93, 03(B) I-3152-85 \2\
aspiration.
ICPA/AES....... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... I-4471-97 \50\
DCP, or........ ...................... ...................... ...................... ....................... ..................... Note 34
Titrimetric ...................... 3500-Ca D 3500-Ca B 3500-Ca B-97 D511-93, 03(A)
(EDTA).
Ion ...................... ...................... ...................... ....................... D 6919-03
Chromatography.
14. Carbonaceous Biochemical Dissolved Oxygen ...................... 5210 B 5210 B 5210 B-01
oxygen demand (CBOD5), mg/L12. Depletion with
nitrification
inhibitor.
15. Chemical oxygen demand Titrimetric...... 410.3 (Rev. 1978) \1\ 5220 C 5220 C 5220 C-97 D1252-95, 00 (A) 973.46,\3\ p. 17.\9\
(COD), mg/L. I-3560-85 \2\
[[Page 18197]]
Spectrophotometri 410.4, Rev. 2.0 (1993) 5220 D 5220 D 5220 D-97 D1252-95, 00 (B) Notes 13, 14. I-3561-
c, manual or 85 \2\
automatic.
16. Chloride, mg/L............ Titrimetric ...................... 4500-Cl B 4500-Cl B 4500-CL B-97 D512-89 (99) (B) I-1183-85 \2\
(silver nitrate)
or
(Mercuric ...................... 4500-Cl-C 4500-Cl-C 4500-Cl-C-97 D512-89(99) (A) 973.51,\3\ I-1184-85
nitrate). \2\
Colorimetric, ...................... ...................... ...................... ....................... ..................... I-1187-85 \2\
manual or.
Automated ...................... 4500-Cl-E 4500-CI-E 4500-CI-E-97 ..................... I-2187-85 \2\
(Ferricyanide).
Potentiometric ...................... 4500-Cl-D 4500-CI-D 4500-CI-D-97
Titration.
Ion Selective ...................... ...................... ...................... ....................... D512-89(99) (C) .....................
Electrode.
Ion 300.0 Rev. 2.1 (1993) 4110 B 4110 B 4110 B-00 D4327-97 993.30 \3\
Chromatography. and 300.1, Rev. 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters \54\
17. Chlorine--Total residual, Amperometric ...................... 4500-Cl D 4500-Cl D 4500-CI D-00
mg/L; Titrimetric: direct, or
Amperometric ...................... 4500-Cl E 4500-Cl E 4500-Cl E-00
direct (low
level).
Iodometric direct ...................... 4500-Cl B 4500-Cl B 4500-Cl B-00
Back titration ...................... 4500-Cl C 4500-Cl C 4500-Cl C-00
ether end-point
\15\ or.
DDP-FAS.......... ...................... 4500-Cl F 4500-Cl F 4500-Cl F-00
Spectriogitinetru ...................... 4500-CI G 4500-CI G 4500-CI G-00 ..................... .....................
cm.
DPD.............. ...................... ...................... ...................... ....................... ..................... .....................
Or Electrode..... ...................... ...................... ...................... ....................... ..................... Note 16
18. Chromium VI dissolved, mg/ 0.45 micron ...................... ...................... ...................... ....................... ..................... .....................
L. Filtration
followed by:
AA chelatoin- ...................... 3111 C ...................... 3111 C-99 ..................... I-1232-85
extraction or
Ion 218.6, Rev. 3.3 (1994) 3500-Cr E 3500-Cr C 3500-Cr C-01 D5257-97 993.23
Chromatography.
Colorimetric ...................... 3500-Cr D 3500-Cr B 3500-CR B-01 D1687-92, 02 (A) I-1230-85
(Diphenyl-
carbazide).
19. Chromium--Total,\4\ mg/L.. Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:
AA direct ...................... 3111B ...................... 3111 B-99 D1687-92, 02 (B) 974.27 \3\, I-3236-95
aspriation \2\
\36\.
AA chelation- ...................... 3111 C ...................... 3111 C-99 ..................... .....................
extraction.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D1687 92, 02 (C) I-3233-93 \46\
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES \36\... 200.7, Rev/ 4/4 (1994) 3120 B 3120 B 3120 B-99 ..................... .....................
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP,\36\....... ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Colorimetric ...................... 3500-Cr D 3500-Cr B 3500-Cr B 01 ..................... .....................
(Diphenylcarba
zide).
20. Cobalt--Total,\4\ mg/L.... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 B or C ...................... 3111 B or C-99 D3558-94, 03 (A or B) p. 37 \9\, I-3239-85
aspriation. \2\
AA furnace..... ...................... 3113 B ...................... 311 B-99 D3558-94, 03 (C) I-4243-89 \51\
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... I-4471-97 \50\
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP............ ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
21. Color platinum cobalt Colorimetric ...................... 2120 E 2120E ....................... ..................... Note 18
units or dominant wavelength, (ADMI), or
hue luminance purity:.
(Platinum ...................... 2120 B 2120 B 2120 B-01 ..................... I-1250-85 \2\
cobalt), or.
Spectro- ...................... 2120 C 2120 C ....................... ..................... .....................
photometric.
Copper-Total,\4\ mg/L......... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:
AA direct ...................... 3111 B or C ...................... 3111 B or C-99 D1688-95, 02 (A or B) 974.27 \3\ p. 37.\9\
aspiration I-3270-85 \2\ or I-
\36\. 3271-85 \2\
AA furnace..... ...................... 3113 B ...................... 3113 B-99 ..................... I-4274-89 \51\
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
[[Page 18198]]
ICP/AES \36\... 200.7, Rev. 4.4 (1994) 3120 B ...................... 3120 B-99 ..................... I4471-97 \50\
ICP/MS......... 200.8 Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14\3\
DCP\36\ or..... ...................... ...................... ...................... D4190-94, 99 Note 34
Colorimetric ...................... 3500-Cu D 3500-Cu B 3500-Cu B-99
(Neocuproine)
or.
Bicinchoninate) ...................... 3500-Cu B 3500-Cu B 3500-Cu C-99 ..................... Note 19
23. Cyanide-Total, mg/L:...... Automated ...................... ...................... ...................... ....................... ..................... Kelada-01\55\
Distillation and
Colorimetry, or.
Manual 335.4 Rev. 1.0 4500-CN-C 4500-CN-C ....................... D2036-98(A) 10-204-00-1-X\56\
distillation (1993)\57\
with MgCl2
followed by.
Titrimetric, or.. ...................... 4500-CN-D 4500-CN-D 4500-CN-D-99 ..................... p. 22\9\
Spectrophotometri ...................... 4500-CN-E 4500-CN-E 4500-CN-E-99 D2036-98(A) I-3300-85
c, manual or.
Automated\20\, or 335.4, Rev. 1.0 ...................... ...................... ....................... ..................... 10-204-00-1-X\56\, 1-
(1993)\57\ 4302-85\2\
Ion Selective ...................... 4500-CN-F 4500-CN-F 4500-CN-F-99 D2036-98(A)
Electrode.
24. Available Cyanide, mg/L:.. Cyanide Amenable ...................... 4500-CN-G 4500-CN-G 4500-CN-G-99 D2036-98(B)
to Chlorination
(CATC); Manual
distillation
with MgCl2
followed by
Titrimetric or
Spectrophotometr
ic.
Flow injection ...................... ...................... ...................... ....................... D6888-03 OIA-1677\44\
and ligand
exchange,
followed by
amperometry..
Automated ...................... ...................... ...................... ....................... ..................... Keleda-01\55\
Distillation and
Colorimetry.
25. Fluoride--Total, mg/L:.... Manual ...................... 4500-F-B 4500-F-B 4500-F-B-97
distillation\6\
followed by.
Electrode, manual ...................... ...................... ...................... 4500F-C-97 D1179-93, 99 (B)
or.
Automated or..... ...................... ...................... ...................... ....................... ..................... I-4327-85\2\
Colorimetric ...................... 4500-F-D 4500-F-D 4500-F-D-97 D1179-93, 99 (A)
(SPADNS) or.
Automated ...................... 4500-F-E 4500-F-E 4500-F-E-97
complexone.
Ion 300.0, Rev 2.1 (1993) 4110 B 4110 B 4110 B-00 D4327-97,03 993.30\3\
Chromatography. and 300.1 Rev 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters\54\
26. Gold--Total\4\ mg/L....... Digestion\4\
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99
aspiration, or.
AA furnace, or... 231.2 (Rev. 1878)\1\
STGFAA........... 200.9 Rev. 2.2 (1994)
DCP.............. ...................... ...................... ...................... ....................... ..................... Note 34
27. Hardness--Total, as CaCO3, Automated 130.1 (Issued 1971)\1\ ...................... ...................... ....................... ..................... .....................
mg/L. colorimetric,.
Titrimetric ...................... 2340 B or C 2340 B or C 2340 B or C-97 D1136-86(92), 02 973.52B.\3\, I-1338-
(EDTA), or. 85\2\
Ca plus Mg as
their
carbonates, by
inductively
coupled plasma
or AA direct
aspiration. (See
Parameters 13
and 33).
28. Hydrogen ion (pH), pH Electrometric ...................... 4500-H\+\ B 4500-H\+\ B 4500-H\+\ B-00 D1293-84 (90), 99 (A 973.41.\3\, I-1586-85
units. measurement, or. or B) \2\
Automated 150.2 (Dec. 1982) \1\ ...................... ...................... ....................... ..................... Note [21, I-2587-85
electrode. \2\
29. Iridium--Total,\4\ mg/L... Digestion \4\
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99
aspiration or.
AA furnace..... 235.2 (Issued 1978)
\1\
30. Iron--Total,\4\ mg/L...... Digestion \4\
followed by:.
[[Page 18199]]
AA direct ...................... 3111 B or C ...................... 3113 B-89, 93, 99 D1068-96, 03 (A or B) 974.27.\3\, I-3381-85
aspiration \2\
\36\.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D 1068-96, 03 (C) .....................
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES \36\... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... I-4471-97 \50\
DCP \36\....... ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Colorimetric ...................... 3500-Fe D 3500-Fe B 3500-Fe B-97 D1068-96, 03 (D) Note 22
(Phenanthrolin
e).
31. Kjeldahl Nitrogen \5\-- Digestion and ...................... 4500-Norg B or C with 4500-Norg B or C with 4500-Norg B or C-97 D3590-89, 02 (A) .....................
Total, (as N), mg/L. distillation 4500-NH3 B 4500-NH3 B with 4500-NH3 B-97
followed by:
\20\.
Titration, or.. ...................... 4500-NH3 C (19th) and 4500-NH3 C 4500-NH3 C-97 D3590-89, 02 (A) 973.48 \3\
4500-NH3 E (18th)
Nesslerization, ...................... 4500-NH3 C (18th Only) ...................... ....................... D3590-89, 02 (A) .....................
or.
Electrode...... ...................... 4500-NH3 F or G (18th) 4500-NH3 D or E 4500-NH3 D or E-97 ..................... .....................
and 4500-NH3 D or E
(19th)
Automated 351.1 (Rev. 1978) \1\ ...................... ...................... ....................... ..................... I-4551-78 \8\
phenate
colorimetric.
Semi-automated 351.2, Rev. 2.0 (1993) ...................... ...................... ....................... D3590-89, 02(B) I-4515-91 \45\
block digestor
colorimetric.
Manual or block ...................... ...................... ...................... ....................... D3590-89, 02 (A) .....................
digestor
potentiometric.
Block digester, ...................... ...................... ...................... ....................... ..................... Note 39
followed by
Auto
distillation
and Titration,
or.
Nesslerization, ...................... ...................... ...................... ....................... ..................... Note 40
or.
Flow injection ...................... ...................... ...................... ....................... ..................... Note 41
gas diffusion.
32. Lead--Total,\4\ mg/L...... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 B or C ...................... 3111 B or C-99 D3559-96, 03 (A or B) \3\ 974.27, \2\ I-
aspiration 3399-85
\36\.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D3559-96, 03 (D) \51\ I-4403-89
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES \36\... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... \50\ I-4471-97
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 \3\ 993.14
DCP............ ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Voltametry \11\ ...................... ...................... ...................... ....................... D3559-96, 03 (c) .....................
or.
Colorimetric ...................... 3500-Pb D 3500-Pb B 3500-Pb B-97 ..................... .....................
(Dithizone).
33. Magnesium--Total,\4\ mg/L. Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99 D511-93, 93 (b) \3\ 974.27, \2\ I-
aspiration. 3447-85
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... \50\ I-4471-97
DCP or......... ...................... ...................... ...................... ....................... ..................... Note 34
Gravimetric.... ...................... 3500-Mg D ...................... ....................... ..................... .....................
Ion ...................... ...................... ...................... ....................... D6919-03 .....................
Chromatography.
34. Manganese--Total,\4\ mg/L. Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99 D858-95 (A or B) \3\ 974.27, \2\ I-
Aspiration 3454-85
\36\.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D858-95, 02 (c) .....................
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES \36\... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... \50\ I-4471-97
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 \3\ 993.14
DCP \36\, or... ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Colorimetric ...................... 3500-Mn D 3500-Mn B 3500-Mn B-99 ..................... \3\ 920.203
(Persulfate),
or.
(Periodate).... ...................... ...................... ...................... ....................... ..................... Note 23
[[Page 18200]]
35. Mercury--Total \4\, mg/L:. Cold vapor, 245.1, Rev. 3.0 (1994) 3112 B ...................... 3112 B-99 D3223-91 \3\ 977.22, \2\ I3462-
manual or. 85
Automated...... 245.2 (Issued 1974) ...................... ...................... ....................... ..................... .....................
Cold vapor 245.7 (Dec. 2003) \58\ ...................... ...................... ....................... ..................... .....................
atomic
fluorescence
spectrometry
(CVAFS).
Purge and Trap 1631E \43\ ...................... ...................... ....................... ..................... .....................
CVAFS.
Molybedenum--Total \4\, mg/L.. Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 D ...................... 3111 D-99 ..................... \2\ I-3490-85
aspiration.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 ..................... \47\ I-3492-96
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B ...................... 3120 B-99 ..................... \50\ I-4471-97
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 \3\ 993.14
DCP............ ...................... ...................... ...................... ....................... ..................... Note 34
37. Nickel-Total, \4\ mg/L.... Digestion \4\ ...................... ...................... ...................... ....................... .....................
followed by:.
AA direct ...................... 3111 B or C ...................... 3111 B or C-99 D1886-90, 94 (98) (A I-3499-85 \2\
aspiration or B)
\36\.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D1886-90, 94 (98)(C) I-4503-89 \51\
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ......................
ICP/AES \36\... 200.7, Rev. 4.4 (1994) ...................... ...................... .......................
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP \36\, or... ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Colorimetric ...................... 3500-NI D (17th ...................... ....................... .....................
(heptoxime). Edition)
38. Nitrate (as N), mg/L...... Ion 300.0, Rev 2.1 (1993) 4110 B 4110 B 4110 B-00 D4327-97, 03 993.30 \3\
Chromatography. and 300.1, Rev 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters \54\
Ion Selective ...................... 4500 NO3 \-\ D 4500 NO3 \-\ D 4500 NO3 \-\ D-00 ..................... .....................
Electrode.
Colorimetric 352.1 \1\ ...................... ...................... ....................... ..................... 97.50 \3\ 419D \17\,
(Brucine p. 28.\9\
sulfate), or.
Nitrate-nitrite N ...................... ...................... ...................... ....................... .....................
minus Nitrite N
(See parameters
39 and 40).
39. Nitrate-nitrite (as N), mg/ Cadmimum ...................... 4500-NO3 \-\ E 4500-NO3 \-\ E 4500-NO3 \-\ E-00 D3867-99(B) .....................
L. reduction,
Manual or.
Automated, or.... 353.2, Rev. 2.0 (1993) 4500-NO3 \-\ F 4500-NO3 \-\ F 4500-NO3 \-\ F-00 D3867-99(A) I-4545-85 \2\
Automated ...................... 4500-NO3 \-\ H 4500-NO3 \-\ H 4500-NO3 \-\ H-00 D4327-97 .....................
hydrazine.
Ion 300.0, Rev 2.1 (1993) 4110 B 4110 B 4110 B-00 4327-97, 03 993.30 \3\
Chromatography. and 300.1, Rev 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters \54\
40. Nitrite (as N), mg/L...... Spectrophoto- ...................... 4500-NO2 B 4500-NO2 B 4500-NO2 B-00 ..................... Note 25
metric: Manual
or.
Automated ...................... ...................... ...................... ....................... ..................... I-4540-85 \2\
(Diazotization).
Automated 353.2, Rev. 2.0 (1993) 4500-NO3 \-\ F 4500-NO3 \-\ F 4500-NO3 \-\ F-00 D3867-99(A) .....................
(*bypass cadmium
reduction).
Manual (* bypass ...................... 4500-NO3 \-\ E 4500-NO3 \-\ E 4500-NO3 \-\ E-00 ..................... .....................
cadmium
reduction).
[[Page 18201]]
Ion 300.0, Rev 2.1 (1993) 4110 B 4110 B 4110 B-00 D4327-97, 03 993.30 \3\
Chromatography. and 300.1, Rev 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters \54\
41. Oil and grease--Total Hexane 1664A \42\ 5520 B \38\ 5520 B \38\ 5520 B-01 \38\ ..................... .....................
recoverable, mg/L. extractable
material (HEM);
n-Hexane
extraction and
gravimetry.
Silica gel 1664A\42\ ...................... ...................... ....................... ..................... .....................
treated HEM (SGT-
HEM): Silica gel
treatment and
gravimetry.
42. Organic carbon--Total Combustion or ...................... 5310 B, C, or D 5310 B, C, or D 5310 B, C, or D-00 2579-93 (A or B) 973.47,\3\ p. 14.\24\
(TOC), mg/L. oxidation.
43. Organic nitrogen (as N), Total Kjeldahl N ...................... ...................... ...................... ....................... ..................... .....................
mg/L. (Parameter 31)
minus ammonia N
(Parameter 4).
44. Orthophosphate (as P), mg/ Ascorbic acid ...................... ...................... ...................... ....................... ..................... .....................
L. method:.
Automated, or.... 365.1, Rev. 2.0 (1993) 4500-P F 4500-P F ....................... ..................... 973.56 \3\, 1-4601-85
\2\
Manual single ...................... 4500-P E 4500-P E ....................... D515-88(A) 973.55 \3\
reagent.
Manual two 365.3, (Issued ...................... ...................... ....................... ..................... .....................
reagent. 1978)\1\
Ion 300.0, Rev. 2.1 (1993) 4110 B 4110 B 4110 B-00 D4327-97, 03 993.30 \33\
Chromatography. and 300.1 Rev. 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters \54\
45. Osmium-Total \4\, mg/L.... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 D ...................... 3111 D-99 ..................... .....................
aspiration, or.
AA furnace..... 252.2 (Issued 1978)\1\ ...................... ...................... ....................... ..................... .....................
46. Oxygen, dissolved, mg/L... Winkler (Azide ...................... 4500-O C 4500-O C 4500-O C-01 888-92, 03 (A) I-1576-78 \8\
modification),
or.
Electrode........ ...................... 4500-O G 4500-O G 4500-O G-01 D888-92, 03 (B) 1-1576-78 \8\
47. Palladium--Total,\4\ mg/L. Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by.
AA direct ...................... 3141 B ...................... 3111 B-99 ..................... p. S27.\10\
aspiration, or.
AA furnace..... 253.2 \1\ (Issued ...................... ...................... ....................... ..................... p. S28.\10\
1978)
DCP............ ...................... ...................... ...................... ....................... ..................... Note 34.
48. Phenois, mg/L............. Manual 420.1 \1\ (Rev. 1978) ...................... ...................... ....................... ..................... Note 27.
distillation
\26\ Followed
by:.
