Clean Water Act Methods Update Rule for the Analysis of Effluent, 10724-10771 [2023-02391]
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
ENVIRONMENTAL PROTECTION
AGENCY
40 CFR Part 136
[EPA–HQ–OW–2022–0901; FRL–9346–01–
OW]
RIN 2040–AG25
Clean Water Act Methods Update Rule
for the Analysis of Effluent
Environmental Protection
Agency (EPA).
ACTION: Proposed rule.
AGENCY:
The Environmental Protection
Agency (EPA) is proposing changes to
its test procedures required to be used
by industries and municipalities when
analyzing the chemical, physical, and
biological properties of wastewater and
other samples for reporting under EPA’s
National Pollutant Discharge
Elimination System (NPDES) permit
program. The Clean Water Act (CWA)
requires EPA to promulgate these test
procedures (analytical methods) for
analysis of pollutants. EPA anticipates
that these proposed changes would
provide increased flexibility for the
regulated community in meeting
monitoring requirements while
improving data quality. In addition, this
proposed update to the CWA methods
would incorporate technological
advances in analytical technology and
make a series of minor changes and
corrections to existing approved
methods. As such, EPA expects that
there would be no negative economic
impacts resulting from these proposed
changes.
SUMMARY:
Comments on this proposed rule
must be received on or before April 24,
2023.
ADDRESSES: You may send comments,
identified by Docket ID No. EPA–HQ–
OW–2022–0901 by any of the following
methods:
• Federal eRulemaking Portal:
https://www.regulations.gov (our
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DATES:
preferred method). Follow the online
instructions for submitting comments.
• Email: OW-Docket@epa.gov.
Include Docket ID No. EPA–HQ–OW–
2022–0901 in the subject line of the
message.
• Mail: U.S. Environmental
Protection Agency, EPA Docket Center,
Office of Water Docket, Mail Code
28221T, 1200 Pennsylvania Avenue
NW, Washington, DC 20460.
• Hand Delivery or Courier: EPA
Docket Center, WJC West Building,
Room 3334, 1301 Constitution Avenue
NW, Washington, DC 20004. The Docket
Center’s hours of operations are 8:30
a.m.–4:30 p.m., Monday–Friday (except
Federal Holidays).
Instructions: All submissions received
must include the Docket ID No. for this
rulemaking. Comments received may be
posted without change to https://
www.regulations.gov/, including any
personal information provided. For
detailed instructions on sending
comments and additional information
on the rulemaking process, see the
‘‘Public Participation’’ heading of the
SUPPLEMENTARY INFORMATION section of
this document.
FOR FURTHER INFORMATION CONTACT:
Tracy Bone, Engineering and Analysis
Division (4303T), Office of Water,
Environmental Protection Agency, 1200
Pennsylvania Avenue NW, Washington,
DC 20460–0001; telephone number:
202–564–5257; email address:
Bone.tracy@epa.gov.
SUPPLEMENTARY INFORMATION:
Table of Contents
I. Public Participation
II. General Information
III. Background
IV. Incorporation by Reference
V. Statutory and Executive order Reviews
I. Public Participation
A. Written Comments
Submit your comments, identified by
Docket ID No. EPA–HQ–OW–2022–
0901, at https://www.regulations.gov
(our preferred method), or the other
methods identified in the ADDRESSES
section. Once submitted, comments
cannot be edited or removed from the
docket. EPA may publish any comment
received to its public docket. Do not
submit to EPA’s docket at https://
www.regulations.gov any information
you consider to be Confidential
Business Information (CBI), Proprietary
Business Information (PBI), or other
information whose disclosure is
restricted by statute. Multimedia
submissions (audio, video, etc.) must be
accompanied by a written comment.