Colorimetric 420.1 \1\ (Rev. 1978) ...................... ...................... ....................... ..................... Note 27.
(4AAP) manual,
or.
Automated........ 420.4 Rev. 1.0 (1993) ...................... ...................... ....................... ..................... .....................
49. Phosphorus (elemental), mg/ Gas-liquid ...................... ...................... ...................... ....................... ..................... Note 28.
L. chromatography.
50. Phosphorus--Total, mg/L... Persulfate ...................... 4500-P B.5 4500-P B.5 ....................... ..................... 973.55 \3\
digestion
followed by:
\29\.
Manual or........ 365.3 \1\ (Issued 4500-P E 4500-P E ....................... D515-88(A) .....................
1978)
Automated 365.1 Rev. 2.0 (1993) 4500-P F 4500-P F ....................... ..................... 973.56 \3\, I-400-85
ascorbic acid \2\
reduction.
Semi-automated 365.4 \1\ (Issued ...................... ...................... ....................... D515-88(B) I-4610-91 \48\
block digestor. 1974)
51. Platinum-Total,\4\ mg/L... Digestion \4\
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99
aspiration.
AA furnace....... 255.2 \1\
DCP.............. ...................... ...................... ...................... ....................... ..................... Note 34
52. Potassium-Total,\4\ mg/L:. Digestion \4\
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99 ..................... 973.l53 \3\, 1-3630-
aspiration. 85 \2\
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99
Flame ...................... 3500-K D 3500-K B 3500-K B-99
photometric or.
Colorimetric... ...................... ...................... ...................... ....................... ..................... 317 B \17\
Ion ...................... ...................... ...................... ....................... D 6919-03
Chromatography.
53. Residue-Total, mg/L....... Gravimetric, 103- ...................... 2540 B 2540 B 2540 B-97 ..................... I-3750-85 \2\
105[deg].
54. Residue-filterable, mg/L.. Gravimetric, ...................... 2540 C 2540 C 2540 C-97 ..................... I-1750-85 \2\
180[deg].
[[Page 18202]]
55. Residue-non-filterable Gravimetric, 103- ...................... 2540 D 2540 D 2540 D-97 ..................... I-3765-85 \2\
(TSS), mg/L. 105[deg] post
washing of
residue.
56. Residue-settleable, mg/L:. Volumetric, ...................... 2540 F 2540 F 2540 F-97
(lmhoff cone),
or gravimetric.
57. Residue-Volatile, mg/L.... Gravimetric, 160.4 \1\ ...................... ...................... ....................... ..................... I-3753-85 \2\
550[deg].
58. Rhodium-total,\4\ mg/L.... Digestion \4\
followed by:.
AA direct ...................... 3111 B 3111 B 3111 B-99
aspiration, or.
AA furnace..... 265.2 \1\
STGFAA......... 200.9, Rev. 2.2 (1994)
59. Ruthenium-Total,\4\ mg/L.. Digestion \4\
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99
aspiration, or.
AA furnace..... 267.2 \1\
STGFAA......... 200.9, Rev. 2.2 (1994)
60. Selenium-Total,\4\ mg/L... Digestion \4\
followed by:.
AA furnace..... ...................... 3113 B ...................... 3113 B-99 D3859-98, 03 (B) I-4668-98 \49\
STGFAA......... 200.9, Rev. 2.2 (1994)
ICP/AES,\36\... 200.7 \5\, Rev. 4.4 3120 B 3120 B 3120 B-99
(1994)
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
AA gaseous ...................... 3114 B 3114 B 3114 B-97 D3859-98, 03 (A) I-3667-85 \2\
hydride.
61. Silica \37\-Dissolved, mg/ 0.45 micron
L. filtration
followed by:.
Colorimetric, ...................... 4500-Si D 4500-SiO2 4500-SiO2 C-97 D859-94, 00 I-1700-85 \2\
Manual or.
Automated ...................... ...................... ...................... ....................... ..................... I-2700-85 \2\
(Molybdosilica
te), or.
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... I-4471-97 \50\
62. Silver-Total,\4\ mg/L..... Digestion 4, 29
followed by:.
AA direct ...................... 3111 B or C ...................... 3111 B or C-99 ..................... 974.27 \3\, p. 37
aspiration. \9\, I-3720-85 \2\
AA furnace..... ...................... 3113 B ...................... 3113 B-99 ..................... I-4724-89 \51\
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
............... ICP/AES 200.7, Rev. 4.4 (1994) 3210 B 3120 B 3120 B-99 I-4471-97 \50\
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP............ ...................... ...................... ...................... ....................... ..................... Note 34
63. Sodium-Total,\4\ mg/L..... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99 ..................... 973.54 \3\, I-3735-85
aspiration. \2\
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... I-4471-97 \50\
DCP, or........ ...................... ...................... ...................... ....................... ..................... Note 34
Flame ...................... 3500-Na D 3500-Na B 3500-Na B-97 ..................... .....................
photometric.
Ion ...................... ...................... ...................... ....................... D 6919-03 .....................
Chromatography.
64. Specific conductance, Wheatstone bridge 120.1 \1\ (Rev. 1982) 2510 B 2510 B 2510 B-97 D1125-95 (99)(A) 973.40 \3\, I-2781-85
micromhos/cm at 25[deg], C. \2\
65. Sulfate (as SO4), mg/L.... Automated 375.2, Rev. 2.0 (1993) ...................... ...................... ....................... ..................... .....................
colorimetric.
Gravimetric...... ...................... 4500-SO4 -\2\ C 4500-SO4 -\2\ C ....................... ..................... 925.54. \3\
Turbidimetric.... ...................... ...................... ...................... ....................... D516-90, 02 426C.\30\
[[Page 18203]]
Ion 300.0, Rev 2.1 (1993) 4110 B 4110 B 4110 B-00 D4327-97, 03 993.30 \33\
Chromatography. and 300.1, Rev 1.0
(1997)
CIE/UV........... ...................... ...................... ...................... ....................... ..................... Waters \54\
66. Sulfide (as S), mg/L...... Titrimetric ...................... 4500-S -\2\F (19th) 4500-S -\2\F-00 ....................... I-3840-85 \2\
(iodine), or. 4500-S -\2\E (18th)
Colorimetric ...................... 4500-S -\2\D 4500-S -\2\D-00 4500-S -\2\ ..................... .....................
(methylene blue).
Ion Selective ...................... 4500-S -\2\G 4500-S -\2\G 4500-S -\2\G-00 4652-03 .....................
Electrode.
67. Sulfite (as SO 3), mg/L... Titrimetric ...................... 4500-SO \3\ -\2\B 4500-SO \3\ -\2\B 4500-SO \3\ -\2\B-00 ..................... .....................
(iodine-iodate).
68. Surfactants, mg/L......... Colorimetric ...................... 5540 C 5540 C 5540 C-00 D2330-88, 02 .....................
(methylene blue).
69. Temperature, [deg]C....... ................. Thermometric 2550 B 2550 B 2550 B-00 ..................... Note 32
70. Thallium-Total,\4\ mg/L... Digestion \4\ by: ...................... ...................... ...................... ....................... ..................... .....................
AA direct ...................... 3111 B ...................... 3111 B-99 ..................... .....................
aspiration.
AA furnace..... 279.2 \1\ (Issued ...................... ...................... ....................... ..................... .....................
1978)
STGFAA......... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... .....................
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02. 993.14 \3\
71. Tin-Total,\4\ mg/L........ Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 B ...................... 3111 B-99 ..................... I-3850-78 \8\
aspiration.
AA furnace, or. ...................... 3113 B ...................... 3113 B-99 ..................... .....................
STGFAA........... 200.9, Rev. 2.2 (1994) ...................... ...................... ....................... ..................... .....................
ICP/AES.......... 200.7, Rev. 4.4 (1994) ...................... ...................... ....................... ..................... .....................
72. Titanium-total,\4\ mg/L... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 D ...................... 3111 D-99 ..................... .....................
aspiration.
AA furnace..... 283.2 \1\ (Issued ...................... ...................... ....................... ..................... .....................
1978)
DCP............ ...................... ...................... ...................... ....................... ..................... Note 34
73. Turbidity, NTU \53\....... Nephelometric.... 180.1, Rev. 2.0 (1993) 2130 B 2130 B 2130 B-01 D1889-94, 00 (A) I-3860-85 \2\
74. Vanadium-total,\4\ mg/L... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 D ...................... 3111 D-99 ..................... .....................
aspiration.
AA furnace..... ...................... ...................... ...................... ....................... D3373-93, 03 .....................
ICP/AES........ 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 ..................... I-4471-97 \50\.
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... ....................... D5673-02 993.14 \3\
DCP, or.......... ...................... ...................... ...................... ....................... D4190-94, 99 Note 34.
Colorimetric ...................... 3500-V D 3500-V B 3500-V B-97 ..................... .....................
(Gallic Acid).
75. Zinc-total,\4\ mg/L....... Digestion \4\ ...................... ...................... ...................... ....................... ..................... .....................
followed by:.
AA direct ...................... 3111 B or C ...................... 3111 B or C-99 D1691-95, 02 (A or B) 974.27 \3\, p. 37
aspiration \9\, I-3900-85 \2\.
\36\.
AA furnace..... 289.2 \1\ (Issued ...................... ...................... ....................... ..................... .....................
1978)
ICP/AES \36\... 200.7, Rev. 4.4 (1994) 3120 B 3120 B 3120 B-99 \59\ ..................... I-4471-97 \50\.
ICP/MS......... 200.8, Rev. 5.4 (1994) ...................... ...................... D5673-02 993.14 \3\
DCP,\36\ or.... ...................... ...................... ...................... ....................... D4190-94, 99 Note 34
Colorimetric ...................... 3500-ZN E ...................... ....................... ..................... .....................
(Dithizone) or.
(Zincon)....... ...................... 3500-Zn F 3500-Zn B 3500-ZN B-97 ..................... Note 33.
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
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 (NTIS PB 84-
128677), 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, 16th ed.
[[Page 18204]]
\4\ For the determination of total metals (which are equivalent to total recoverable metals) the sample is not filtered before processing. A digestion procedure is required to solubilize
analytes in suspended material and to break down organic-metal complexes (to convert the analyte to a detectable form for colorimetric analysis). For non-platform graphite furnace atomic
absorption determinations a digestion using nitric acid is required prior to analysis. The procedure used should subject the sample to gentle, acid refluxing and at no time should the sample
be taken to dryness. For direct aspiration flame atomic absorption determinations (FLAA) a combination acid (nitric and hydrochloric acids) digestion is preferred prior to analysis. The
approval total recoverable digestion is described as Method 200.2 in Supplement I of ``Methods for the Determination of Metals in Environmental Samples'' EPA/600R-94/111, May, 1994, and is
reproduced in EPA Methods 200.7, 200.8, and 200.9 from the same Supplement. However, when using the gaseous hydride technique or for the determination of certain elements such as antimony,
arsenic, selenium, silver, and tin by non-EPA graphite furnace atomic absorption methods, mercury by cold vapor atomic absorption, the noble metals and titanium by FLAA, a specific or
modified sample digestion procedure may be required and in all cases the referenced method write-up should be consulted for specific instruction and/or cautions. For analyses using
inductively coupled plasma-atomic emission spectrometry (ICP-AES), the direct current plasma (DCP) technique or the EPA spectrochemical techniques (platform furnace AA, ICP-AES, and ICP-MS)
use EPA Method 200.2 or an approved alternate procedure (e.g., CEM microwave digestion, which may be used with certain analytes as indicated in Table IB); the total recoverable digestion
procedures in EPA Methods 200.7, 200.8, and 200.9 may be used for those respective methods. Regardless of the digestion procedure, the results of the analysis after digestion procedure are
reported as ``total'' metals.
\5\ Copper sulfate must be used in place of mercuric sulfate.
\6\ Manual distillation is not required if comparability data on representative effluent samples are on file to show that this preliminary distillation step is not necessary: however, manual
distillation will be required to resolve any controversies.
\7\ Ammonia, Automated Electrode Method, Industrial Method Number 379-75 WE, dated February 19, 1976, Bran & Luebbe (Technicon) Auto Analyzer II, Bran & Luebbe Analyzing Technologies, Inc.,
Elmsford, NY 10523.
\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).
\9\ American National Standard on Photographic Processing Effluents, Apr. 2, 1975. Available from ANSI, 1430 Broadway, New York, NY 10018.
\10\ 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).
\11\ The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable.
\12\ Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test method with measures ``total BOD.'' The addition of the nitrification inhibitor is not a
procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit requires reporting the traditional BOD5 may not use a nitrification inhibitor in the
procedure for reporting the results. Only when a discharger's permit specifically states CBOD5 is required can the permittee report data using a nitrification inhibitor.
\13\ OIC Chemical Oxygen Demand Method, Oceanography International Corporation, 1978, 512 West Loop, P.O. Box 2980, College Station, TX 77840.
\14\ Chemical Oxygen Demand, Method 8000, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.
\15\ The back titration method will be used to resolve controversy.
\16\ Orion Research Instruction Manual, Residual Chlorine Electrode Model 97-70, 1977, Orion Research Incorporated, 840 Memorial Drive, Cambridge, MA 02138. The calibration graph for the Orion
residual chlorine method must be derived using a reagent blank and three standard solutions, containing 0.2, 1.0, and 5.0 mL 0.00281 N potassium iodate/100 mL solution, respectively.
\17\ The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition, 1976.
\18\ National Council of the Paper Industry for Air and Stream Improvement, Inc. Technical Bulletin 253, December 1971.
\19\ Copper, Biocinchoinate Method, Method 8506, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.
\20\ When using a method with block digestion, this treatment is not required.
\21\ Hydrogen ion (pH) Automated Electrode Method, Industrial Method Number 378-75WA, October 1976, Bran & Luebbe (Technicon) Autoanalyzer II. Bran & Luebbe Analyzing Technologies, Inc.,
Elmsford, NY 10523.
\22\ Iron, 1,10-Phenanthroline Method, Method 8008, 1980, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.
\23\ Manganese, Periodate Oxidation Method, Method 8034, Hach Handbook of Wastewater Analysis, 1979, pages 2-113 and 2-117, Hach Chemical Company, Loveland, CO 80537.
\24\ Wershaw, R.L., et al, ``Methods for Analysis of Organic Substances in Water,'' Techniques of Water-Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A3, (1972 Revised
1987) p. 14.
\25\ Nitrogen, Nitrite, Method 8507, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.
\26\ Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH.
\27\ The approved method is cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition. The colorimetric reaction is conducted at a pH of 10.0
0.2. The approved methods are given on pp 576-81 of the 14th Edition: Method 510A for distillation, Method 510B for the manual colorimetric procedure, or Method 510C for the manual
spectrometric procedure.
\28\ R.F. Addition and R.G. Ackman, ``Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography,'' Journal of Chromatography, Vol. 47, No. 3, pp. 421-426, 1970.
\29\ Approved methods for the analysis of silver in industrial wastewaters at concentrations of 1 mg/L and above are inadequate where silver exists as an inorganic halide. Silver halides such
as the bromide and chloride are relatively insoluble in reagents such as nitric acid but are readily soluble in an aqueous buffer of sodium thiosulfate and sodium hydroxide to pH of 12.
Therefore, for levels of silver above 1 mg/L, 20 mL of sample should be diluted to 100 mL by adding 40 mL each of 2 M Na2S2O3 and NaOH. Standards should be prepared in the same manner. For
levels of silver below 1 mg/L the approved method is satisfactory.
\30\ The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 15th Edition.
\31\ EPA Methods 335.2 and 335.3 require the NaOH absorber solution final concentration to be adjusted to 0.25 N before colorimetric determination of total cyanide.
\32\ Stevens, H.H., Ficke, J.F., and Smoot, G.F., ``Water Temperature--Influential Factors, Field Measurement and Data Presentation,'' Techniques of Water-Resources Investigations of the U.S.
Geological Survey, Book 1, Chapter D1, 1975.
\33\ Zinc, Zincon Method, Method 8009, Hach Handbook of Water Analysis, 1979, pages 2-231 and 2-333, Hach Chemical Company, Loveland, CO 80537.
\34\ ``Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes, Method AES0029,'' 1986--Revised 1991, Thermo Jarrell Ash Corporation,
27 Forge Parkway, Franklin, MA 02038.
\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''.
\36\ ``Closed Vessel Microwave Digestion of Wastewater Samples for Determination of Metals'', CEM Corporation, P.O. Box 200, Matthews, NC 28106-0200, April 16, 1992. Available from the CEM
Corporation.
\37\ When determining boron and silica, only plastic, PTFE, or quartz laboratory ware may be used from start until completion of analysis.
\38\ Only use n-hexane extraction solvent when determining Oil and Grease parameters--Hexane Extractable Material (HEM), or Silica Gel Treated HEM (analogous to EPA Method 1664A). Use of other
extraction solvents is prohibited.
\39\ Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block Digestion, Steam Distillation, Titrimetric Detection), revised 12/22/94, OI Analytical/ALPKEM, PO Box 9010, College Station, TX 77842.
\40\ Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion, Steam Distillation, Colorimetric Detection), revised 12/22/94, OI Analytical/ALPKEM, PO Box 9010, College Station, TX 77842.
\41\ Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion, Automated FIA Gas Diffusion), revised 12/22/94, OI Analytical/ALPKEM, PO Box 9010, College Station, TX 77842.
\42\ Method 1664, Revision A ``n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM; Non-polar Material) by Extraction and
Gravimetry'' EPA-821-R-98-002, February 1999. Available at NTIS, PB-121949, U.S. Department of Commerce, 5285 Port Royal, Springfield, VA 22161.
\43\ USEPA. 2001. Method 1631, Revision E, ``Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Automic Fluorescence Spectrometry.'' September 2002, Office of Water, U.S.
Environmental Protection Agency (EPA-821-R-02-024). The application of clean techniques described in EPA's draft Method 1669: Sampling Ambient Water for Trace Metals at EPA Water Quality
Criteria Levels (EPA-821-R-96-011) are recommended to preclude contamination at low-level, trace metal determinations.
\44\ Available Cyanide, Method OIA-1677 (Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry), ALPKEM, A Division of OI Analytical, P.O. Box 9010, College Station, TX 77842-
9010.
\45\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Ammonia Plus Organic Nitrogen by a Kjeldahl Digestion Methods,'' Open File Report
(OFR) 00-170.
\46\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Chromium in Water by Graphite Furnace Atomic Absorption Spectrophotometry,'' Open
File Report (OFR) 93-449.
\47\ ``Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Molybdenum by Graphite Furnace Atomic Absorption Spectrophotometry,'' Open File
Report (OFR) 97-198.
\48\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Total Phosphorus by Kjeldahl Digestion Method and an Automated Colorimetric Finish
That Includes dialysis'' Open File Report (OFR) 92-146.
[[Page 18205]]
\49\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Arsenic and Selenium in Water and Sediment by Graphite Furnace--Atomic Absorption
Spectrometry'' Open File Report (OFR) 98-639.
\50\ ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Elements in Whole-water Digests Using Inductively Coupled Plasma-Optical Emission
Spectrometry and Inductively Coupled Plasma-Mass Spectrometry,'' Open File Report (OFR) 98-165.
\51\ Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory --Determination of Inorganic and Organic Constituents in Water and Fluvial Sediment,'' Open File Report
(OFR) 93-125.
\52\ All methods, excluding EPA Method 300.1, are published in ``Methods for the Determination of Metals in Environmental Samples,'' Supplement I, National Exposure Risk Laboratory-Cincinnati
(NERL-CI), EPA/600/R-94;11, May 1994; and ``Methods for the Determination of Inorganic Substances in Environmental Samples,'' NERL-CI, EPA/600/R-93/100, August, 1993. EPA Method 300.1 is
available from http://www.epa.gov/safewater/methods/met300.pdf.
\53\ AMCO-AEPA-1styrene divinyl beads and Hach StablCal are acceptable substitutes for formazin.
\54\ Method D6508, Rev. 2, ``Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and Chromate Electrolyte.'' available from
Waters Corp, 34 Maple St., Milford, MA, 01y757, 508/482-2131 (Office), 508/482-3625 (FAX).
\55\ Kelada-01, ``Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, and Thiocyanate,'' EPA 821-B-91-009 National Technical Information Service (NTIS), 5285 Port Royal
Road, Springfield, VA 22161 [Order Number PB 2001-108275]. Phone: 800-553-6847.
\56\ QuikChem Method 10-204-00-1-X, ``Digestion and Distillation of Total Cyanide in Drinking and Wastewaters using MICRO DIST and Determination of Cyanide by Flow Injection Analysis'' is
available from Lachat Instruments 6645 W. Mill Rd., Milwaukee, WI 53218, USA. Phone: 414-358-4200.
\57\ When using sulfide removal test procedures described in Method 335.4 reconstitute particulate that is filtered with the sample prior to distillation.
\58\ Unless otherwise stated, if the language of this table specifies a sample digestion and/or distillation ``followed by'' analysis with a method, approved digestion and/or distillation are
required prior to analysis.
\59\ Method 245.7, ``Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry'' [December 2003] (EPA-821-D-03-001).
[[Page 18206]]
Table 1C.--List of Approved Test Procedures for Non-Pesticide Organic Compounds
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
EPA method number,\2 7\ Other Approved Methods
--------------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter \1\ Standard methods
GC GC/MS HPLC [edition(s)] Standard methods on-line ASTM Other
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acenaphthene.................. 610 625, 1625B........... 610 6440 B [18th, 19th, ........................ D4657-92(99)............ Note 9, p. 27.
20th].
2. Acenaphthylene................ 610 625, 1625B........... 610 6440 B, 6410 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
3. Acrolein...................... 603 \4\ 624, 1624B.......
4. Acrylonitrile................. 603 \4\ 624, 1624B.......
5. Anthracene.................... 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
6. Benzene....................... 602 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97.........
[18th, 19th], 6200 C
[20th] and 6220 B
[18th, 19th].
7. Benzidine..................... .............. \5\ 625, 1625B....... 605 ........................ ........................ ........................ Note 3, p. 1.
8. Benzo(a)anthracene............ 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
9. Benzo(a)pyrene................ 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
10. Benzo(b)fluoranthene......... 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
11. Benzo(g,h,i)perylene......... 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
12. Benzo(k)fluoranthene......... 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
13. Benzyl chloride.............. .............. ..................... .............. ........................ ........................ ........................ Note 3, p. 130: Note 6,
p. S102.
14. Benzyl butyl phthalate....... 606 625, 1625 B.......... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
15. Bis(2-chloroethoxy) methane.. 611 625, 1625 B.......... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
16. Bis(2-chloroethoxy) ether.... 611 625, 1625 B.......... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
17. Bis(2-ethylhexyl) phthalate.. 606 625, 1625 B.......... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
18. Bromodichloro-methane)....... 601 624, 1624 B.......... .............. 6200 C [20th, and 6230 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 B
[20th] and 6210 B
[18th, 19th].
19. Bromoform.................... 601 624, 1624 B.......... .............. 6200 C [20th] and 6230 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 B
[20th] and 6210 B
[18th, 19th].
20. Bromomethane................. 601 624, 1624 B.......... .............. 6200 C [20th] and 6230 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 B
[20th] and 6210 B
[18th, 19th].
21. 4-Bromophenylphenyl ether.... 611 625, 1625 B.......... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
22. Carbon tetrachloride......... 601 624, 1624 B.......... .............. 6200 C [20th] and 6230 B ........................ ........................ Note 3, p. 130.
[18th, 19th].
23. 4-Chloro-3-methylphenol...... 604 625, 1625 B.......... .............. 6410 B, 6420 B [18th, 6410 B-00, 6420 B-00.... ........................ Note 9, p. 27.
19th, 20th].
24. Chlorobenzene................ 601, 602 624, 1624 B.......... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ Note 3, p. 130.
[18th, 19th], 6200 C
[20th] and 6220 B
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
25. Chloroethane................. 601 624, 1624B........... .............. 6200 B [20TH] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th] 6200 C
[20th] and 6230 B
[18th, 19th].
26. 2-Chloroethylvinylether...... 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
[[Page 18207]]
27. Chloroform................... 601 624, 1624B........... .............. 6200 B[20th] and 6210 B 6200 B and C-97......... ........................ Note 3, p. 130.
[18th, 19th]. 6200 C
[20th] and 6230 B.
28. Chloromethane................ 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th] 6200 C
[20th] and 6230 B
[18th, 19th].
29. 2-Chloronaphthalene.......... 612 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
30. 2-Chlorophenol............... 604 625, 1625B........... .............. 6410 B, 6420 B [18th, 6410-B-00,.............. ........................ Note 9, p. 27.
19th, 20th]. 6420 B-00...............
31. 4-Chlorophenylphenylether.... 611 625, 1625B........... 6410 B [18th, 6410 B-00............... ........................ Note 9, p. 27...........
19th, 20th]
32. Chrysene..................... 610 625, 1625B........... 610 6410 B, 6440............ 6410 B-00............... 4657-92(99)............. Note 9, p. 27.
B [18th, 19th, 20th]....
33. Dibenzo(a,h)anth-racene...... 610 625, 1625B........... 610 6410 B, 6440............ 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
B [18th, 19th, 20th]....
34. Dibromochloro-methane........ 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th] 6200 C
[20th] and 6230 B
[18th, 19th].
35. 1,2-Dichlorobenzene.......... 601, 602 624, 1625B........... .............. 6200 C [20th] and 6220 B 6200 B and C-97......... ........................ Note 9, p27
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
36. 1,3-Dichlorobenzene.......... 601, 602 624, 1625B........... .............. 6200C [20th] and 6220B 6200B and C-97.......... ........................ Note 9, p. 27
(18th, 19th], 6200C
[20th] and 6230B [18th,
19th].
37. 1,4-Dichlorobenzene.......... 601, 602 624, 1625B........... .............. 6200C [20th] and 6220B 6200B and C-97.......... ........................ Note 9, p. 27
[18th, 19th], 6200C
[20th] and 6230B [18th,
19th].
38. 3,3-Dichlorobenzidine........ .............. 625, 1625B........... 605 6410B [18th, 19th, 20th] 6410B-00................ ........................ ........................
39. Dichlorodifluoro-methane..... 601 ..................... .............. 6200C [20th] and 6230B 6200 C-97............... ........................ ........................
[18th, 19th].
40. 1,1-Dichloroethane........... 601 624, 1624B........... .............. 6200B [20th] and 6210B 6200B and C-97.......... ........................ ........................
[18th, 19th], 6200C
[20th] and 6230B [18th,
19th].
41. 1,2-Dichloroethane........... 601 624, 1624B........... .............. 6200B [20th] and 6210B 6200B and C-97.......... ........................ ........................
[18th, 19th], 6200C
[20th] and 6230B [18th,
19th].
42. 1,1-Dichloroethene........... 601 624, 1624B........... .............. 6200B [20th] and 6210B 6200B and C-97.......... ........................ ........................
[18th, 19th], 6200C
[20th] and 6230B [18th,
19th].
43. trans-1,2-Dichloroethene..... 601 624, 1624B........... .............. 6200B [20th] and 6210B 6200B and C-97.......... ........................ ........................
[18th, 19th], 6200C
[20th] and 6230B [18th,
19th].
44. 2,4-Dichlorophenol........... 604 625, 1625B........... .............. 6410B, 6420B [18th, 6410B-00, 6420B-00...... ........................ Note 9, p. 27
19th, 20th].
45. 1,2-Dichloropropane.......... 601 624, 1624B........... .............. 6200 B [20th] and 6010 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
[[Page 18208]]
46. cis-1,3-Dichloropropene...... 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
47. trans-1,3-Dichloropropene.... 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
48. Diethyl phthalate............ 606 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27
20th].
49. 2,4-Dimethylphenol........... 604 625, 1625B........... .............. 6410 B, 6420 B [18th, 6410 B-00, 6420 B-00.... ........................ Note 9, p. 27
19th, 20th].
50. Dimethyl phthalate........... 606 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27
20th].
51. Di-n-butyl phthalate......... 606 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27
20th].
52. Di-n-octyl phthalate......... 606 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27
20th].
53. 2,3-Dinitrophenol............ 604 625, 1625B........... .............. 6410 B, 6420 B [18th, 6410 B-00, 6420 B-00.... ........................ ........................
19th, 20th].
54. 2,4-Dinitrotoluene........... 609 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27
20th].
55. 2,6-Dinitrotoluene........... 609 625, 1625B........... .............. 6410 B [16th, 19th, 6410 B-00............... ........................ Note 9, p. 27
20th].
56. Epichlorohydrin.............. .............. ..................... .............. ........................ ........................ ........................ Note 3, p. 130; Note 6,
p. S102.
57. Ethylbenzene................. 602 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 C
[20th] and 6220 B
[18th, 19th].
58. Fluoranthene................. 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657--92(99)........... Note 9, p. 27
19th, 20th].
59. Fluorene..................... 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657--92(99)........... Note 9, p. 27
19th, 20th].
60. 1,2,3,4,5,6,7-Heptachlorodi- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
benzofuran.
61. 1,2,3,4,7,8,9-Heptachlorodi- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
benzofuran.
62. 1,2,3,4,6,7,8- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
Heptachlorodibenzo-p-dioxin.
63. Hexachlorobenzene............ 612 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
64. Hexachlorobutadiene.......... 612 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
65. Hexachlorocyclopentadiene.... 612 625,\5\ 1625B........ .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
66. 1,2,3,4,7,8- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
Hexachlorodibenzofuran.
67. 1,2,3,6,7,8- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
Hexachlorodibenzofuran.
68. 1,2,3,7,8,9- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
Hexachlorodibenzofuran.
69. 2,3,4,6,7,8- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
Hexachlorodibenzofuran.
70. 1,2,3,4,7,8-Hexachlorodibenzo- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
p-dioxin.
71. 1,2,3,6,7,8-Hexachlorodibenzo- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
p-dioxin.
72. 1,2,3,7,8,9-Hexachlorodibenzo- .............. 1613B \10\........... .............. ........................ ........................ ........................ ........................
p-dioxin.
73. Hexachloroethane............. 612 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
74. Ideno(1,2,3-cd) pyrene....... 610 625, 1625B........... 610 6410 B, 6440 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
75. Isophorone................... 609 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
[[Page 18209]]
76. Methylene chloride........... 601 624, 1624B........... .............. 6200 C [20th] and 6230 B 6200 C-97............... ........................ Note 3, p. 130
[18th, 19th].
77. 2-Methyl-4,6-dinitrophenol... 604 625, 1625B........... .............. 6420 B, 6410 B [18th, 6410 B-00, 6420 B-00.... ........................ Note 9, p. 27.
19th, 20th].
78. Naphthalene.................. 610 625, 1625B........... 610 6440 B, 6410 B [18th, 6410 B-00............... ........................ Note 9, p. 27.
19th, 20th].
79. Nitrobenzene................. 609 625, 1625B........... .............. 6410 B [18th, 19th, 6410B-00................ D4657-92(99)............ Note 9, p. 27.
20th].
80. 2-Nitrophenol................ 604 625, 1625B........... .............. 6410 B, 6420 B [18th, 64310 B-00, 64320 B-00.. ........................ Note 9, p. 27.
19th, 20th].
81. 4-Nitrophenol................ 604 625, 1625B........... .............. 6410 B, 6420 B [18th, 6410 B-00, 6420 B-00.... ........................ Note 9, p. 27.
19th, 20th].
82. N-Nitrosodimethylamine....... 607 625,\5\ 1625B........ .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
83. N-Nitrosodi-n-propylamine.... 607 625,\5\ 1625B........ .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
84. N-Nitrosodiphenylamine....... 607 625,\5\ 1625B........ .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 9, p. 27.
20th].
85. Octachlorodibenzofuran....... .............. 1613B \10\...........
86. Octachlorodibenzo-p-dioxin... .............. \10\1613B............
87. 2,2'-Oxybis(2-chloropropane) 611 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00...............
[also known as bis(2- 20th].
chloroisopropyl) ether].
88. PCB-1016..................... 608 625.................. .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 3, p. 43.
20th].
89. PCB-1221..................... 608 625.................. .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 3, p. 43.
20th].
90. PCB-1232..................... 608 625.................. .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 3, p. 43.
20th].
91. PCB-1242..................... 608 625.................. .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 3, p. 43.
20th].
92. PCB-1248..................... 608 625..................
93. PCB-1254..................... 608 625.................. .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 3, p. 43.
20th].
94. PCB-1260..................... 608 625.................. .............. 6410 B, 6630 B [18th, 6410 B-00............... ........................ Note 3, p. 43.
19th, 20th].
95. 1,2,3,7,8- .............. 1613B \10\...........
Pentachlorodibenzofuran.
96. 2,3,4,7,8- .............. 1613B \10\...........
Pentachlorodibenzofuran.
97. 1,2,3,7,8,-Pentachlorodibenzo- .............. 1613B \10\...........
p-dioxin.
98. Pentachlorophenol............ 604 625, 1625B........... .............. 6410 B, 6630 B [18th, 6410 B-00............... ........................ Note 3, p. 140;
19th, 20]. Note 9, p. 27.
99. Phenanthrene................. 610 625, 1625B........... 610 6410 B 6440 B [18th, 6410 B-00............... D4657-92 (99)........... Note 9, p. 27.
19th, 20th].
100. Phenol...................... 604 625, 1625B........... .............. 6420 B, 6410 B [18th, 6410 B-00............... ........................ Note 9, p. 27.
19th, 20th]. 6420 B-00...............
101. Pyrene...................... 610 625, 1625B........... 610 6440 B, 6410 B [18th, 6410 B-00............... D4657-92(99)............ Note 9, p. 27.
19th, 20th].
102. 2,3,7,8- .............. 1613B \10\...........
Tetrachlorodibenzofuran.
103. 2,3,7,8-Tetrachlorodibenzo-p- .............. 613, 625,\5a\ 1613B
dioxin. \10\.
104. 1,1,2,2-Tetrachloroethane... 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ Note 3, p. 130
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
105. Tetrachloroethene........... 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ Note 3, p. 130
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
106. Toluene..................... 602 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97.........
[18th, 19th], 6200 C
[20th] and 6220 B
[18th, 19th].
107. 1,2,4-Trichlorobenzene...... 612 625, 1625B........... .............. 6410 B [18th, 19th, 6410 B-00............... ........................ Note 3, p. 130;
20th]. Note 9, p.27
[[Page 18210]]
108. 1,1,1-Trichloroethane....... 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97.........
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
109. 1,1,2-Trichloroethane....... 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ Note 3, p. 130
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
110. Trichloroethene............. 601 624, 1624B........... .............. 6200 B [20th] and 6210 B 6200 B and C-97.........
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
111. Trichlorofluoromethane...... 601 624.................. .............. 6200 B [20th] and 6210 B 6200 B and C-97......... ........................ ........................
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
112. 2,4,6-Trichlorophenol....... 604 625, 1625 B.......... .............. 6420 B, 6410 B [18th, 6410 B-00, 6420 B-00.... ........................ Note 9, p. 27
19th, 20th].
113. Vinyl chloride.............. 601 624, 1624 B.......... .............. 6200 B [20th] and 6210 B 6200B and C-97.......... ........................ ........................
[18th, 19th], 6200 C
[20th] and 6230 B
[18th, 19th].
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Table IC notes
\1\ All parameters are expressed in micrograms per liter ([mu]g/L) except for Method 1613B in which the parameters are expressed in picograms per liter (pg/L).
\2\ The full text of Methods 601-613, 624, 625, 1624B, and 1625B, are given at Appendix A, ``Test Procedures for Analysis of Organic Pollutants,'' of this part 136. The full text of Method
1613B is incorporated by reference into this part 136 and is available from the National Technical Information Services as stock number PB95-104774. 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.
\4\ Method 624 may be extended to screen samples for Acrolein and Acrylonitrile. However, when they are known to be present, the preferred method for these two compounds is Method 603 or
Method 1624B.
\5\ Method 625 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, and N-nitrosodiphenylamine. However, when they are known to be present, Methods 605,
607, and 612, or Method 1625B, are preferred methods for these compounds.
\5a\ 625, Screening only.
\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 601-603, 624, 625, 1624B, and 1625B (See Appendix A of
this part 136) in accordance with procedures each in Section 8.2 of each of these Methods. Additionally, each laboratory, on an on-going basis must spike and analyze 10% (5% for Methods 624
and 625 and 100% for methods 1624B and 1625B) 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. The results should be reported, but cannot be used 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 Empore TM Disk'' 3M Corporation Revised 10/28/94.
\9\ USGS Method 0-3116-87 from ``Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory--Determination of Inorganic and Organic Constituents in Water and Fluvial
Sediments'' U.S. Geological Survey, Open File Report 93-125.
\10\ Analysts may use Fluid Management Systems, Inc. PowerPrep system in place of manual cleanup provided that analysts meet the requirements of Method 1613B (as specified in Section 9 of the
method) and permitting authorities.
Table 1D.--List of Approved Test Procedures for Pesticides \1\
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Standard methods 18th,
Parameter Method EPA \2,7\ 19th, 20th Ed. Standard methods on-line ASTM Other
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1. Aldrin........................ GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
2. Ametryn....................... GC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68.
3. Aminocarb..................... TLC ........... ........................ ........................ ........................ Note 3, p. 94; Note 6, p. S16.
4. Atraton....................... GC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68.
5. Atrazine...................... GC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68; Note 9.
6. Azinphos methyl............... GC ........... ........................ ........................ ........................ Note 3, p. 25; Note 6, p. S51.
7. Barban........................ TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
8. [alpha]-BHC................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 8.
D5812-96(02)
GC/MS \5\ 625 6410 B
9. [beta]-BHC.................... GC 608 6630 C ........................ D3086-90, Note 8.
D5812-96(02)
GC/MS \5\ 625 6410 B 6410 B-00
10. [delta]-BHC.................. GC 608 6630 C ........................ D3086-90, Note 8.
D5812-96(02)
GC/MS \5\ 625 6410 B 6410 B-00
11. [gamma]-BHC (Lindane)........ GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
[[Page 18211]]
12. Captan....................... GC ........... 6630 B ........................ D3086-90, Note 3, p. 7.
D5812-96(02)
13. Carbaryl..................... TLC ........... ........................ ........................ ........................ Note 3, p. 94, Note 6, p. S60.
14. Carbo-phenothion............. GC ........... ........................ ........................ ........................ Note 4, p. 27; Note 6, p. S73.
15. Chlordane.................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
16. Chloro-propham............... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
17. 2,4-D........................ GC ........... 6640 B ........................ ........................ Note 3, p. 115; Note 4, p. 40.
18. 4,4,-DDD..................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
19. 4,4,-DDE..................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
20. 4,4,-DDT..................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
21. Demeton-O.................... GC ........... ........................ ........................ ........................ Note 3, p. 25; Note 6, p. S51.
22. Demeton-S.................... GC ........... ........................ ........................ ........................ Note 3, p. 25; Note 6, p. S51.
23. Diazinon..................... GC ........... ........................ ........................ ........................ Note 3, p. 25; Note 4, p. 27; Note 6, p.
S51.
24. Dicamba...................... GC ........... ........................ ........................ ........................ Note 3, p. 115.
25. Dichlofenthion............... GC ........... ........................ ........................ ........................ Note 4, p. 27; Note 6, p. S73.