The written comment is considered the
official comment and should include
discussion of all points you wish to
make. EPA will generally not consider
comments or comment contents located
outside of the primary submission (i.e.,
on the web, cloud, or other file sharing
system). Please visit https://
www.epa.gov/dockets/commenting-epadockets for additional submission
methods; the full EPA public comment
policy; information about CBI, PBI, or
multimedia submissions; and general
guidance on making effective
comments. Publicly available docket
materials are available electronically in
www.regulations.gov at the Water
Docket in EPA Docket Center, EPA/DC,
EPA West William J. Clinton Building,
Room 3334, 1301 Constitution Avenue
NW, Washington, DC. The Public
Reading Room is open from 8:30 a.m. to
4:30 p.m., Monday through Friday,
excluding legal holidays. Any copyright
material can be viewed at the Reading
Room, please contact the EPA Docket
Center, public Reading Room. The
telephone number for the Public
Reading Room is 202–566–1744, and the
telephone number for the Water Docket
is 202–566–2426. Fax: 202–566–9744.
Email: docket-customerservice@epa.gov.
II. General Information
A. Does this action apply to me?
Entities potentially affected by the
requirements of this proposed action
include:
Category
Examples of potentially affected entities
State, Territorial, and Indian Tribal Governments.
Industry .........................
Municipalities ................
States authorized to administer the National Pollutant Discharge Elimination System (NPDES) permitting program;
states, territories, and tribes providing certification under CWA section 401; state, territorial, and tribal-owned facilities that must conduct monitoring to comply with NPDES permits.
Facilities that must conduct monitoring to comply with NPDES permits; the environmental monitoring industry.
Publicly Owned Treatment Works (POTWs) or other municipality-owned facilities 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
affected by this action. This table lists
types of entities that EPA is now aware
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of that could potentially be affected by
this action. Other types of entities not
listed in the table could also be affected.
To determine whether your facility is
affected by this action, you should
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carefully examine the applicability
language at 40 CFR 122.1 (NPDES
purpose and scope), 40 CFR 136.1
(NPDES permits and CWA) and 40 CFR
403.1 (pretreatment standards purpose
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and 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.
B. What action is the Agency taking?
Periodically, EPA proposes to update
the approved methods in 40 CFR part
136. In general, the changes proposed in
this action fall into the following
categories. The first category is updated
versions of EPA methods currently
approved in 40 CFR part 136. The
second category is new or revised
methods published by a voluntary
consensus standard body (VCSB) or the
United States Geologic Survey (USGS)
that are similar to methods previously
adopted as EPA-approved methods in
40 CFR part 136. The third category is
methods EPA has reviewed under the
agency’s national Alternate Test
Procedure (ATP) program and
preliminarily concluded are appropriate
for nationwide use. Finally, EPA is
proposing certain corrections or
amendments to the text and tables of 40
CFR part 136. EPA is proposing
adoption of these revisions to improve
data quality, update methods to keep
current with technology advances, and
provide the regulated community with
greater flexibility. The following
paragraphs provide details on the
proposed revisions.
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C. What is the agency’s authority for
taking this action?
EPA is proposing this regulation
under the authorities of sections 301(a),
304(h), and 501(a) of the CWA; 33
U.S.C. 1251, 1311(a), 1314(h) and
1361(a). Section 301(a) of the CWA
prohibits the discharge of any pollutant
into navigable waters unless the
discharge complies with, among other
provisions, an NPDES permit issued
under section 402 of the CWA. Section
304(h) of the CWA requires EPA
Administrator 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 the CWA] or permit
application pursuant to [section 402 of
the CWA].’’ Section 501(a) of the CWA
authorizes the Administrator to ‘‘. . .
prescribe such regulations as are
necessary to carry out this function
under [the CWA].’’ EPA generally has
codified its test procedure regulations
(including analysis and sampling
requirements) for CWA programs at 40
CFR part 136, though some
requirements are codified in other parts
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(e.g., 40 CFR Chapter I, Subchapters N
and O).
III. Background
This preamble describes the
abbreviations and acronyms; reasons for
the proposed rule; and a summary of the
proposed changes and clarifications; the
legal authority for the proposed rule;
methods incorporated by reference; a
summary of the proposed changes and
clarifications and solicits comment from
the public.