26. Dichloran.................... GC ........... 6630 B & C ........................ ........................ Note 3, p. 7.
27. Dicofol...................... GC ........... ........................ ........................ D3086-90,
D5812-96(02)
28. Dieldrin..................... GC 608 6630 B & C ........................ ........................ Note 3, p. 7; Note 4, p. 27; Note 8.
GC/MS 625 6410 B 6410 B-00
29. Dioxathion................... GC ........... ........................ ........................ ........................ Note 4, p. 27; Note 6, p. S73.
30. Disulfoton................... GC ........... ........................ ........................ ........................ Note 3, p. 25; Note 6 p. S51.
31. Diuron....................... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
32. Endosulfan I................. GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS \5\ 625 6410 B 6410 B-00
33. Endosulfan II................ GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 8.
D5812-96(02)
GC/MS \5\ 625 6410 B 6410 B-00
34. Endosulfan Sulfate........... GC 608 6630 C ........................ ........................ Note 8.
GC/MS 625 6410 B 6410 B-00
35. Endrin....................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS \5\ 625 6410 B 6410 B-00
36. Endrin aldehyde.............. GC 608 ........................ ........................ ........................ Note 8.
GC/MS 625
37. Ethion....................... GC ........... ........................ ........................ ........................ Note 4, p. 27; Note 6, p. S73.
38. Fenuron...................... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
39. Fenuron-TCA.................. TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
40. Heptachlor................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
41. Heptachlor epoxide........... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 6, p. S73;
D5812-96(02) Note 8.
GC/MS 625 6410 B 6410 B-00
42. Isodrin...................... GC ........... ........................ ........................ ........................ Note 4, p. 27; Note 6, p. S73.
43. Linuron...................... GC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
44. Malathion.................... GC ........... 6630 C ........................ ........................ Note 3, p. 25; Note 4, p. 27; Note 6, p.
S51.
45. Methiocarb................... TLC ........... ........................ ........................ ........................ Note 3, p. 94; Note 6, p. S60.
46. Methoxychlor................. GC ........... 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
47. Mexacarbate.................. TLC ........... ........................ ........................ ........................ Note 3, p. 94; Note 6, p. S60.
48. Mirex........................ GC ........... 6630 B & C ........................ ........................ Note 3, p. 7; Note 4, p. 27.
49. Monuron...................... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
50. Monuron-TCA.................. TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
51. Nuburon...................... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
52. Parathion methyl............. GC ........... 6630 C ........................ ........................ Note 3, p. 25; Note 4, p. 27.
53. Parathion ethyl.............. GC ........... 6630 C ........................ ........................ Note 3, p. 25; Note 4, p. 27.
54. PCNB......................... GC ........... 6630 B & C ........................ ........................ Note 3, p. 7.
55. Perthane..................... GC ........... ........................ ........................ D3086-90, Note 4, p. 27.
D5812-96(02)
56. Prometron.................... GC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68; Note 9.
57. Prometryn.................... GC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68; Note 9.
58. Propazine.................... GC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68; Note 9.
59. Propham...................... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
60. Propoxur..................... TLC ........... ........................ ........................ ........................ Note 3, p. 94; Note 6, p. S60.
61. Secbumeton................... TLC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68.
62. Siduron...................... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
63. Simazine..................... GC ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68; Note 9.
64. Strobane..................... GC ........... 6630 B & C ........................ ........................ Note 3, p. 7.
65. Swep......................... TLC ........... ........................ ........................ ........................ Note 3, p. 104; Note 6, p. S64.
[[Page 18212]]
66. 2,4,5-T...................... GC ........... 6640 B ........................ ........................ Note 3, p. 115; Note 4, p. 40.
67. 2,4,5-TP (Silvex)............ GC ........... 6640 B ........................ ........................ Note 3, p. 115; Note 4, p. 40.
68. Terbuthylazine GC............ .................... ........... ........................ ........................ ........................ Note 3, p. 83; Note 6, p. S68.
69. Toxaphene.................... GC 608 6630 B & C ........................ D3086-90, Note 3, p. 7; Note 4, p. 27; Note 8.
D5812-96(02)
GC/MS 625 6410 B 6410 B-00
70. Trifluralin.................. GC ........... 6630 B ........................ ........................ Note 3, p. 7; Note 9.
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Table ID notes:
\1\ Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides may be found under Table 1C, 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 [alpha]-BHC, [gamma]-BHC, endosulfan I, endosulfan II, and endrin. However, when they are known to exist, Method 608 is the preferred method.
\6\ ``Selected Analytical Methods Approved and Cited by the U.S. 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. The results should be reported, but cannot be used 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.
\9\ USGS Method 0-3106-93 from ``Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Triazine and Other Nitrogen-containing Compounds by Gas
Chromatography with Nitrogen Phosphorus Detectors'' U.S. Geological Survey Open File Report 94-37.
Table 1E.--List of Approved Radiologic Test Procedures
--------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method number or page)
---------------------------------------------------------------------------------------------
Parameter and units Method Standard methods
EPA \1\ 18th, 19th, 20th Standard methods ASTM USGS \2\
ed. on-line
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Alpha-Total, pCi per Proportional or 900.0........... 7110 B.......... 7110 B-00....... D1943-90, 96.... pp. 75 and 78\3\.
liter. scintillation counter.
2. Alpha-Counting error, pCi Proportional or Appendix B...... 7110 B.......... 7110 B-00....... D1943-90, 96.... p. 79.
per liter. scintillation counter.
3. Beta-Total, pCi per liter Proportional counter........ 900.0........... 7110 B.......... 7110 B-00....... D1890-90, 96.... pp. 75 and 78\3\.
4. Beta-Counting error, pCi. Proportional counter........ Appendix B...... 7110 B.......... 7110 B-00....... D1890-90, 96.... p. 79.
5. (a) Radium Total pCi per Proportional counter........ 903.0........... 7500Ra B........ 7500-Ra B-01.... D2460-90, 97.... ....................
liter.
(b) Ra, pCi per liter....... Scintillation counter....... 903.1........... 7500RaC......... 7500-RA C-01.... D3454-91, 97.... p. 81.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table 1E notes:
\1\ ``Prescribed Procedures for Measurement of Radioactivity in Drinking Water,'' EPA-600/4-80-032 (1980), U.S. Environmental Protection Agency, August
1980.
\2\ Fishman, M.J. and Brown, Eugene, ``Selected Methods of the U.S. Geological Survey of Analysis of Wastewaters,'' U.S. Geological Survey, Open-File
Report 76-177 (1976).
\3\ The method found on p. 75 measures only the dissolved portion while the method on p. 78 measures only the suspended portion. Therefore, the two
results must be added to obtain the ``total''.
* * * * *
Table IG.--Test Methods for Pesticide Active Ingredients (40 CFR Part 455)
----------------------------------------------------------------------------------------------------------------
EPA survey code Pesticide name CAS No. EPA analytical method No.(s)
----------------------------------------------------------------------------------------------------------------
8.................................. Triadimefon................ 43121-43-3 507/633/525.1/1656
12................................. Dichlorvos................. 00062-73-7 1657/507/622/525.1
16................................. 2,4-D; 2,4-D Salts and 00094-75-7 1658/515.1/615/515.2/555
Esters [2,4-
Dichlorophenoxyacetic
acid].
17................................. 2,4-DB; 2,4-DB Salts and 00094-82-6 1658/515.1/615/515.2/555
Esters [2,4-
Dichlorophenoxybutyric
acid].
22................................. Mevinphos.................. 07786-34-7 1657/507/622/525.1
25................................. Cyanazine.................. 21725-46-2 629/507
26................................. Propachlor................. 01918-16-7 1656/508/608.1/525.1
27................................. MCPA; MCPA Salts and Esters 00094-74-6 1658/615/555
[2-Methyl-4-
chlorophenoxyacetic acid].
30................................. Dichlorprop; Dichlorprop 00120-36-5 1658/515.1/615/515.2/555
Salts and Esters [2-(2,4-
Dichlorophenoxy) propionic
acid].
31................................. MCPP; MCPP Salts and Esters 00093-65-2 1658/615/555
[2-(2-Methyl-4-
chlorophenoxy) propionic
acid].
35................................. TCMTB [2- 21564-17-0 637
(Thiocyanomethylthio)
benzothiazole].
39................................. Pronamide.................. 23950-58-5 525.1/507/633.1
41................................. Propanil................... 00709-98-8 632.1/1656
45................................. Metribuzin................. 21087-64-9 507/633/525.1/1656
52................................. Acephate................... 30560-19-1 1656/1657
[[Page 18213]]
53................................. Acifluorfen................ 50594-66-6 515.1/515.2/555
54................................. Alachlor................... 15972-60-8 505/507/645/525.1/1656
55................................. Aldicarb................... 00116-06-3 531.1
58................................. Ametryn.................... 00834-12-8 507/619/525.1
60................................. Atrazine................... 01912-24-9 505/507/619/525.1/1656
62................................. Benomyl.................... 17804-35-2 631
68................................. Bromacil; Bromacil Salts 00314-40-9 507/633/525.1/1656
and Esters.
69................................. Bromoxynil................. 01689-84-5 1625/1661
69................................. Bromoxynil octanoate....... 01689-99-2 1656
70................................. Butachlor.................. 23184-66-9 507/645/525.1/1656
73................................. Captafol................... 02425-06-1 1656
75................................. Carbaryl [Sevin]........... 00063-25-2 531.1/632/553
76................................. Carbofuran................. 01563-66-2 531.1/632
80................................. Chloroneb.................. 02675-77-6 1656/508/608.1/525.1
82................................. Chlorothalonil............. 01897-45-6 508/608.2/525.1/1656
84................................. Stirofos................... 00961-11-5 1657/507/622/525.1
86................................. Chlorpyrifos............... 02921-88-2 1657/508/622
90................................. Fenvalerate................ 51630-58-1 1660
103................................ Diazinon................... 00333-41-5 1657/507/614/622/525.1
107................................ Parathion methyl........... 00298-00-0 1657/614/622
110................................ DCPA [Dimethyl 2,3,5,6- 01861-32-1 508/608.2/525.1/515.1/515.2/
tetrachloroterephthalate]. 1656
112................................ Dinoseb.................... 00088-85-7 1658/515.1/615/515.2/555
113................................ Dioxathion................. 00078-34-2 1657/614.1
118................................ Nabonate [Disodium 00138-93-2 630.1
cyanodithioimidocarbonate].
119................................ Diuron..................... 00330-54-1 632/553
123................................ Endothall.................. 00145-73-3 548/548.1
124................................ Endrin..................... 00072-20-8 1656/505/508/608/617/525.1
125................................ Ethalfluralin.............. 55283-68-6 \1\ 1656/ \1\ 627
126................................ Ethion..................... 00563-12-2 1657/614/614.1
127................................ Ethoprop................... 13194-48-4 1657/507/622/525.1
132................................ Fenarimol.................. 60168-88-9 507/633.1/525.1/1656
133................................ Fenthion................... 00055-38-9 1657/622
138................................ Glyphosate [N- 01071-83-6 547
(Phossphonomethyl)
glycine].
140................................ Heptachlor................. 00076-44-8 1656/505/508/608/617/525.1
144................................ Isopropalin................ 33820-53-0 1656/627
148................................ Linuron.................... 00330-55-2 553/632
150................................ Malathion.................. 00121-75-5 1657/614
154................................ Methamidophos.............. 10265-92-6 1657
156................................ Methomyl................... 16752-77-5 531.1/632
158................................ Methoxychlor............... 00072-43-5 1656/505/508/608.2/617/525.1
172................................ Nabam...................... 00142-59-6 630/630.1
173................................ Naled...................... 00300-76-5 1657/622
175................................ Norflurazon................ 27314-13-2 507/645/525.1/1656
178................................ Benfluralin................ 01861-40-1 \1\ 1656/ \1\ 627
182................................ Fensulfothion.............. 00115-90-2 1657/622
183................................ Disulfoton................. 00298-04-4 1657/507/614/622/525.1
185................................ Phosmet.................... 00732-11-6 1657/622.1
186................................ Azinphos Methyl............ 00086-50-0 1657/614/622
192................................ Organo-tin pesticides...... 12379-54-3 Ind-01/200.7/200.9
197................................ Bolstar.................... 35400-43-2 1657/622
203................................ Parathion.................. 00056-38-2 1657/614
204................................ Pendimethalin.............. 40487-42-1 1656
205................................ Pentachloronitrobenzene.... 00082-68-8 1656/608.1/617
206................................ Pentachlorophenol.......... 00087-86-5 625/1625/515.2/555/515.1/525.1
208................................ Permethrin................. 52645-53-1 608.2/508/525.1/1656/1660
212................................ Phorate.................... 00298-02-2 1657/622
218................................ Busan 85 [Potassium 00128-03-0 630/630.1
dimethyldithiocarbamate].
219................................ Busan 40 [Potassium N- 51026-28-9 630/630.1
hydroxymethyl-N-
methyldithiocarbamate].
220................................ KN Methyl [Potassium N- 00137-41-7 630/630.1
methyldithiocarbamate].
223................................ Prometon................... 01610-18-0 507/619/525.1
224................................ Prometryn.................. 07287-19-6 507/619/525.1
226................................ Propazine.................. 00139-40-2 507/619/525.1/1656
230................................ Pyrethrin I................ 00121-21-1 1660
232................................ Pyrethrin II............... 00121-29-9 1660
236................................ DEF [S,S,S-Tributyl 00078-48-8 1657
phosphorotrithioate].
239................................ Simazine................... 00122-34-9 505/507/619/525.1/1656
241................................ Carbam-S [Sodium 00128-04-1 630/630.1
dimethyldithiocarbanate].
243................................ Vapam [Sodium 00137-42-8 630/630.1
methyldithiocarbamate].
252................................ Tebuthiuron................ 34014-18-1 507/525.1
254................................ Terbacil................... 05902-51-2 507/633/525.1/1656
255................................ Terbufos................... 13071-79-9 1657/507/614.1/525.1
256................................ Terbuthylazine............. 05915-41-3 619/1656
257................................ Terbutryn.................. 00886-50-0 507/619/525.1
259................................ Dazomet.................... 00533-74-4 630/630.1/1659
262................................ Toxaphene.................. 08001-35-2 1656/505/508/608/617/525.1
263................................ Merphos [Tributyl 00150-50-5 1657/507/525.1/622
phosphorotrithioate].
264................................ Trifluralin................ 01582-09-8 1656/508/617/627/525.1
268................................ Ziram [Zinc 00137-30-4 630/630.1
dimethyldithiocarbamate].
----------------------------------------------------------------------------------------------------------------
\1\ Monitor and report as total Trifluralin.
[[Page 18214]]
(b) * * *
REFERENCES, SOURCES, COSTS, AND TABLE CITATIONS:
* * * * *
(6) American Public Health Association. 1992, 1995, and 1998.
Standard Methods for the Examination of Water and Wastewater. 18th,
19th, and 20th Edition (respectively). Available from: American Public
Health Association, 1015 15th Street, NW., Washington, DC 20005.
Standard Methods On-Line are available through the Standard Methods Web
site (www.standardmethods.org). Tables IA, IB, IC, ID, IE.
* * * * *
(10) ASTM International. Annual Book of ASTM Standards, Water, and
Environmental Technology, Section 11, Volumes 11.01 and 11.02, 1994,
1996, 1999, Volume 11.02, 2000, and individual standards published
after 2000. Available from: ASTM International, 100 Barr Harbor Drive,
P.O. Box C700, West Conshohocken, PA 19428-2959, or www.astm.org.
Tables IA, IB, IC, ID, and IE.
* * * * *
(17) AOAC--International. Official Methods of Analysis of AOAC--
International, 16th Edition, (1995). Available from: AOAC--
International, 481 North Frederick Avenue, Suite 500, Gaithersburg, MD
20877. Table 1B, Note 3.
* * * * *
(63) Waters Corporation. Method D6508, Rev. 2, ``Test Method for
Determination of Dissolved Inorganic Anions in Aqueous Matrices Using
Capillary Ion Electrophoresis and Chromate Electrolyte,'' available
from Waters Corp, 34 Maple St., Milford, MA 01757, 508/482-2131
(Office), 508/482-3625 (FAX). Table IB, Note 54.
(64) Kelada-01, ``Kelada Automated Test Methods for Total Cyanide,
Acid Dissociable Cyanide, and Thiocyanate,'' EPA 821-B-01-009 is
available from National Technical Information Service (NTIS), 5285 Port
Royal Road, Springfield, VA 22161 [Order Number PB 2001-108275]. Phone:
800-553-6847. Table IB, Note 55.
(65) QuikChem Method 10-204-00-1-X, ``Digestion and Distillation of
Total Cyanide in Drinking and Wastewaters Using MICRO DIST and
Determination of Cyanide by Flow Injection Analysis'' is available from
Lachat Instruments, 6645 W. Mill Rd., Milwaukee, WI 53218, USA. Phone:
414-358-4200. Table IB, Note 56.
(66) ``Methods for the Determination of Metals in Environmental
Samples,'' Supplement I, National Exposure Risk Laboratory--Cincinnati
(NERL-CI), EPA/600/R-94/11, May 1994; and ``Methods for the
Determination of Inorganic Substances in Environmental Samples,'' NERL-
CI, EPA/600/R-93/100, August 1993 are available from National Technical
Information Service (NTIS), 5285 Port Royal Road, Springfield, VA
22161. Phone: 800-553-6847. Table IB.
(67) ``Determination of Inorganic Ions in Drinking Water by Ion
Chromatography,'' Rev. 1.0, 1997 is available from from http://www.epa.gov/safetwater/methods/met300.pdf. Table IB.
(68) Table IG Methods are available in ``Methods for the
Determination of Nonconventional Pesticides in Municipal and Industrial
Wastewater, Volume I,'' EPA 821-R-93-010A (August 1993, Revision I) and
``Methods for the Determination of Nonconventional Pesticides in
Municipal and Industrial Wastewater, Volume I,'' EPA 821-R-93-010B
(August 1993) are available from National Technical Information Service
(NTIS), 5285 Port Royal Road, Springfield, VA 22161. Phone: 800-553-
6847. Table IB.
(69) ``Mercury in Water by Cold Vapor Atomic Fluorescence
Spectrometry'' [December 2003]. Available at http://www.epa.gov/waterscience/methods/.
* * * * *
(c) Under certain circumstances, the Regional Administrator or the
Director in the Region or State where the discharge will occur may
determine for a particular discharge that additional parameters or
pollutants must be reported. Under such circumstances, additional test
procedures for analysis of pollutants may be specified by the Regional
Administrator, or the Director upon recommendation of the Alternate
Test Procedure Program Coordinator, Washington, DC.
(d) Under certain circumstances, the Administrator may approve,
upon recommendation by the Alternate Test Procedure Program
Coordinator, Washington, DC, additional alternate test procedures for
nationwide use.
(e) Sample preservation procedures, container materials, and
maximum allowable holding times for parameters are cited in Tables IA,
IB, IC, ID, IE, IF, and IG are prescribed in Table II. Information in
the table takes precedence over information in specific methods or
elsewhere. Any person may apply for a variance from the prescribed
preservation techniques, container materials, and maximum holding times
applicable to samples taken from a specific discharge. Applications for
variances may be made by letters to the Regional Administrator in the
Region in which the discharge will occur. Sufficient data should be
provided to assure such variance does not adversely affect the
integrity of the sample. Such data will be forwarded by the Regional
Administrator to the Alternate Test Procedure Program Coordinator,
Washington, DC, for technical review and recommendations for action on
the variance application. Upon receipt of the recommendations from the
Alternate Test Procedure Program Coordinator, the Regional
Administrator may grant a variance applicable to the specific discharge
to the applicant. A decision to approve or deny a variance will be made
within 90 days of receipt of the application by the Regional
Administrator.?
Table II.--Required Containers, Preservation Techniques, and Holding Times
----------------------------------------------------------------------------------------------------------------
Preservation\2, 3,
Parameter no./name Container\1\ 17\ Maximum holding time\4, 17\
----------------------------------------------------------------------------------------------------------------
Table IA--Bacteria Tests:
----------------------------------------------------------------------------------------------------------------
1-5 Coliform, total, fecal, PA,G.................... Cool, <=6.00 [deg]C 6 hours.
and E. coli. \18\, 0.008%.
Na2S2O3\5\..........
6 Fecal streptococci......... PA,G.................... Cool, <=6.00 [deg]C do.
\18\, 0.008%.
Na2S2O35............
7 enterococci PA,G.................... Cool, <=6.00 [deg]C do.
\18\, 0.008%.
Na2S2O35............
------------------------------
Table IA--Protozoa Tests:
----------------------------------------------------------------------------------------------------------------
8 Cryptosporidium............ LDPE.................... <=6.00 [deg]C \18\.. 96 hours.
[[Page 18215]]
9 Giardia LDPE.................... <=6.00 [deg]C \18\.. 96 hours.
------------------------------
Table IA--Aquatic Toxicity Tests:
----------------------------------------------------------------------------------------------------------------
6-10 Toxicity, acute and P,G..................... Cool, <=6.00 [deg]C 36 hours.
chronic. \16 18\.
------------------------------
Table IB--Inorganic Tests:
----------------------------------------------------------------------------------------------------------------
1. Acidity................... P,G..................... Cool, <=6.00 [deg]C 14 days.
\18\.
2. Alkalinity................ P,G..................... do.................. do.
4. Ammonia................... P,G..................... Cool, <=6.00 [deg]C 28 days.
\18\, H2SO4 to pH<2.
9. Biochemical oxygen demand. P,G..................... Cool, <=6.00 [deg]C 48 hours.
\18\.
10. Boron.................... P or Quartz............. HNO3 to pH<2........ 6 months.
11. Bromide.................. P,G..................... none required....... 28 days.
14. Biochemical oxygen P,G..................... Cool, <=6.00 [deg]C 48 hours.
demand, carbonaceous. \18\.
15. Chemical oxygen demand... P,G..................... Cool, <=6.00 [deg]C 28 days.
\18\, H2SO4 to pH<2.
16. Chloride................. P,G..................... none required....... do.
17. Chlorine, total residual. P,G..................... do.................. Analyze within 15 minutes.
21. Color.................... P,G..................... Cool, <=6.00 [deg]C 48 hours.
\18\.
23-24. Cyanide, total and P,G..................... Cool, <=6.00 [deg]C 14 days\6\.
available (or CATC). \18\, NaOH to
pH<12, reducing
agent \5\.
25. Fluoride................. P....................... None required....... 28 days.
27. Hardness................. P,G..................... HNO3 to pH<2, H2SO4 6 months.
to pH<2.
28. Hydrogen ion (pH)........ P,G..................... None required....... Analyze within 15 minutes.
31, 43. Kjeldahl and organic P,G..................... Cool, <=6.00 [deg]C 28 days.
N. \18\, H2SO4 to pH<2.
------------------------------
Metals\7\
----------------------------------------------------------------------------------------------------------------
18. Chromium VI \7\.......... P,G..................... Cool, <=6.00 [deg]C do.
\18\, pH = 9.3-9.7
\21\.
35. Mercury (CVAA)........... P,G..................... HNO3 to pH<2........ do.
35. Mercury (CVAFS) \17\..... FP, G; and FP-lined 5 mL/L 12N HCl or 5 28 days\17\.
cap\17\. mL/L BrCl \17\.
3, 5-8, 12, 13, 19, 20, 22, P,G..................... HNO3 to pH<2 at 6 months.
26, 29, 30, 32-34, 36, 37, least 24 hours
45, 47, 51, 52, 58-60, 62, prior to
63, 70-72, 74, 75. Metals, analysis.\20\.
except boron, chromium VI
and mercury\7\.
38. Nitrate.................. P,G..................... Cool, <=6.00 [deg]C 48 hours.
\18\.
39. Nitrate-nitrite.......... P,G..................... Cool, <=6.00 [deg]C 28 days.
\18\, H2SO4 to pH<2.
40. Nitrite.................. P,G..................... Cool, <=6.00 [deg]C 48 hours.
\18\.
41. Oil and grease........... G....................... Cool to <=6.00 28 days.
[deg]C \18\, HCl or
H2SO4 to pH<2.
42. Organic Carbon........... P,G..................... Cool to <=6.00 do.
[deg]C \18\, HCl or
H2SO4 or H3PO4, to
pH<2.
44. Orthophosphate........... P,G..................... Filter within 15 48 hours.
minutes of
collection, Cool,
<=6.00 [deg]C \18\.
46. Oxygen, Dissolved Probe.. G Bottle and top........ None required....... Analyze within 15 minutes.
47. Winkler.................. do...................... Fix on site and 8 hours.
store in dark.
48. Phenols.................. G only.................. Cool, <=6.00 [deg]C 28 days.
\18\, H2SO4 to pH<2.
49. Phosphorous (elemental).. G....................... Cool, <=6.00 [deg]C 48 hours.
\18\.
50. Phosphorous, total....... P,G..................... Cool, <=6.00 [deg]C 28 days.
\18\, H2SO4 to pH<2.
53. Residue, total........... P,G..................... Cool, <=6.00 [deg]C 7 days.
\18\.
54. Residue, Filterable...... P,G..................... do.................. do.
55. Residue, Nonfilterable P,G..................... do.................. do.
(TSS).
56. Residue, Settleable...... P,G..................... do.................. 48 hours.
57. Residue, Volatile........ P,G..................... do.................. 7 days.
61. Silica................... P or Quartz............. Cool, <=6.00 [deg]C 28 days.
\18\.
64. Specific conductance..... P,G..................... do.................. do.
65. Sulfate.................. P,G..................... do.................. do.
66. Sulfide.................. P,G..................... Cool, <=6.00 [deg]C 7 days.
\18\ add zinc
acetate plus sodium
hydroxide to pH9.
67. Sulfite.................. P,G..................... None required....... Analyze within 15 minutes.
68. Surfactants.............. P,G..................... Cool, <=6.00 [deg]C 48 hours.
\18\.
69. Temperature.............. P,G..................... None required....... Analyze.
73. Turbidity................ P,G..................... Cool, <=6.00 [deg]C 48 hours.
\18\.
------------------------------
Table IC.--Organic Tests.\8\
----------------------------------------------------------------------------------------------------------------
13, 18-20, 22, 24-28, 34-37, G, Teflon-lined septum.. Cool, <=6.00 [deg]C 14 days.
39-43, 45-47, 56, 76, 104, \18\, 0.008%.
105, 108-111, 113. Purgeable Na2S2O3\5\..........
Halocarbons.
6,57, 106. Purgeable aromatic do...................... Cool, <=6.00 [deg]C do.
hydrocarbons. \18\, 0.008%.
Na2S2O3\5\, HCI to
pH 2\9\.
3,4, Acrolein and do...................... Cool, <=6.00 [deg]C do.
acrylonitrile. \18\, 0.008%.
Na2S2O3\5\, adjust
pH to 4-5 \10\.
23, 30, 44, 49, 53, 77, 80, G, Teflon-lined cap..... Cool, <=6.00 [deg]C 7 days until extraction, 40 days
81, 98, 100, 112. \18\, 0.008%. after extraction.
Phenols\11\. Na2S2O3\5\..........
7, 38. Benzidines\11\........ do...................... do.................. 7 days until extraction.\13\
14, 17, 48, 50-52. Phthalate do...................... Cool, <=6.00 [deg]C 7 days until extraction, 40 days
esters.\11\. \18\. after extraction.
82-84. Nitrosamines\11, 14\.. do...................... Cool, <=6.00 [deg]C do.
\18\, store in
dark, 0.008%.
Na2S2O3\5\..........
88-94. PCBs\11\.............. do...................... Cool, <=6.00 [deg]C 1 year.
\18\.
54, 55, 75, 79. do...................... Cool, <=6.00 [deg]C do.
Nitroaromatics and \18\ store in dark,
isophorone\11\. 0.008%.
Na2S2O3\5\..........
[[Page 18216]]
1, 2, 5, 8-12, 32, 33, 58, do...................... do.................. do.
59, 74, 78, 99, 101.
Polynuclear aromatic
hydrocarbons\11\.
15, 16, 21, 31, 87. do...................... Cool, <=6.00 [deg]C do.
Haloethers\11\. \18\, 0.008%.
Na2S2O3\5\..........
29, 35-37, 63-65, 107. do...................... Cool, <=6.00 [deg]C do.
Chlorinated \18\.
hydrocarbons.\11\.
60-62, 66-72, 85, 86, 95-97, ........................ .................... .................................
102, 103. CDDs/CDFs.\11\.
Aqueous Samples: Field and G....................... Cool, <=6.00 [deg]C 1 year.
Lab Preservation. \18\, 0.008%.
Na2S2O3\5\, pH<9....
Solids & Mixed Phase Samples: do...................... Cool, <=6.00 [deg]C 7 days.
Field Preservation. \18\.
Tissue Samples: Field do...................... Cool, <=6.00 [deg]C 24 hours.
Preservation. \18\.
Solids, Mixed Phase, and do...................... Freeze, <= -10 1 year.
Tissue Samples: Lab [deg]C.
Preservation.
------------------------------
Table ID-Pesticides Tests:
----------------------------------------------------------------------------------------------------------------
1-70. Pesticides.\11\........ do...................... Cool, <=6.00 [deg]C do.
\18\, pH 5-9 \15\.
------------------------------
Table IE-Radiological Tests:
----------------------------------------------------------------------------------------------------------------
1-5. Alpha, beta and radium.. P,G..................... HNO3 to pH<2........ 6 months.
----------------------------------------------------------------------------------------------------------------
\1\ ``P'' is polyethylene or polytetrafluoroethylene (PTFE; Teflon), or other fluoropolymer, unless otherwise
stated in this Table II. ``FP'' is fluoropolymer. ``G'' is glass. ``PA'' is any plastic that is made of a
sterlizable material (polypropylene or other autoclavable plastic). LDPE is low density polyethylene.
\2\ Except where noted in this Table II and the method for the parameter, preserve each grab sample within 15
minutes of collection. For a composite sample to be collected automatically over time (e.g., using a 24-hour
composite sampler; see 40 CFR 122.21(g)(7) and 40 CFR part 403, Appendix E), refrigerate the sample at <=6.00
[deg]C during collection unless otherwise specified in this Table II or in the method(s). For a composite
sample collected automatically over time to be split into separate aliquots for preservation and/or analysis,
maintain the sample at <=6.00 [deg]C unless otherwise specified in this Table II or in the method(s), until
collection, splitting, and preservation is completed. Add the preservative to the sample container prior to
sample collection when the preservative will not compromise the integrity of a grab sample, a composite
sample, or any of the aliquots split from a composite sample collected automatically over time; otherwise,
preserve the sample or aliquots within 15 minutes of collection. If a composite measurement is required but a
composite sample collected automatically over time would compromise sample integrity, individual grab samples
must be collected at prescribed time intervals (e.g., 4 samples over the course of a day at 6-hr. intervals).
Grab samples must be analyzed separately and the concentrations averaged. Alternatively, grab samples may be
collected in the field and composited in the laboratory if the compositing procedure produces results
equivalent to results produced by arithmetic averaging of the results of analysis of individual grab samples.
For examples of laboratory compositing procedures, see EPA Method 1664A (oil and grease) and the procedures at
40 CFR 141.34(f)(14)(iv) and (v) (volatile organics).
\3\ When any sample is to be shipped by common carrier or sent through the United States mails, it must comply
with the Department of Transportation Hazardous Materials Regulations (49 CFR part 172). The person offering
such material for transportation is responsible for ensuring such compliance. For the preservation
requirements of Table II, the Office of Hazardous Materials, Materials Transportation Bureau, Department of
Transportation has determined that the Hazardous Materials Regulations do not apply to the following
materials: Hydrochloric acid (HCl) in water solutions at concentrations of 0.04% by weight or less (pH about
1.96 or greater); Nitric acid (HNO3) in water solutions at concentrations of 0.15% by weight or less (pH about
1.62 or greater); Sulfuric acid (H2SO4) in water solutions at concentrations of 0.35% by weight or less (pH
about 1.15 or greater); and Sodium hydroxide (NaOH) in water solutions at concentrations of 0.080% by weight
or less (pH about 12.30 or less).
\4\ Samples should be analyzed as soon as possible after collection. The times listed are the maximum times that
samples may be held before the start of analysis and still be considered valid (e.g., samples analyzed for
fecal coliforms may be held up to six hours prior to commencing analysis). Samples may be held for longer
periods only if the permittee, or monitoring laboratory has data on file to show that for the specific types
of samples under study, the analytes are stable for the longer time, and has received a variance from the
Regional Administrator under Sec. 136.3(e). For a grab sample, the holding time begins at the time of
collection for a composite sample collected automatically over time (e.g., using a 24-hour composite sample;
see 40 CFR 122.21(g)(7) and 40 CFR part 403, Appendix E), the holding time begins at the time of the end of
collection of the composite samples. Some samples may not be stable for the maximum time period given in the
table. A permittee, or monitoring laboratory, is obligated to hold the sample for a shorter time if they know
it is necessary to maintain sample stability. See Sec. 136.3(e) for details.
\5\ Add ascorbic acid or sodium borohydride (NaBH4) reagent if (and only if) oxidants (e.g., chlorine) are
present. Add enough reagent to reduce any oxidants that are present. Generally, 0.1 g/L NaBH4 can reduce 50 mg/
L of chlorine (see method ``Kelada-01'' for more information). Methods recommending ascorbic acid generally
specify to increase ascorbic acid in 0.6 mg/L increments until oxidants are removed. After adding reagent,
test the sample using KI paper or a chlorine/oxidant test method to make sure all chlorine/oxidant is removed.
If chlorine/oxidant remains, add more reagent. Do not add excess reagent, however, because this may interfere
with test results.
\6\ Collect the sample in an amber glass bottle with PTFE-lined cap. Immediately after collection, preserve the
sample using any or all of the following techniques, as necessary, followed by adjustment of the sample pH to
=12 by addition of sodium hydroxide and refrigeration as specified:
(1) Sulfide: The maximum holding time for an untreated sample is 24 hours when sulfide is present. Optionally,
the sample may be treated and the maximum holding time extended to 14 days. Generally, the laboratory should
test the sample with lead acetate test paper to determine the presence or absence of sulfide ion. However, for
cyanide methods using amperometric detection systems (e.g., OIA-1677 for available cyanide), sulfide levels
below those detectable with lead acetate paper (approximately 5 ppm) may produce a false positive signal for
cyanide. If there is reason to suspect sulfide levels below the detectable level of lead acetate paper when
using an amperometric method, test the sample using a more sensitive sulfide method to determine if the
treatment (described below) is required. If sulfide ion is present, treat the sample immediately (within 15
minutes of collection) with sufficient solid lead carbonate to remove sulfide (as evidenced by a lead acetate
test paper), and immediately filter into another sample bottle to remove precipitated lead sulfide. If sulfide
ion is suspected to be present, but its presence is not detected by the lead acetate paper test, two samples
must be collected. One is treated for the presence of sulfide and immediately filtered, while the second is
not treated for sulfide. Analyze both samples and report the lower of the two results.
(2) Sulfide and particulate matter: If the sample contains sulfide and particulate matter that would be removed
by filtration, filter the sample prior to treatment with lead carbonate to assure that cyanides associated
with the particulate matter are included in the measurement. Save the particulate matter and treat the
filtrate using the sulfide removal procedure above. Combine and homogenize the collected particulate and
treated filtrate prior to shipment to the laboratory for analysis.
(3) Aldehydes: Treat samples known or suspected to contain formaldehyde, acetaldehyde, or other water soluble
aldehydes with 20 mL of 3.5% ethylenediamine solution per liter of sample.
(4) Chlorine, hypochlorite, or other oxidants: Treat samples known or suspected to contain chlorine,
hypochlorite, or other oxidants as directed in footnote 5. EPA Method 330.4 or 330.5 may be used for the
measurement of residual chlorine.
\7\ For dissolved metals, filter the sample within 15 minutes of collection and before adding preservatives.
\8\ Guidance applies to samples to be analyzed by GC, LC, or GC/MS for specific compounds.
\9\ Sample receiving no pH adjustment must be analyzed within seven days of sampling.
\10\ The pH adjustment is not required if acrolein will not be measured. Samples for acrolein receiving no pH
adjustment must be analyzed within 3 days of sampling.
\11\ When the extractable analytes of concern fall within a single chemical category, the specified preservative
and maximum holding times should be observed for optimum safeguard of sample integrity (i.e., use all
necessary preservatives and hold for the shortest time listed). When the analytes of concern fall within two
or more chemical categories, the sample may be preserved by cooling to <=6.00 [deg]C, reducing residual
chlorine with 0.008% sodium thiosulfate, storing in the dark, and adjusting the pH to 6-9; samples preserved
in this manner may be held for seven days before extraction and for forty days after extraction. Exceptions to
this optional preservation and holding time procedure are noted in footnote 5 (regarding the requirement for
thiosulfate reduction), and footnotes 12, 13 (regarding the analysis of benzidine).
\12\ If 1,2-diphenylhydrazine is likely to be present, adjust the pH of the sample to 4.0
0.2 to prevent rearrangement to benzidine.
\13\ Extracts may be stored up to 30 days at <0 [deg]C.
\14\ For the analysis of diphenylnitrosamine, add 0.008% Na2S2O3 and adjust pH to 7-10 with NaOH within 24 hours
of sampling.
\15\ The pH adjustment may be performed upon receipt at the laboratory and may be omitted if the samples are
extracted within 72 hours of collection. For the analysis of aldrin, add 0.008% Na2S2O3.
\16\ Sufficient ice should be placed with the samples in the shipping container to ensure that ice is still
present when the samples arrive at the laboratory. However, even if ice is present when the samples arrive, it
is necessary to immediately measure the temperature of the samples and confirm that the 6.00 [deg]C
temperature maximum has not been exceeded. In the isolated cases where it can be documented that this holding
temperature cannot be met, the permittee can be given the option of on-site testing or can request a variance.
The request for a variance should include supportive data which show that the toxicity of the effluent samples
is not reduced because of the increased holding temperature.
\17\ Samples collected for the determination of trace level mercury (100 ng/L) using EPA Method 1631 must be
collected in tightly-capped fluoropolymer or glass bottles and preserved with BrCl or HCl solution within 48
hours of sample collection. The time to preservation may be extended to 28 days if a sample is oxidized in the
sample bottle. Samples collected for dissolved trace level mercury should be filtered in the laboratory.
However, if circumstances prevent overnight shipment, samples should be filtered in a designated clean area in
the field in accordance with procedures given in Method 1669. Samples that have been collected for
determination of total or dissolved trace level mercury must be analyzed within 90 days of sample collection.
\18\ Samples must be preserved at <=6.00 [deg]C, and should not be frozen unless data demonstrating that sample
freezing does not adversely impact sample analysis is maintained on file and accepted as valid by the
permitting authority. Also, for the purposes of NPDES monitoring, the specification of ``<=6.00 [deg]C'' is
used in place of the ``4 [deg]C'' and ``< 4 [deg]C'' sample temperature requirements listed in some methods.
\19\ ``do'' means ditto, or same as the entry immediately above this column.
\20\ Samples can be collected and shipped without acid preservation. However, acid must be added at least 24
hours before analysis to dissolve any metals that adsorb to the container walls.