Abbreviations and Acronyms Used in
the Preamble and Proposed Rule Text
ADMI: American Dye Manufacturers Institute
ASTM: ASTM International 1
ATP: Alternate Test Procedure
BHI: Brain heart infusion
BOD5: 5-day Biochemical Oxygen Demand
CATC: Cyanide Amenable to Chlorination
CBI: Confidential Business Information
CFR: Code of Federal Regulations
CIE: Capillary Ion Electrophoresis
CNCl: Cyanogen Chloride
CWA: Clean Water Act
EC–MUG: EC broth with 4methylumbelliferyl-b-D-glucuronide
EDTA: Ethylenediaminetetraacetic acid
EPA: Environmental Protection Agency
DO: Dissolved Oxygen
GC: Gas Chromatography
GC/MS/MS: Gas Chromatography-Tandem
Mass Spectrometry
GC/HRMS: Gas Chromatography-High
Resolution Mass Spectrometry
ICP/AES: Inductively Coupled PlasmaAtomic Emission Spectroscopy
MIBK: Methyl Isobutyl Ketone
NED: N-(1-naphthyl)-ethylenediamine
dihydrochloride
MF: Membrane Filtration
MgCl2: Magnesium Chloride
MPN: Most Probable Number
nm: Nanometer
NPDES: National Pollutant Discharge
Elimination System
NTTAA: National Technology Transfer and
Advancement Act
QC: Quality Control
STGFAA: Stabilized Temperature Graphite
Furnace Atomic Absorption Spectroscopy
TKN: Total Kjeldahl Nitrogen
TOC: Total Organic Carbon
USGS: United States Geological Survey
VCSB: Voluntary Consensus Standards Body
NPDES permits must include
conditions designed to ensure
compliance with the technology-based
and water quality-based requirements of
the CWA, including in many cases,
restrictions on the quantity of specific
pollutants that can be discharged as
well as pollutant measurement and
reporting requirements. Often, entities
have a choice in deciding which
approved test procedure they will use
for a specific pollutant because EPA has
1 Formerly
known as the American Society for
Testing and Materials (ASTM).
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approved the use of more than one
method.2
The procedures for the analysis of
pollutants required by CWA section
304(h) are a central element of the
NPDES permit program. Examples of
where these EPA-approved analytical
methods must be used include the
following: (1) applications for NPDES
permits, (2) sampling or other reports
required under NPDES permits, (3)
other requests for quantitative or
qualitative effluent data under the
NPDES regulations, (4) State CWA 401
certifications, and (5) sampling and
analysis required under EPA’s General
Pretreatment Regulations for Existing
and New Sources of Pollution, 40 CFR
136.1 and 40 CFR 403.12(b)(5)(v).
Periodically, EPA proposes to update
the approved methods in 40 CFR part
136. In general, the changes proposed in
this action fall into the following
categories. The first category is updated
versions of EPA methods currently
approved in 40 CFR part 136. The
second is new or revised methods
published by the VCSBs or the USGS
that are similar to methods previously
adopted as EPA-approved methods in
40 CFR part 136. The third category is
methods EPA has reviewed under the
Agency’s national ATP program and
preliminarily concluded are appropriate
for nationwide use. Finally, EPA is
proposing certain corrections or
amendments to the text and tables of 40
CFR part 136. EPA is proposing
adoption of these revisions to improve
data quality, update methods to keep
current with technology advances, and
provide the regulated community with
greater flexibility. The following
paragraphs provide details on the
proposed revisions.
A. Changes to 40 CFR 136.3 To Include
New Versions of Previously Approved
EPA Methods
EPA proposes to approve revised
versions of the EPA membrane filtration
methods 1103.2, 1106.2, 1600.1, and
1603.1 found in Tables IA and IH. These
methods were approved from 2002 to
2014. The revisions include
standardizing language between the
related methods, updating to reflect
current lab practices and clarifying
edits. Copies of these proposed method
updated versions are available in the
docket to this rule.
These methods each describe a
membrane filter (MF) procedure for the
detection and enumeration of either
enterococci or Escherichia coli bacteria
2 NPDES permit regulations also specify that the
approved method needs to be sufficiently sensitive.
See 40 CFR 122.21(e)(3).
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by their growth after incubation on
selective media. These methods provide
a direct count of bacteria in water
samples based on the development of
colonies on the surface of the membrane
filter.
1. E. coli. Method 1103.2 describes a
MF procedure for the detection and
enumeration of Escherichia coli bacteria
in ambient (fresh) water and is currently
approved in Table IH. This is a two-step
method which requires transferring the
membrane filter after incubation on
membrane-Thermotolerant Escherichia
coli Agar (mTEC) to a pad saturated
with urea substrate.
2. Enterococci. Method 1106.2
describes a MF procedure for the
detection and enumeration of
enterococci bacteria in ambient water
and is currently approved in Table IH.
This is a two-step method which
requires transferring the membrane filter
after incubation on
membraneEnterococcus (mE) agar to
Esculin Iron Agar (EIA) medium.
3. Enterococci. Method 1600.1
describes a MF procedure for the
detection and enumeration of
enterococci bacteria in ambient (fresh
and marine) water and wastewater and
is currently approved in Tables IA and
IH. This is a single-step method that is
a modification of EPA Method 1106.1
(mE–EIA). The membrane filter
containing the bacterial cells is placed
on membrane-Enterococcus Indoxyl-bD-Glucoside Agar (mEI).
4. E. coli. Method 1603.1 describes a
MF procedure for the detection and
enumeration of thermotolerant
Escherichia coli bacteria in ambient
(fresh) waters and wastewaters using
Modified membrane-Thermotolerant
Escherichia coli Agar (modified mTEC)
and is currently approved in Table IA
and IH.
B. Changes to 40 CFR 136.3 To Include
New Versions of Approved ASTM
Methods
EPA is proposing to approve new
versions of ASTM methods previously
approved in 40 CFR part 136. These
changes to currently approved ASTM
methods in 40 CFR part 136 include
minor clarifications and editorial
changes. As an example, ASTM added
text to the appropriate method scope
sections to indicate that the method was
developed in accordance with the
‘‘Decision on Principles for the
Development of International Standards,
Guides and Recommendations’’ issued
by the World Trade Organization
Technical Barriers to Trade (TBT)
Committee. None of these proposed
changes will affect the performance of
the method. The following describes the
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changes to current ASTM methods that
EPA proposes to include in 40 CFR part
136. Each entry contains (in the
following order): the parameter,
proposed ASTM method number (the
last two digits in the method number
represent the year ASTM published), a
brief description of the analytical
technique, and a brief description of any
minor procedural changes (if there are
any) in this revision from the last
approved version of the method.
Method revisions that are only
formatting in nature will have no
description of the changes. The methods
listed below are organized according to
the table at 40 CFR part 136 in the order
in which they appear.
EPA proposes the following changes
to ASTM methods found in Table IB,
and Table II at 40 CFR part 136:
1. Dissolved Oxygen. D888–18 (A, B,
C), Dissolved Oxygen, Winkler,
Electrode, Luminescent-based Sensor.
Standard D888–18A measures dissolved
oxygen using the Winkler iodometric
titration procedure. The volume of
titrant used is proportional to the
concentration of dissolved oxygen in the
sample. Standard D888–18B measures
dissolved oxygen in the sample with an
electrochemical probe that produces an
electrical potential which is
logarithmically proportional to the
concentration of dissolved oxygen in the
sample. Standard D888–18C measures
dissolved oxygen with a luminescencebased sensor probe that employs
frequency domain lifetime-based
luminescence quenching and signal
processing. The 2012 versions, D888–12
(A), (B) and (C), currently are approved
in Table IB for determination of
dissolved oxygen.
2. Hydrogen Ion (pH). In D1293–18
(A, B), pH, Electrometric. The activity of
hydrogen ion (H+) in the sample is
determined electrometrically with an
ion-selective electrode in comparison to
at least two standard reference buffers
and pH is reported as the negative log
of that activity. The 1999 version
currently is approved in Table IB.
3. Metals Series. In D1976–20,
Elements in Water by InductivelyCoupled Plasma Atomic Emission
Spectroscopy for determination of
aluminum, antimony, arsenic,
beryllium, boron, cadmium, chromium,
cobalt, copper, iron, lead, magnesium,
manganese, molybdenum, nickel,
selenium, silver, thallium, vanadium,
and zinc. The sample is acid digested
and analyzed by inductively-coupled
plasma atomic emission spectroscopy
(ICP/AES) for the simultaneous or
sequential determination of 29
elements. The changes include changing
the initial instrument calibration from
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using four standards as the first option
to using only one standard and a
calibration blank. The 2012 version of
this method, D1976–12, currently is
approved in Table IB for 20 of the 29
elements.