\21\ To achieve the 28 day holding time, use sodium hydroxide and the ammonium sulfate buffer solution specified
in EPA Method 218.6.
[[Page 18217]]
3. Section 136.4 is amended by revising the first sentence of
paragraph (d) introductory text to read as follows:
Sec. 136.4 Application for alternate test procedures.
(d) An application for approval of an alternate test procedure for
nationwide use may be made by letter in triplicate to the Alternate
Test Procedure Program Coordinator, Office of Science and Technology
(4303), Office of Water, U.S. Environmental Protection Agency, 1200
Pennsylvania Ave., NW., Washington, DC 20460. * * *
4. Section 136.5 is amended:
a. In paragraph (b) by revising the second sentence.
b. By revising paragraph (c).
c. In paragraph (d) by revising the second and third sentences.
d. By revising paragraphs (e)(1) and (e)(2).
The revisions read as follows:
Sec. 136.5 Approval of alternate test procedures.
* * * * *
(b) * * * Where the Director recommends rejection of the
application for scientific and technical reasons which he provides, the
Regional Administrator shall deny the application and shall forward
this decision to the Director of the State Permit Program and to the
Alternate Test Procedure Program Coordinator, Washington, DC.
(c) Before approving any application for an alternate test
procedure proposed by the responsible person or firm making the
discharge, the Regional Administrator shall forward a copy of the
application to the Alternate Test Procedure Program Coordinator,
Washington, DC.
(d) * * * Prior to the expiration of such ninety day period, a
recommendation providing the scientific and other technical basis for
acceptance or rejection will be forwarded to the Regional Administrator
by the Alternate Test Procedure Program Coordinator, Washington, DC. A
copy of all approval and rejection notifications will be forwarded to
the Alternate Test Procedure Program Coordinator, Washington, DC, for
the purposes of national coordination.
(e) Approval for nationwide use. (1) As expeditiously as is
practicable after receipt by the Alternate Test Procedure Program
Coordinator, Washington, DC, of an application for an alternate test
procedure for nationwide use, the Alternate Test Procedure Program
Coordinator, Washington, DC, shall notify the applicant in writing
whether the application is complete. If the application is incomplete,
the applicant shall be informed of the information necessary to make
the application complete.
(2) As expeditiously as is practicable after receipt of a complete
package, the Alternate Test Procedure Program Coordinator shall perform
any analysis necessary to determine whether the alternate test
procedure satisfies the applicable requirements of this part, and the
Alternate Test Procedure Program Coordinator shall recommend to the
Administrator that he/she approve or reject the application and shall
also notify the application of the recommendation.
* * * * *
5. Section 136.6 is added to part 136 to read as follows:
Sec. 136.6 Method modifications and analytical requirements.
(a) Definitions. As used in this section:
(1) Analyst means the person or laboratory using a test procedure
(analytical method) in this part.
(2) Chemistry of the method means the reagents and reactions used
in a test procedure that allow determination of the analyte(s) of
interest in an environmental sample.
(3) Determinative technique means the way in which an analyte is
identified and quantified (e.g., colorimetery, mass spectrometry).
(4) Equivalent performance means that the modified method produces
results that meet the QC acceptance criteria of the approved method at
this part.
(5) Method-defined analyte means an analyte defined solely by the
method used to determine the analyte. Such an analyte may be a physical
parameter, a parameter that is not a specific chemical, or a parameter
that may be comprised of a number of substances. Examples include
temperature, oil and grease, total suspended solids, total phenolics,
turbidity, chemical oxygen demand, and biochemical oxygen demand.
(6) QC means ``quality control.''
(b) Method modifications.--(1) Allowable changes. Except as set
forth in paragraph (b)(3) of this section, an Analyst may modify a test
procedure (analytical method) provided that the chemistry of the method
or the determinative technique is not changed, and provided that the
requirements of paragraph (b)(2) of this section are met.
(i) Potentially allowable modifications regardless of current
method performance include changes between automated and manual
discrete instrumentation; changes in the calibration range (provided
that the modified range covers any relevant regulatory limit); changes
in equipment such as using similar equipment from a vendor other than
that mentioned in the method (e.g., a purge-and-trap device from OIA
rather than Tekmar), changes in equipment operating parameters such as
changing the monitoring wavelength of a colorimeter or modifying the
temperature program for a specific GC column; changes to
chromatographic columns (treated in greater deal in paragraph (d) of
this section); and increases in purge-and-trap sample volumes (provided
specifications in paragraph (e) of this section are met). The changes
are only allowed provided that all the requirements of paragraph (b)(2)
of this section are met.
(ii) If the characteristics of a wastewater matrix prevent
efficient recovery of organic pollutants and prevent the method from
meeting QC requirements, the Analyst may attempt to resolve the issue
by using salts as specified in Guidance on Evaluation, Resolution, and
Documentation of Analytical Problems Associated with Compliance
Monitoring (EPA 821-B-93-001, June 1993), provided that such salts do
not react with or introduce the target pollutant into the sample (as
evidenced by the analysis of method blanks, laboratory control samples,
and spiked samples that also contain such salts) and that all
requirements of paragraph (b)(2) of this section are met. Chlorinated
samples must be dechlorinated prior to the addition of such salts.
(iii) If the characteristics of a wastewater matrix result in poor
sample dispersion or reagent deposition on equipment and prevents the
Analyst from meeting QC requirements, the Analysts may attempt to
resolve the issue by adding an inert surfactant (i.e. a surfactant that
will not affect the Chemistry of the Method), which may include Brij-35
or sodium dodecyl sulfate (SDS), provided that such surfactant does not
react with or introduce the target pollutant into the sample (as
evidenced by the analysis of method blanks, laboratory control samples,
and spiked samples that also contain such surfactant) and that all
requirements of paragraph (b)(2) of this section are met. Chlorinated
samples must be dechlorinated prior to the addition of such surfactant.
(2) Requirements. A modified method must produce Equivalent
Performance for the analyte(s) of interest, and the Equivalent
Performance must be documented.
(i) Requirements for Establishing Performance.
[[Page 18218]]
(A) If the approved method contains QC tests and QC acceptance
criteria, the QC tests must be used with the modified method and the QC
acceptance criteria must be met. The Analyst may only rely on QC tests
and QC acceptance criteria in a method if it includes wastewater matrix
QC tests and QC acceptance criteria (i.e., as matrix spikes) and both
initial (start-up) and ongoing QC tests and QC acceptance criteria.
(B) If the approved method does not contain QC tests and QC
acceptance criteria, or if the QC tests and QC acceptance criteria in
the method do not meet the requirements of paragraph (b)(2)(i)(A) of
this section, the analyst must employ QC tests specified in Protocol
for EPA Approval of Alternate Test Procedures for Organic and Inorganic
Analytes in Wastewater and Drinking Water (EPA-821-B-98-002; March
1999) and meet the QC provisions specified therein. In addition, the
Analyst must perform on-going QC tests, including assessment of
performance of the modified method on the sample matrix (e.g., analysis
of a matrix spike/matrix spike duplicate pair for every twenty samples
of a discharge analyzed), and analysis of an ongoing precision and
recovery sample and a blank with each batch of 20 or fewer samples.
(C) Calibration must be performed using the modified method and the
modified method must be tested with every wastewater matrix to which it
will be applied (up to nine distinct matrices; as described in the ATP
Protocol, after validation in nine distinct matrices, the method may be
applied to all wastewater matrices), in addition to any and all reagent
water tests. If the performance in the wastewater matrix or reagent
water does not meet the QC acceptance criteria the method modification
may not be used.
(D) Analysts are obligated to test representative effluents. In
addition, the non-modified approved method may be required to resolve
any controversies.
(ii) Requirements for documentation. The modified method must be
documented in a method write-up or an addendum that describes the
modification(s) to the approved method. The write-up or addendum must
include a reference number (e.g., method number), revision number, and
revision date so that it may be referenced accurately. In addition, the
organization that uses the modified method must document the results of
QC tests and keep these records, along with a copy of the method write-
up or addendum, for review by an auditor.
(3) Restrictions. This paragraph does not apply to a method for a
method-defined analyte or a change that would result in measurement of
a different form or species of an analyte (e.g., a change to a metals
digestion or total cyanide distillation). This paragraph (b)(3) also
does not apply to changes in sample preservation and/or holding time.
(c) Analytical requirements for multi-analyte methods (target
analytes). For the purpose of NPDES reporting, the discharger or
permittee must meet QC requirements only for the analyte(s) being
measured and reported under the NPDES permit.
(d) Capillary column. Use of a capillary (open tubular) GC column
with EPA Methods 601-613, 624, 625, and 1624B in appendix A to this
part is allowed provided that all QC tests in the method are performed
and all QC acceptance criteria are met. When changing from a packed
column to a capillary column, the analyst must establish a new record
of analyte retention times and keep these on file along with other
startup test and ongoing QC data.
(e) Increased sample volume in purge and trap methodology.
Increased sample volumes, up to a maximum of 25 mL, are allowed
provided that the height of the water column in the purge vessel is at
least 5 cm. The analyst should also use one or more surrogate analytes
that are chemically similar to the analytes of interest in order to
demonstrate that the increased sample volume does not adversely affect
the analytical results.
6. Section 136.7 is added to part 136 to read as follows:
Sec. 136.7 Reporting.
(a) Demonstration of compliance with a permit must be based upon
testing which meets QC requirements in this part, including QC
requirements in the method used for the testing.
(b) Failure to meet the QC requirements in this part, including QC
requirements in the approved method, does not relieve a discharger or
permittee of timely reporting of test results.
(c) Results from tests must be reported to the level specified in
the analytical method or permit, whichever is lower.
(d) Where a conflict is created between reporting requirements in
this section and the reporting requirements in an analytical method
listed in this part, reporting requirements in this section supersede
reporting requirements in the analytical method.
Appendices C and D [Removed]
7. Appendices C and D to part 136 are removed.
PART 141--NATIONAL PRIMARY DRINKING WATER REGULATIONS
1. The authority citation for part 141 continues to read as
follows:
Authority: 42 U.S.C. 300f, 300g-1, 300g-2 300g-3, 300g-4, 300g-
5, 300g-6, 300j-4, 300j-9, and 300j-11.
2. Section 141.21 is amended by adding a sentence to the end of
footnote 1 to the Table in paragraph (f)(3) to read as follows:
Sec. 141.21 Coliform sampling.
* * * * *
(f) * * *
(3) * * *
\1\ * * * In addition, the following on-line versions with the
noted approval date may also be used: 2310 B-01, 9215 B-00, 9221 A,
B, D-99, 9222 A, B, C-97, and 9223-97.
* * * * *
3. Section 141.23 is amended:
a. In paragraph (a)(4)(i) by revising the entries for ``Cyanide,''
``Nitrate,'' and ``Nitrite'' in the table, and by adding a new footnote
9 to the table.
b. In paragraph (k)(1) by revising the table. The revisions and
addition read as follows:
Sec. 141.23 Inorganic chemical sampling and analytical requirements.
* * * * *
(a) * * *
(4) * * *
(i) * * *
Detection Limits for Inorganic Contaminants
--------------------------------------------------------------------------------------------------------------------------------------------------------
Contaminant MCL (mg/L) Methodology Detection Limit (mg/L)
--------------------------------------------------------------------------------------------------------------------------------------------------------
* * * * * * *
Cyanide................................. 0.2 Distillation, Spectrophotometric \3\............... 0.02
................................ Distillation, Automated, Spectrophotometric \3\.... 0.005
................................ Distillation, Amenable, Spectrophotometric \4\..... 0.02
................................ Distillation, Selective Electrode \3\.............. 0.05
[[Page 18219]]
................................ UV, Distillation, Spectrophotometric \9\........... 0.0005
................................ Distillation, Spectrophotometric \3\............... 0.0006
................................ Ligand Exchange with Amperometry \4\............... 0.0005
* * * * * * *
Nitrate................................. 10 (as N) Manual Cadmium Reduction........................... 0.01
................................ Automated Hydrazine Reduction...................... 0.01
................................ Automated Cadmium Reduction........................ 0.05
................................ Ion Selective Electrode............................ 1
................................ Ion Chromatography................................. 0.01
................................ Capillary Ion Electrophoresis...................... 0.076
Nitrite................................. 1 (as N) Spectrophotometric................................. 0.01
................................ Automated Cadmium Reduction........................ 0.05
................................ Manual Cadmium Reduction........................... 0.01
................................ Ion Chromatography................................. 0.004
................................ Capillary Ion Electrophoresis...................... 0.103
* * * * * * *
--------------------------------------------------------------------------------------------------------------------------------------------------------
* * * * *
\3\ Screening method for total cyanides.
\4\ Measures ``free'' cyanides.
* * * * *
\9\ Measures total cyanides when UV-digestor is used, and ``free'' cyanides when UV-digestor is bypassed.
* * * * *
(k) * * *
(1) * * *
--------------------------------------------------------------------------------------------------------------------------------------------------------
SM \4\ (18th, SM \4\ (20th
Contaminant Methodology \13\ EPA ASTM \3\ 19th ed.) ed.) SM on-line\22\ Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Alkalinity................ Titrimetric...... ................ D1067-92, 02 B.. 2320 B......... 2320 B......... 2320 B-97...... ...............
Electrometric ................ ................ ............... ............... ............... I-030-85 \5\
titration.
2. Antimony.................. Inductively 200.8 \2\.......
Coupled Plasma
(ICP)--Mass
Spectrometry.
Hydride-Atomic ................ D3697-92........ ............... ............... ............... ...............
Absorption.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Atomic ................ ................ 3113 B......... ............... 3113 B-99...... ...............
Absorption;
Furnace.
3. Arsenic \14\.............. Inductively 200.7\2\........ ................ 3120 B......... 3120 B......... 3120 B-99...... ...............
Coupled Plasma
\15\.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
Atomic Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Atomic Absorption ................ D2972-97, 03 C.. 3113 B......... ............... 3113 B-99......
Furnace.
Hydride Atomic ................ D2972-97, 03 B.. 3114 B......... ............... 3114 B-97...... ...............
Absorption.
4. Asbestos.................. Transmission 100.1 \9\....... ................ ............... ............... ............... ...............
Electron
Microscopy.
Transmission 100.2 \10\...... ................ ............... ............... ............... ...............
Electron
Microscopy.
5. Barium.................... Inductively 200.7 \2\....... ................ 3120 B......... 3120 B......... 3120 B-99...... ...............
Coupled Plasma.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
Atomic ................ ................ 3111 D......... ............... 3111 D-99...... ...............
Absorption;
Direct.
Atomic ................ ................ 3113 B......... ............... 3113 B-99...... ...............
Absorption;
Furnace.
6. Beryllium................. Inductively 200.7 \2\....... ................ 3120 B......... 3120 B......... 3120 B-99...... ...............
Coupled Plasma.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Atomic ................ D3645-97, 03 B.. 3113 B......... 3113 B-99...... ............... ...............
Absorption;
Furnace.
7. Cadmium................... Inductively 200.7 \2\....... ................ ............... ............... ............... ...............
Coupled Plasma.
ICP-Mass 200.8 \2\.......
Spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Atomic ................ ................ 3113 B......... ............... 3113 B-99...... ...............
Absorption;
Furnace.
8. Calcium................... EDTA titrimetric. ................ D511-93, 03 A... 3500-Ca D...... 3500-Ca B...... 3500-Ca B-97... ...............
Atomic ................ D511-93, 03 B... 3111 B......... ............... 3111 B-99...... ...............
Absorption;
Direct
Aspiration.
Inductively 200.7 \2\....... ................ 3120 B......... 3120 B......... 3120 B-99...... ...............
Coupled Plasma.
[[Page 18220]]
Ion ................ D6919-03........ ............... ............... ............... ...............
Chromatography.
9. Chromium.................. Inductively 200.7 \2\....... ................ 3120 B......... 3120 B......... 3120 B-99...... ...............
Coupled Plasma.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Atomic ................ ................ 3113 B......... ............... 3113 B-99...... ...............
Absorption;
Furnace.
10. Copper................... Atomic ................ D1688-95, 02 C.. 3113 B......... ............... 3113 B-99...... ...............
Absorption;
Furnace.
Atomic ................ D1688-95, 02 A.. 3111 B......... ............... 3111 B-99...... ...............
Absorption;
Direct
Aspiration.
Inductively 200.7 \2\....... ................ 3120 B........ 3120 B......... 3120 B-99...... ...............
Coupled Plasma.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
11. Conductivity............. Conductance...... D1125-95 (99) A. 2510 B.......... 2510 B......... 2510 B-97...... ...............
12. Cyanide.................. Manual ................ D2036-98A....... 4500-CN C...... 4500-CN-C...... ............... ...............
Distillation
followed by.
Spectro- ................ D2036-98B....... 4500-CN G...... 4500-CN G...... 4500-CN G-99... ...............
photometric,
Amenable.
Spectro- ................ D2036-98A....... 4500-CN E...... 4500-CN E...... 4500-CN E99.... I-3300-85 \5\
photometric
Manual.
Spectro- 335.4 \6\....... ................ ............... ............... ............... ...............
photometric Semi-
automated.
Selective ................ ................ 4500-CN F...... 4500-CN F...... 4500-CN F-99... ...............
Electrode.
UV, Distillation, ................ ................ ............... ............... ............... Kelada-01 \17\
Spectro-
photometric.
Distillation, ................ ................ ............... ............... ............... QuikChem 10-204-
Spectro- 00-1-X \18\
photometric.
Ligand Exchange ................ D6888-03........ ............... ............... ............... OIA-1677, DW
[and Amperometry \20\
\21\.
13. Fluoride................. Ion 300.0 \6\....... D4327-97, 03.... 4110 B......... 4110 B......... 4110 B-00...... ...............
Chromatography.
Manual Distill.; ................ ................ 4500-F B, D.... 4500-F B, D.... 4500-F B, D-97.
Color. SPADNS.
Manual Electrode. ................ D1179-93, 99 B.. 4500-F C....... 4500-F C....... 4500-F C-97.... ...............
Automated ................ ................ ............... ............... ............... 380-75WE \11\
Electrode.
Automated ................ ................ 4500-F E....... 4500-F E....... 4500-F E-97.... 129-71W \11\
Alizarin.
Capillary Ion ................ ................ ............... ............... ............... D6508, Rev. 2
Electrophoresis. \19\
14. Lead..................... Atomic Absorption ................ D3559-96, 03 D.. 3113 B......... ............... 3113 B-99...... ...............
Furnace.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Differential ................ ................ ............... ............... ............... Method 1001
Pulse Anodic \16\
Stripping
Voltametry.
15. Magnesium................ Atomic Absorption ................ D511-93, 03 B... 3111 B......... ............... 3111 B-99...... ...............
ICP.............. 200.7 \2\....... ................ 3120 B......... 3120 B......... 3120 B-99...... ...............
Complexation ................ D511-93, 03 A... 3500-Mg E...... 3500-Mg B...... 3500-Mg B-97... ...............
Titrimetric
Methods.
Ion ................ D6919-03........ ............... ............... ............... ...............
Chromatography.
16. Mercury.................. Manual, Cold 245.1 \2\....... D3223-97, 02.... 3112 B......... ............... 3112 B-99......
Vapor.
Automated, Cold 245.2 \1\....... ................ ............... ............... ............... ...............
Vapor.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
17. Nickel................... Inductively 200.7 \2\....... ................ 3120 B........ 3120 B......... 3120 B-99...... ...............
Coupled Plasma.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Atomic ................ ................ 3111 B......... ............... 3111 B-99...... ...............
Absorption;
Direct.
Atomic ................ ................ 3113........... ............... 3113 B-99...... ...............
Absorption;
Furnace.
18. Nitrate.................. Ion 300.0 \6\....... D4327-97, 03.... 4110 B......... 4110 B......... 4110 B-00...... B-1011 \8\
Chromatography.
Automated Cadmium 353.2 \6\....... D3867-90 A...... 4500-NO3 F..... 4500-No3 F..... 4500-NO3 F-00.. ...............
Reduction.
Ion Selective ................ ................ 4500-NO3 D..... 4500-NO3 D..... 4500-NO3 D-00.. 601 \7\
Electrode.
Manual Cadmium ................ D3867-90 B...... 4500-NO3 E..... 4500-NO3 E..... 4500-NO3 E-00.. ...............
Reduction.
Capillary Ion ................ ................ ............... ............... ............... D6508, Rev. 2
Electrophoresis. \19\
19. Nitrite.................. Ion 300.0 \6\....... D4327-97........ 4110 B......... 4110 B......... 4110 B-00...... B-1011 \8\
Chromatography.
Automated Cadmium 353.2 \6\....... D3867-90 A...... 4500-NO3 F..... 4500-NO3 F..... 4500-NO3 F-00.. ...............
Reduction.
Manual Cadmium ................ D3867-90 B...... 4500-NO3 E..... 4500-NO3 E..... 4500-NO3 E-00.. ...............
Reduction.
Spectro- ................ ................ 4500-NO2 B..... 4500-NO2 B..... 4500-NO2 B-00.. ...............
photometric.
[[Page 18221]]
Capillary Ion ................ ................ ............... ............... ............... D6508, Rev. 2
Electrophoresis. \19\
20. Ortho-phosphate \12\..... Colorimetric, 365.1 \6\....... ................ 4500-P F....... 4500-P F....... ............... ...............
Automated,
Ascorbic Acid.
Colorimetric, ................ D515-88A........ 4500-P E....... 4500-P E....... ............... ...............
ascorbic acid,
single reagent.
Colorimetric ................ ................ ............... ............... ............... I-1601-85 \5\
Phospho-
molybdate;.
Automated- ................ ................ ............... ............... ............... I-2601-90 \5\
segmented Flow;.
Automated ................ ................ ............... ............... ............... I2598-85 \5\
Discrete.
Ion 300.0 \6\....... D4327-97, 03.... 4110 B......... 4110 B......... 4110 B-00...... ...............
Chromatography.
Capillary Ion ................ ................ ............... ............... ............... D6508, Rev. 2
Electrophoresis. \19\
21. pH....................... Electrometric.... 150.1, 150.2 \1\ D1293-95, 99.... 4500-H+ B...... 4500-H+ B...... 4500-H+B-00.... ...............
22. Selenium................. Hydride-Atomic ................ D3859-98, 03 A.. 3114 B......... ............... 3114 B-97...... ...............
Absorption.
ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
Atomic ................ D3859-98, 03 B.. 3113 B......... ............... 3113 B-99...... ...............
Absorption;
Furnace.
23. Silica................... Colorimetric, ................ ................ ............... ............... ............... I-1700-85 \5\
Molybdate Blue;.
Automated- ................ ................ ............... ............... ............... I-2700-85 \5\
segmented Flow.
Colorimetric..... ................ D859-95, 00..... ............... ............... ............... ...............
Molybdosilicate.. ................ ................ 4500-Si D...... 4500-SiO2 C.... 4500-SiO2 C-97. ...............
Heteropoly blue.. ................ ................ 4500-Si E...... 4500-SIO2 D.... 4500-SiO2 D-97. ...............
Automated for ................ ................ 4500-Si F...... 4500-SiO2 E.... 4500-SiO2 E-97. ...............
Molybdate-
reactive Silica.
Inductively 200.7 \2\....... ................ 3120 B......... 3120 B......... 3120 B-99...... ...............
Coupled Plasma.
24. Sodium................... Inductively 200.7 \2\....... ................ ............... ............... ............... ...............
Coupled Plasma.
Atomic ................ ................ 3111 B......... ............... 3111 B-99...... ...............
Absorption;
Direct
Aspiration.
Ion ................ D6919-03........ ............... ............... ............... ...............
Chromatography.
25. Temperature.............. Thermometric..... ................ ................ 2550........... 2550........... 2550-00........ ...............
26. Thallium................. ICP-Mass 200.8 \2\....... ................ ............... ............... ............... ...............
Spectrometry.
Atomic 200.9 \2\....... ................ ............... ............... ............... ...............
Absorption;
Platform.
--------------------------------------------------------------------------------------------------------------------------------------------------------
The procedures shall be done in accordance with the documents listed below. The incorporation by reference of the following documents listed in
footnotes 1-11, 16-20 and 22 was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the
documents may be obtained from the sources listed below. Information regarding obtaining these documents can be obtained from the Safe Drinking Water
Hotline at 800-426-4791. Documents may be inspected at EPA's Drinking Water Docket, 1301 Constitution Avenue, NW., EPA West, Room B102, Washington, DC
20460 (Telephone: 202-566-2426); or at the Office of the Federal Register, 800 North Capitol Street, NW., Suite 700, Washington, DC 20408.
\1\ ``Methods for Chemical Analysis of Water and Wastes,'' EPA/600/4-79/020, March 1983. Available at NTIS, PB84-128677.
\2\ ``Methods for the Determination of Metals in Environmental Samples--Supplement I,'' EPA/600/R-94/111, May 1994. Available at NTIS, PB95-125472.
\3\ Annual Book of ASTM Standards, 1994, 1996, 1999, or 2003, Vols. 11.01 and 11.02, ASTM International; any year containing the cited version of the
method may be used. The previous versions of D1688-95A, D1688-95C (copper), D3559-95D (lead), D1293-95 (pH), D1125-91A (conductivity) and D859-94
(silica) are also approved. These previous versions D1688-90A, C; D3559-90D, D1293-84, D1125-91A and D859-88, respectively are located in the Annual
Book of ASTM Standards, 1994, Vol. 11.01. Copies may be obtained from ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428.
\4\ Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or 20th edition (1998). American Public
Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005. The cited methods published in any of these three editions may be used, except
that the versions of 3111 B, 3111 D, 3113 B and 3114 B in the 20th edition may not be used.
\5\ Method I-2601-90, Methods for Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Inorganic and Organic
Constituents in Water and Fluvial Sediments, Open File Report 93-125, 1993; For Methods I-1030-85; I-1601-85; I-1700-85; I-2598-85; I-2700-85; and I-
3300-85 See Techniques of Water Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A-1, 3rd ed.,1989; Available from Information
Services, U.S. Geological Survey, Federal Center, Box 25286, Denver, CO 80225-0425.
\6\ ``Methods for the Determination of Inorganic Substances in Environmental Samples,'' EPA/600/R-93/100, August 1993. Available at NTIS, PB94-120821.
Available at NTIS, PB94-120821, 5285 Port Royal Road, Springfield, VA 22161. The toll free telephone number is 800-553-6847.
\7\ The procedure shall be done in accordance with the Technical Bulletin 601 ``Standard Method of Test for Nitrate in Drinking Water,'' July 1994, PN
221890-001, Analytical Technology, Inc. Copies may be obtained from ATI Orion, 529 Main Street, Boston, MA 02129.
\8\ Method B-1011, ``Waters Test Method for Determination of Nitrite/Nitrate in Water Using Single Column Ion Chromatography,'' August 1987. Copies may
be obtained from Waters Corporation, Technical Services Division, 34 Maple Street, Milford, MA 01757.
\9\ Method 100.1, Analytical Method For Determination of Asbestos Fibers in Water,'' EPA/600/4-83/043, EPA, September 1983. Available at NTIS, PB83-
260471.
\10\ Method 100.2, ``Determination of Asbestos Structure Over 10-um In Length In Drinking Water,'' EPA/600/R-94/134, June 1994. Available at NTIS, PB94-
201902.
\11\ Industrial Method No. 129-71W, ``Fluoride in Water and Wastewater,'' December 1972, and Method No. 380-75WE, ``Fluoride in Water and Wastewater,''
February 1976, Technicon Industrial Systems. Copies may be obtained from Bran & Luebbe, 1025 Busch Parkway, Buffalo Grove, IL 60089.
\12\ Unfiltered, no digestion or hydrolysis.
\13\ Because MDLs reported in EPA Methods 200.7 and 200.9 were determined using a 2X preconcentration step during sample digestion, MDLs determined when
samples are analyzed by direct analysis (i.e., no sample digestion) will be higher. For direct analysis of cadmium and arsenic by Method 200.7, and
arsenic by Method 3120 B sample preconcentration using pneumatic nebulization may be required to achieve lower detection limits. Preconcentration may
also be required for direct analysis of antimony, lead, and thallium by Method 200.9; antimony and lead by Method 3113 B; and lead by Method D3559-90D
unless multiple in-furnace depositions are made.
\14\ If ultrasonic nebulization is used in the determination of arsenic by Methods 200.7, 200.8, or SM 3120 B, the arsenic must be in the penta-valent
state to provide uniform signal response. For methods 200.7 and 3120 B, both samples and standards must be diluted in the same mixed acid matrix
concentration of nitric and hydrochloric acid with the addition of 100 mL of 30% hydrogen peroxide per 100 mL of solution. For direct analysis of
arsenic with method 200.8 using ultrasonic nebulization, samples and standards must contain one mg/L of sodium hypochlorite.
\15\ After January 23, 2006 analytical methods using the ICP-AES technology, may not be used because the detection limits for these methods are 0.008 mg/
L or higher. This restriction means that the two ICP-AES methods (EPA Method 200.7 and SM 3120 B) approved for use for the MCL of 0.05 mg/L may not be
used for compliance determinations for the revised MCL of 0.01 mg/L. However, prior to 2005 systems may have compliance samples analyzed with these
less sensitive methods.
\16\ The description for Method Number 1001 for lead is available from Palintest, LTD, 21 Kenton Lands Road, P.O. Box 18395, Erlanger, KY 41018. Or from
the Hach Company, P.O. Box 389, Loveland, CO 80539.
\17\ The description for the Kelada-01 Method, ``Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, And Thiocyanate,'' Revision
1.2, August 2001, EPA 821-B-01-009 for cyanide is available from the National Technical Information Service (NTIS), PB 2001-108275, 5285 Port
Royal Road, Springfield, VA 22161.
\18\ The description for the QuikChem Method 10-204-00-1-X, ``Digestion and distillation of total cyanide in drinking and wastewaters using MICRO DIST
and determination of cyanide by flow injection analysis,'' Revision 2.1, November 30, 2000 for cyanide is available from Lachat Instruments, 6645 W.
Mill Rd., Milwaukee, WI 53218, USA. Phone: 414-358-4200.
\19\ Method D6508, Rev. 2, ``Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and
Chromate Electrolyte,'' available from Waters Corp, 34 Maple St, Milford, MA, 01757, 508/482-2131 (Office), 508/482-3625 (FAX).
\20\ Method OIA-1677, DW ``Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry,'' January 2004. Available at NTIS, 5285 Port Royal
Road, Springfield, VA 22161. The toll free telephone number is 800-553-6847.
[[Page 18222]]
\21\ Sulfide levels below those detected using lead acetate paper may produce positive method interferences. Test samples using a more sensitive sulfide
method to determine if a sulfide interference is present, and treat samples accordingly.
\22\ Standard Methods On-line are available at http://www.standardmethods.org.
* * * * *
4. Section 141.24 is amended by revising the entries 23, 24, 26,
49, and 50 in the table in paragraph (e)(1) to read as follows:
Sec. 141.24 Organic chemicals, sampling and analytical requirements.
* * * * *
(e) * * *
(1) * * *
Standard
Contaminant EPA method \1\ methods ASTM Other
* * * * * * *
23. 2,4-D \4\ (as acids, salts, and 515.2, 555, 515.1, .............. D5317-93, 98 ..............
esters)................................ 515.3, 515.4 (2003)
24. 2,4,5-TP \4\ (Silvex)............... 515.2, 555, 515.1, .............. D5317-93, 98 ..............
515.3, 515.4 (2003)
* * * * * * *
26. Atrazine \2\........................ 507, 525.2, 508.1, .............. .................. ..............
505, 551.1
* * * * * * *
49. Pentachlorophenol................... 515.2, 525.2, 555, .............. D5317-93, 98 ..............
515.1, 515.3, (2003)
515.4
50. Picloram \4\........................ 515.2, 555, .............. D5317-93, 98 ..............
515.1, 515.3, (2003)
515.4
* * * * * * *
\1\ For previously approved EPA methods which remain available for compliance monitoring until June 1, 2001,
see paragraph (e)(2) of this section.
\2\ Substitution of the detector specified in 505, 507, 508, 508.1 for the purpose of achieving lower detection
limits is allowed as follows. Either an electron capture or nitrogen phosphorus detector may be used provided
all regulatory requirements and quality control criteria are met.
* * * * *
\4\ Each community and non-transient non-community water system shall take four consecutive quarterly samples
for each contaminant listed in Sec. 141.61(a)(2) through (21) during each compliance period, beginning in
the initial compliance period.
5. Section 141.25 is amended by revising the table in paragraph (a)
to read as follows.
Sec. 141.25 Analytical methods for radioactivity.
(a) * * *
--------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (method of page number)
--------------------------------------------------------------------------------------------------------
Contaminant Methodology EPA
\1\ EPA \2\ EPA \3\ EPA \4\ SM \5\ ASTM \6\ USGS \7\ DOE \8\ Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Naturally Occurring:
Gross alpha and beta.\11\.... Evaporation..... 900.0 p 1 00-01 p 1 302, 7110 B, ........... R-1120-76 .......... ........
7110 B-00
Gross alpha \11\............. Co-precipitation ...... ....... 00-02 ....... ............... 7110 C, .............. .......... ........
7110 C-00
Radium 226................... Radon Emanation. 903.1 p 16 Ra-04 p 19 305, 7500-Ra C, D3454-97 R-1141-76 Ra-04 NY \9\
7500 Ra C-01
Radio-chemical.. 903.0 p 13 Ra-03 ....... 304, 7500-Ra B, D2460-97 R-1140-76 .......... GA.\13\
7500-Ra B-01
Radium 228................... Radio-chemical.. 904.0 p 24 Ra-05 p 19 7500-Ra D, 7500- ........... R-1142-76 .......... NY \9\,
Ra D-01 NJ\10\
GA\13\
Uranium \12\................. Radio-chemical.. 908.0 ....... ......... ....... 7500-U B, 7500- ........... .............. .......... ........
U B-00
Fluorometric.... 908.1 ....... ......... ....... 7500-U C (17th 2907-97 R-1180-76, R- U-04 ........
Ed.) 1181-76
Alpha ...... ....... 00-07 p 33 7500-U C (18th, D3972-97, R-1182-76 U-02
Spectrometry. 19th, or 20th 02
Ed.), 7500-U-C-
00
Laser Phos- ...... ....... ......... ....... ............... D5174-97,
phorometry. 02
Man-Made:
[[Page 18223]]
Radioactivecesium............ Radio-chemical.. 901.0 p 4 ......... ....... 7500-Cs B, 7500- D2459-72 R-1111-76 .......... ........
Cs B-02
Gamma ray 901.1 ....... ......... p 92 7120, 7120-97 D3649-91, R-1110-76 4.5.2.3 ........
spectrometry. 98a
Radioactive iodine........... Radio-chemical.. 902.0 p 6 ......... ....... 7500-I B, 7500- ........... .............. .......... ........
I B-00
................ ...... p 9 ......... ....... 7500-I C, 7500- ........... .............. .......... ........
I C-00
................ ...... ....... ......... ....... 7500-I D, 7500- 3649-91, .............. .......... ........
I D-00 98a
Gamma ray 901.1 ....... ......... p 92 7120, 7120-97 D4785-93, .............. 4.5.2.3 ........
spectrometry. 00a
Radioactive Strontium 89, 90. Radio-chemical.. 905.0 p 29 Sr-04 p 65 303, 7500-Sr B ........... R-1160-76 Sr-01, Sr- ........
7500-Sr B-01 02
Tritium...................... Liquid 906.0 p 34 H-02 p 87 306, 7500-3H B, D4107-91, R-1171-76 .......... ........
Scintillation. 7500-3H B-00 98 (2002)
Gamma Emitters............... Gamma Ray....... 901.1 ....... ......... p 92 7120, 7120-97 D3649-91, R-1110-76 Ga-01-R ........
98a
Spectrometry.... 902.0 ....... ......... ....... 7500-Cs B, 7500- D4785-93, .............. .......... ........
Cs B-02 00a
................ 901.0 ....... ......... ....... 7500-I B, 7500- ........... .............. .......... ........
I B-00
--------------------------------------------------------------------------------------------------------------------------------------------------------
The procedures shall be done in accordance with the documents listed below. The incorporation by reference of documents 1 through 10 was approved by the
Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the documents may be obtained from the sources listed
below. Information regarding obtaining these documents can be obtained from the Safe Drinking Water Hotline at 800-426-4791. Documents may be
inspected at EPA's Drinking Water Docket, EPA West, 1301 Constitution Avenue, NW., Room B102 , Washington, DC 20460 (Telephone: 202-566-2426); or at
the Office of the Federal Register, 800 North Capitol Street, NW., Suite 700, Washington, DC.
\1\ ``Prescribed Procedures for the Measurement of Radioactivity in Drinking Water.'' EPA 600/4-80-032, August 1980. Available at the U.S. Department of
Commerce, National Technical Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161 (Telephone 800-553-6847), PB 80-224744.
\2\ ``Interim Radiochemical Methodology for Drinking Water,'' EPA 600/4-75-008(revised), March 1976. Available NTIS, 5285 Port Royal Road, Springfield,
VA 22161 (Telephone 800-553-6847), PB 253258.
\3\ ``Radiochemistry Procedures Manual,'' EPA 520/5-84-006, December, 1987. Available NTIS, 5285 Port Royal Road, Springfield, VA 22161 (Telephone 800-
553-6847), PB 84-215581.
\4\ ``Radiochemical Analytical Procedures for Analysis of Environmental Samples,'' EMSL LV 053917, March 1979. Available at NTIS, 5285 Port Royal Road,
Springfield, VA 22161 (Telephone 800-553-6847).
\5\ ``Standard Methods for the Examination of Water and Wastewater,'' 13th, 17th, 18th, 19th Editions, or 20th edition, 1971, 1989, 1992, 1995, 1998.
Available at American Public Health Association, 1015 Fifteenth Street NW., Washington, DC 20005 . Methods 302, 303, 304, 305 and 306 are only in the
13th edition. Methods 7110B, 7500-Ra B, 7500-Ra C, 7500-Ra D, 7500-U B, 7500-Cs B, 7500-I B, 7500-I C, 7500-I D, 7500-Sr B, 7500-3H B are in the 17th,
18th, 19th and 20th editions. Method 7110 C is in the 18th, 19th and 20th editions. Method 7500-U C Fluorometric Uranium is only in the 17th Edition,
and 7500-U C Alpha spectrometry is only in the 18th, 19th and 20th editions. Method 7120 is only in the 19th and 20th editions. Methods 302, 303, 304,
305 and 306 are only in the 13th edition. Method 7110 B-00, 7110 C-00, 7500-Ra B-01, 7500-Ra C-01, 7500-Ra D-01, 7500-U B-00, 7500-U C-00, 7500-I B-
00, 7500-I C-00, 7500-I D-00, 7120-97, 7500-Sr B-01, and 7500-3H B-00 are available on-line at http://www.standardmethods.org.
\6\ Annual Book of ASTM Standards, Vol. 11.02, 2002 ; American Society for Testing and Materials; any year containing the cited version of the method
may be used. Copies may be obtained from the American Society for Testing and Materials, 100 Barr Harbor Drive, West Conshohocken, PA 19428.