4. Surfactants. In D2330–20,
Methylene Blue Active Substances, the
sample is mixed with an acidic aqueous
solution of methylene blue reagent,
which forms a blue-colored ion pair
with any anionic surfactants which is
subsequently extracted with chloroform
and washed with an acidic solution to
remove interferences. The intensity of
the blue color is measured using a
photometer at 650 nanometers (nm).
The concentration of methylene blue
active substances is determined in
comparison to a standard curve. The
2002 version, D2330–02, currently is
approved in Table IB for determination
of surfactants.
5. Residue, filterable and
nonfilterable. In D5907–18 (A and B),
Filterable Matter (Total Dissolved
Solids) and Nonfilterable Matter (Total
Suspended Solids) under Test Method
A, an aliquot of the sample is filtered
through a glass fiber filter and the solids
trapped on the filter are dried at 105 °C
and weighed to determine the
nonfilterable material (total suspended
solids) by difference. Under Test
Method B, the filtrate from Test Method
A, or a separate filtrate, is evaporated to
dryness at 180 °C and the residue
weighed to determine the total
dissolved solids. The 2013 version is
currently approved in Table IB.
6. Cyanide—Free. In D7237–18, Free
Cyanide, Flow Injection, followed by
Gas Diffusion Amperometry an aliquot
of the sample is introduced into a flow
injection analysis instrument, where it
mixes with a phosphate buffer to release
hydrogen cyanide which diffuses
through a hydrophobic gas diffusion
membrane into an alkaline solution and
is detected amperometrically with a
silver electrode. This version also added
new information about sulfide
interferences and potential mitigation
strategies that EPA anticipates will
improve data quality. There are no other
procedural changes. The 2015 version,
D7237–15, currently is approved in
Table IB for determination of free
cyanide.
7. Cyanide—Total. In D7284–20, Total
Cyanide, Manual Distillation with
MgCl2 followed by Flow Injection, Gas
Diffusion Amperometry, the sample is
distilled with acid and a magnesium
chloride catalyst to release cyanide to a
sodium hydroxide solution. An aliquot
of the sodium hydroxide solution is
introduced into a flow injection analysis
instrument, where it is acidified, and
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the hydrogen cyanide diffuses through a
hydrophobic gas diffusion membrane
into an alkaline solution and is detected
amperometrically with a silver
electrode. The 2017 reapproval of
D7284–13 currently is approved in
Table IB for determination of total
cyanide.
8. Organic Carbon. In D7573–18ae1,
Total Organic Carbon, Combustion, the
sample is sparged with an inert gas to
remove dissolved inorganic carbon,
acidified, and then combusted at high
temperature to convert organic carbon to
carbon dioxide. The carbon dioxide is
measured with an infra-red detector.
This version also adds data from an
interlaboratory method validation study
and new method detection limit values,
but there are no procedural changes.
The 2017 reapproval of D7573–09
currently is approved in Table IB for
determination of total organic carbon
(TOC).
C. Changes to 40 CFR 136.3 To Include
New Versions of Approved ‘‘Standard
Methods’’ Methods
EPA is proposing to approve new
versions of methods developed by the
Standard Methods Committee that were
previously approved in 40 CFR part 136.
Standard Methods has reviewed many
of their methods in preparation for
releasing the next edition of ‘‘Standard
Methods for the Examination of Water &
Wastewater.’’ The newer versions
provide clarifications and make
editorial corrections. These edits
include removal of referents to specific
brand names and trademarks,
incorporation of footnotes into the text,
a reformatting of figures, tables and
reference lists, removal of
bibliographical references that are no
longer available, small editorial changes
based on current style guides and
changes to scientific publishing
standards, and minor clarifications to
procedures based on input from users.
For example, the revisions replace
distilled water with reagent water in all
methods. As was the case with the
previous methods update rule (86 FR
27226, May 19, 2021), EPA generally
proposes to approve and include in 40
CFR part 136 only the most recent
version of a method published by the
Standard Methods Committee. EPA is
proposing to list only one version of the
method with the year of publication
designated by the last four digits in the
method number (e.g., 3111 C–2019). The
date indicates the date of the specific
revision to the method. This allows use
of a specific method in any edition of
the hard copy publication of ‘‘Standard
Methods for the Examination of Water &
Wastewater’’ that includes a method
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with the same method number and year
of publication.