\7\ ``Methods for Determination of Radioactive Substances in Water and Fluvial Sediments,'' Chapter A5 in Book 5 of Techniques of Water-Resources
Investigations of the United States Geological Survey, 1977. Available at U.S. Geological Survey (USGS) Information Services, Box 25286, Federal
Center, Denver, CO 80225-0425.
\8\ ``EML Procedures Manual,'' 28th (1997) or 27th (1990) Editions, Volume 1; either edition may be used. In the 27th Edition Method Ra-04 is listed as
Ra-05 and Method Ga-01-R is listed as Sect. 4.5.4.3. Available at the Environmental Measurements Laboratory, U.S. Department of Energy (DOE), 376
Hudson Street, New York, NY 10014-3621.
\9\ ``Determination of Ra-226 and Ra-228 (Ra-02),'' January 1980, Revised June 1982. Available at Radiological Sciences Institute for Laboratories and
Research, New York State Department of Health, Empire State Plaza, Albany, NY 12201.
\10\ ``Determination of Radium 228 in Drinking Water,'' August 1980. Available at State of New Jersey, Department of Environmental Protection, Division
of Environmental Quality, Bureau of Radiation and Inorganic Analytical Services, 9 Ewing Street, Trenton, NJ 08625.
\11\ Natural uranium and thorium-230 are approved as gross alpha calibration standards for gross alpha with co-precipitation and evaporation methods;
americium-241 is approved with co-precipitation methods.
\12\ If uranium (U) is determined by mass, a 0.67 pCi/[mu]g of uranium conversion factor must be used. This conversion factor is based on the 1:1
activity ratio of U-234 and U-238 that is characteristic of naturally occurring uranium.
\13\ ``The Determination of Radium-226 and Radium-228 in Drinking Water by Gamma-ray Spectrometry Using HPGE or Ge(Li) Detectors.'' Available from the
Environmental Resources Center, Georgia Institute of Technology, 620 Cherry Street, Atlanta, GA 30332-0335, USA, Phone: 404-8944-3776.
* * * * *
6. Section 141.74 is amended by adding one sentence to the end of
footnote 1 to the table in paragraph (a)(1); and by revising paragraph
(a)(2) to read as follows:
Sec. 141.74 Analytical and monitoring requirements.
(a) * * *
(1) * * *
* * * * *
\1\* * * In addition, the following on-line versions may also be
used: 2310 B-01, 9215 B-00, 9221 A, B, C, E-99, 9222 A, B, C, D-97, and
9223-97.
* * * * *
(2) Public water systems must measure residual disinfectant
concentrations with one of the analytical methods in the following
table. If approved by the State, residual disinfectant concentrations
for free chlorine and combined chlorine also may be measured by using
DPD colorimetric test kits. In addition States may approve the use of
the ITS free chlorine test strip for the determination of free
chlorine. Use of the test strips is described in Method D99-003, ``Free
Chlorine Species'' (HOCl- and OCl-) by Test Strip,'' [Revision 3.0,
November 21, 2003], available from Industrial Test Systems, Inc., 1875
Langston St., Rock Hill SC 29730. Free and total chlorine residuals may
be measured continuously by adapting a specified chlorine residual
method for use with a continuous monitoring instrument provided the
chemistry, accuracy, and precision remain the same. Instruments used
for continuous monitoring must be calibrated with a grab sample
measurement at least every five days, or with a protocol approved by
the State.
[[Page 18224]]
--------------------------------------------------------------------------------------------------------------------------------------------------------
Residual Methodology SM1 SM on-line2 Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Free Chlorine....................... Amperometric Titration...... 4500-Cl D 4500-Cl D-00 D1253-033
DPD Ferrous Titrimetric..... 4500-Cl F 4500-Cl F-00 .................................
DPD Colorimetric............ 4500-Cl G 4500-Cl G-00 .................................
Syringaldazine (FACTS)...... 4500-Cl H 4500-Cl H-00 .................................
Total Chlorine...................... Amperometric Titration...... 4500-Cl D 4500-Cl D-00 D1253-033
Amperometric Titration (low 4500-Cl E 4500-Cl E-00 .................................
level measurement).
DPD Ferrous Titrimetric..... 4500-Cl F 4500-Cl F-00 .................................
DPD Colorimetric............ 4500-Cl G 4500-Cl G-00 .................................
Iodometric Electrode........ 4500-Cl I 4500-Cl I-00 .................................
Chlorine Dioxide.................... Amperometric Titration...... 4500-ClO2 C 4500-ClO2 C-00 .................................
DPD Method.................. 4500-ClO2 D ....................... .................................
Amperometric Titration...... 4500-ClO2 E 4500-ClO2 E-00 .................................
Spectrophotometric.......... ........................ ....................... 327.0, Revision 1.04
Ozone............................... Indigo Method............... 4500-O3 B 4500-O3 B .................................
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Except for the method for ozone residuals, the listed methods are contained in the 18th, 19th, and 20th editions of Standard Methods for the
Examination of Water and Wastewater, 1992, 1995, and 1998; the cited methods published in any of these three editions may be used. The ozone method,
4500-O3 B, is contained in the 18th, 19th, and 20th editions of Standard Methods for the Examination of Water and Wastewater, 1992, 1995, and 1998,
respectively; any of these editions may be used.
\2\ Standard Methods On-Line are available at http://www.standardmethods.org. The year in which each method was approved by the Standard Methods
Committee is designated by the last two digits in the method number. The methods listed are the only On-Line versions that may be used.
\3\ Annual Book of ASTM Standards, Vol 11.01, 2004 of any year containing the cited version of the method.
\4\ EPA Method 327.0, Revision 1.0, ``Determination of Chlorine Dioxide and Chlorite Ion in Drinking Water Using Lissamine Green B and Horseradish
Peroxidase with Detection of Visible Spectrophotometry,'' USEPA, July 2003. Available on-line at http://www.epa.gov/safewater/methods/sourcalt.html.
* * * * *
7. Section 141.131 is amended by revising paragraph (a)(2) and the
entry for ``Amperometric Detection'' in the table in paragraph (c)(1)
to read as follows:
Sec. 141.131 Analytical requirements.
(a) * * *
(2) The following documents are incorporated by reference. The
Director of the Federal Register approves this incorporation by
reference in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies
may be inspected at EPA's Drinking Water Docket, 1301 Constitution
Avenue, NW., EPA West B-102, Washington, DC 20460, or at the Office of
the Federal Register, 800 North Capitol Street, NW., Suite 700,
Washington DC. EPA Method 552.1 is in Methods for the Determination of
Organic Compounds in Drinking Water-Supplement II, USEPA, August 1992,
EPA/600/R-92/129 (available through National Information Technical
Service (NTIS), PB92-207703). EPA Methods 502.2, 524.2, 551.1, and
552.2 are in Methods for the Determination of Organic Compounds in
Drinking Water-Supplement III, USEPA, August 1995, EPA/600/R-95/131.
(available through NTIS, PB95-261616). EPA Method 300.0 is in Methods
for the Determination of Inorganic Substances in Environmental Samples,
USEPA, August 1993, EPA/600/R-93/100 (available through NTIS, PB94-
121811). EPA Method 300.1 is titled USEPA Method 300.1, Determination
of Inorganic Anions in Drinking Water by Ion Chromatography, Revision
1.0, USEPA, 1997, EPA/600/R-98/118 (available through NTIS, PB98-
169196); also available from: Chemical Exposure Research Branch,
Microbiological & Chemical Exposure Assessment Research Division,
National Exposure Research Laboratory, U.S. Environmental Protection
Agency, Cincinnati, OH 45268, Fax Number: 513-569-7757, Phone number:
513-569-7586. Standard Methods 4500-C1 D, 4500-C1 E, 4500-C1 F, 4500-C1
G, 4500-C1 H, 4500-C1 I, 4500-C1O2 D, 4500-C1O2 E, 6251 B, and 5910 B
shall be followed in accordance with Standard Methods for the
Examination of Water and Wastewater, 19th Edition, American Public
Health Association, 1995; copies may be obtained from the American
Public Health Association, 1015 Fifteenth Street, NW., Washington, DC
20005. Standard Methods 5310 B, 5310 C, and 5310 D shall be followed in
accordance with the Supplement to the 19th Edition of Standard Methods
for the Examination of Water and Wastewater, American Public Health
Association, 1996; copies may be obtained from the American Public
Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005.
Standard Method (SM) on-line are available at http://www.standardmethods.org. ASTM Method D 1253-86 shall be followed in
accordance with the Annual Book of ASTM Standards, Volume 11.01,
American Society for Testing and Materials, 1996 or any year containing
the cited version of the method may be used. ASTM Method D 1253-03
shall be followed in accordance with the Annual Book of ASTM Standards,
Volume 11.01, 2004 or any year containing the cited version of the
method may be used. Copies may be obtained from the American Society
for Testing and Materials, 100 Barr Harbor Drive, West Conshohocken, PA
19428.
* * * * *
(c) * * *
(1) * * *
Approved Methods for Disinfectant Residual Compliance Monitoring
--------------------------------------------------------------------------------------------------------------------------------------------------------
Residual measured1
-------------------------------------------------------------------
Methodology Standard Method ASTM method Combined Chlorine
Free chlorine chlorine Total chlorine dioxide
--------------------------------------------------------------------------------------------------------------------------------------------------------
Amperometric Titration........ 4500-Cl D D 1253-86, 03 X X X ...............
[[Page 18225]]
* * * * * * *
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\X indicates method is approved for measuring specified disinfectant residual.
* * * * *
PART 143--NATIONAL SECONDARY DRINKING WATER REGULATIONS
1. The authority citation for part 143 continues to read as
follows:
Authority: 42 U.S.C. 300f et seq.
2. Section 143.4 is amended by revising the table in paragraph (b)
to read as follows:
Sec. 143.4 Monitoring.
* * * * *
(b) * * *
--------------------------------------------------------------------------------------------------------------------------------------------------------
SM \4\ 18th and
Contaminant EPA ASTM \3\ 19th ed. SM \4\ 20th ed. SM \7\ On-line Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Aluminum................... 200.7\2\ .................. 3120 B 3120 B 3120 B-99 .....................
200.8\2\ .................. 3113 B ........................... 3113 B-99 .....................
200.9\2\ .................. 3111 D ........................... 3111 D-99 .....................
2. Chloride................... 300.01\1\ D4327-97, 03 4110 B 4110 B 4110 B-00 .....................
......... .................. 4500-Cl D 4500-Cl D 4500-Cl D-97 .....................
......... D512-89(99) B 4500-C1 B 4500-CI B 4500-Cl B-97 .....................
......... .................. .................. ........................... ................. D6508, Rev. 2 \6\
3. Color...................... ......... .................. 2120 B 2120 B 2120 B-01 .....................
4. Foaming Agents............. ......... .................. 5540 C 5540 C 5540 C-00 .....................
5. Iron....................... 200.7\2\ .................. 3120 B 3120 B 3120 B-99 .....................
200.9\2\ .................. 3111 B ........................... 3111 B-99 .....................
......... .................. 3113 B ........................... 3113 B-99 .....................
6. Manganese.................. 200.7 \2\ .................. 3120 B 3120 B 3120 B-99 .....................
200.8 \2\ .................. 3111 B ........................... 3111 B-99 .....................
200.9 \2\ .................. 3113 B ........................... 3113 B-99 .....................
7. Odor....................... ......... .................. 2150 B 2150 B 2150 B-97 .....................
8. Silver..................... 200.7\2\ .................. 3120 B 3120 B 3120 B-99 I-3720-85 \5\
200.8 \2\ .................. 3111 B ........................... 3111 B-99 .....................
200.9 \2\ .................. 3113 B ........................... 3113 B-99 .....................
9. Sulfate.................... 300.0 \1\ D4327-97, 03 4110 B 4110 B 4110 B-00 .....................
375.2 \1\ .................. 4500-SO4\2\ F 4500-SO4\2\ F ................. .....................
......... .................. 4500-SO42- C, D 4500-SO42- .................
......... D516-90, 02 4500-SO42- E 4500-SO42- E ................. .....................
......... .................. .................. ........................... ................. .....................
10. Total Dissolved Solids.... ......... .................. 2540 C 2540 C 2540 C-97 D6508, Rev. 2 \6\
11. Zinc...................... 200.7 \2\ .................. 3120 B 3120 B 3120 B-99 .....................
200.8 \2\ .................. 3111 B ........................... 3111 B-99 .....................
--------------------------------------------------------------------------------------------------------------------------------------------------------
The procedures shall be done in accordance with the documents listed below. The incorporation by reference of the following documents was approved by
the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the documents may be obtained from the sources
listed below. Information regarding obtaining these documents can be obtained from the Safe Drinking Water Hotline at 800-426-4791. Documents may be
inspected at EPA's Drinking Water Docket, EPA West, 1301 Constitution Avenue, NW., Room B102, Washington, DC (Telephone: 202-566-2426); or at the
Office of Federal Register, 800 North Capitol Street, NW., Suite 700, Washington, DC 20408.
\1\ ``Methods for the Determination of Inorganic Substances in Environmental Samples'', EPA/600/R-93-100, August 1993. Available at NTIS, PB94-120821.
\2\ ``Methods for the Determination of Metals in Environmental Samples--Supplement I'', EPA/600/R-94-111, May 1994. Available at NTIS, PB 95-125472.
\3\ Annual Book of ASTM Standards, 1994, 1996, or 1999, Vols. 11.01 and 11.02, American Society for Testing and Materials; any year containing the cited
version of the method may be used. Copies may be obtained from the American Society for Testing and Materials, 100 Barr Harbor Drive, West
Conshohocken, PA 19428.
\4\ Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), or 20th edition (1998). American Public
Health Association, 1015 Fifteenth Street, NW., Washington, DC 20005. The cited methods published in any of these three editions may be used, except
that the versions of 3111 B, 3111 D, and 3113 B in the 20th edition may not be used.
\5\ Method I-3720-85, Techniques of Water Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A-1, 3rd ed., 1989; Available from
Information Services, U.S. Geological Survey, Federal Center, Box 25286, Denver, CO 80225-0425.
\6\ Method D6508, Rev. 2, ``Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and
Chromate Electrolyte,'' available from Waters Corp, 34 Maple St, Milford, MA 01757, 508/482-2131 (Office), 508/482-3625 (FAX).
\7\ Standard Methods On-line are available at http://www.standardmethods.org.
PART 403--GENERAL PRETREATMENT REGULATIONS FOR EXISTING AND NEW
SOURCES OF POLLUTION
1. The authority citation for part 403 continues to read as
follows:
Authority: 33 U.S.C. 1251 et seq.
2. Section 403.12 is amended by removing the first sentence of
paragraph (b)(5)(iii) and adding in its place four new sentences to
read as follows:
Sec. 403.12 Reporting requirements for POTW's and industrial users.
* * * * *
(b) * * *
(5) * * *
(iii) Grab samples must be used for pH, temperature, cyanide, total
phenols, residual chlorine, oil and grease, sulfide, fecal coliform,
fecal streptococcus, and volatile organics, unless specified otherwise
at 40 CFR part 136. For all other pollutants, a 24-hour composite
sample, using a minimum of four (4) grab samples, must be obtained
through flow-proportional composite sampling techniques where feasible
and unless specified otherwise at 40 CFR part 136. Results of analyses
of individual grab samples for any parameter may be averaged to form
the daily average. Grab samples that are not required to be analyzed
immediately (see Table II at 40 CFR 136.3(e)) may be composited in the
laboratory, provided that container, preservation, and holding time
requirements are met (see Table II at 40 CFR 136.3(e)) and that
[[Page 18226]]
sample integrity is not compromised by compositing. * * *
* * * * *
PART 430--THE PULP, PAPER, AND PAPERBOARD POINT SOURCE CATEGORY
1. The authority citation for part 430 continues to read as
follows:
Authority: Sections 301, 304, 306, 307, 308, 402, and 501 of the
Clean Water Act, as amended, (33 U.S.C. 1311, 1314, 1316, 1317,
1318, 1342, and 1361), and Section 112 of the Clean Air Act, as
amended (42 U.S.C. 7412).
2. Section 430.02 is amended by adding paragraph (g) to read as
follows:
Sec. 430.02 Monitoring requirements.
* * * * *
(g) Analyst may use NCASI Method CP-86.07, ``Chlorinated Phenolics
in Water by In situ Acetylation and GC/MS Determination'' (January
2002) for determination of certain chlorinated phenols, chlorinated
guaiacols, chlorinated catechols, chlorinated benzaldehydes (i.e.,
vanillins and syringaldehydes), and trichlorsyringol (analytes
specified in the method) in bleach plant filtrate as an alternative to
EPA Method 1653. NCASI Method CP-86.07 is available from the
Publications Coordinator, NCASI, P.O. Box 13318, Research Triangle
Park, NC 27709-3318. Phone 919-588-1987.
PART 455--PESTICIDE CHEMICALS
1. The authority citation for part 455 continues to read as
follows:
Authority: Secs. 301, 304, 306, 307, and 501, Pub. L. 92-500, 86
Stat. 816, Pub. L. 95-217, 91 Stat. 156, and Pub. L. 100-4 (33
U.S.C. 1311, 1314, 1316, 1317, 1361).
2. Section 455.50 is revised to read as follows:
Sec. 455.50 Identification of test procedures.
The pesticide active ingredients to which this section applies and
for which effluent limitations guidelines and standards are specified
in this part are named, together with the Chemical Abstracts Service
(CAS) number (provided to assist in identifying the pesticide active
ingredient only) and analytical method(s) designation(s) in Table IG at
40 CFR 136.3(a). Except as provided in 40 CFR 136.5, the discharge
parameter values required under the Clean Water Act must be determined
by one of the analytical methods cited and described in Table IG at 40
CFR 136.3(a). Pesticide manufacturers may not use the analytical method
cited in Table 1B, Table 1C, or Table 1D of 40 CFR 136.3(a) to make
these determinations (except where the method cited in those tables is
identical to the method specified in Table IG at 40 CFR 136.3(a)). The
full texts of the analytical methods cited in Table IG at 40 CFR
136.3(a) are contained in the Methods For The Determination of
Nonconventional Pesticides In Municipal and Industrial Wastewater,
Volume I, EPA 821-R-93-010A (August 1993 Revision I) and Volume II, EPA
821-R-93-010B (August 1993) (the ``Compendium''). Each pesticide
chemical manufacturer that is required to determine discharge parameter
values under this part using one of the analytical methods cited in
Table IG at 40 CFR 136.3(a) must request in writing a copy of the
Compendium from the permit authority or local control authority (as
applicable) prior to determining such discharge parameter values,
unless the manufacturer already has a copy.
Table 7 to Part 455 [Removed and Reserved]
3. Table 7 to part 455 is removed and reserved.
PART 465--COIL COATING POINT SOURCE CATEGORY
1. The authority citation for part 465 continues to read as
follows:
Authority: Secs. 301, 304 (b), (c), (e), and (g), 306 (b) and
(c), 307 (b) and (c), and 501 of the Clean Water Act (the Federal
Water Pollution Control Act of 1972, as amended by the Clean Water
Act of 1977)(the ``Act''); 33 U.S.C. 1311, 1314 (b), (c), (e), and
(g), 1316 (b) and (c), 1317 (b) and (c), and 1361; 86 Stat. 816,
Pub. L. 92-500; 91 Stat. 1567, Pub. L. 95-217.
2. Section 465.03 is amended by revising paragraph (c) to read as
follows:
Sec. 465.03 Monitoring and reporting requirements.
* * * * *
(c) The analytical method required for determination of petroleum
hydrocarbons (non-polar material) is given under the listing for ``oil
and grease'' at 40 CFR 136.3(a), Table IB and must be used after
December 31, 2005.
* * * * *
[FR Doc. 04-6427 Filed 4-5-04; 8:45 am]
BILLING CODE 6560-50-P