The proposed revisions to methods
previously approved in 40 CFR part 136
will not affect the performance of the
method. Below is a list of the methods
EPA is proposing to include in 40 CFR
part 136. Each entry contains the
proposed Standard Methods number
and date, the parameter, and a brief
description of the analytical method.
The methods listed below are organized
according to the table at 40 CFR part
136.
EPA proposes to make the following
changes to Tables IA, IB, IC, ID and IH
at 40 CFR part 136 for the following
parameters:
1. Color. 2120 B–2021, Visual
Comparison Method, is a platinumcobalt method of measuring color, the
unit of color being that produced by one
mg platinum per liter in the form of the
chloroplatinate ion. The 1:2 ratio of
cobalt to platinum resulting from the
preparation of the standard platinumcobalt solution matches the color of
natural waters. The 2011 editorial
revision currently is approved in Table
IB for determination of color. 2120 F–
2021, American Dye Manufacturers
Institute (ADMI) Weighted-Ordinate
Spectrophotometric Method. In
accordance with the Adams-Nickerson
chromatic value formula, this method
calculates single-number color
difference values (i.e., uniform color
differences). Values are independent of
chroma and hue. Transmittance of light
is measured spectrophotometrically at
multiple wavelengths and converted to
a set of abstract numbers, which then
are converted to a single number that
indicates color value. This number is
expressed on a scale used by the ADMI.
The 2011 editorial revision currently is
approved in Table IB for determination
of color.
2. Turbidity. 2130 B–2020,
Nephelometric Method is based on a
comparison of the intensity of light
scattered by the sample under defined
conditions with the intensity of light
scattered by a standard reference
suspension under the same conditions.
The higher the intensity of scattered
light, the higher the turbidity. Formazin
polymer is used as the primary standard
reference suspension. The 2011 editorial
revision currently is approved in Table
IB for determination of turbidity.
3. Acidity. 2310 B–2020, Titration
Method measures the hydrogen ions
present in a sample as a result of
dissociation or hydrolysis of solutes that
react with additions of standard alkali.
Acidity thus depends on the endpoint
pH or indicator used. The construction
of a titration curve by recording a
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sample’s pH after successive small,
measured additions of titrant permits
identification of inflection points and
buffering capacity, if any, and allows
the acidity to be determined with
respect to any pH of interest. Samples
of industrial wastes, acid mine drainage,
or other solutions that contain
appreciable amounts of hydrolyzable
metal ions such as iron, aluminum, or
manganese are treated with hydrogen
peroxide to ensure the oxidation of any
reduced forms of polyvalent cations and
are boiled to hasten hydrolysis. Acidity
results may be highly variable if this
procedure is not followed exactly. The
2011 editorial revision currently is
approved in Table IB for determination
of acidity.
4. Alkalinity. 2320 B–2021 Titration
Method, measures the hydroxyl ions
present in a sample resulting from
dissociation or hydrolysis of solutes that
react with additions of standard acid.
Alkalinity thus depends on the
endpoint pH used. For samples of low
alkalinity (less than 20 mg/L CaCO3) an
extrapolation technique based on the
near proportionality of concentration of
hydrogen ions to excess of titrant
beyond the equivalence point is used.
The amount of standard acid required to
reduce the pH exactly 0.30 pH unit is
measured carefully. Because this change
in pH corresponds to an exact doubling
of the hydrogen ion concentration, a
simple extrapolation can be made to the
equivalence point. The 2011 editorial
revision currently is approved in Table
IB for determination of alkalinity.
5. Hardness. 2340 B–2021, Hardness
by Calculation is the preferred method
for determining hardness by calculating
it from the results of separate
determinations of calcium and
magnesium by any approved method
provided that the sum of the lowest
point of quantitation for Ca and Mg is
below the NPDES permit requirement
for hardness. The 2011 editorial revision
currently is approved in Table IB for
determination of hardness. In 2340 C–
2021, Ethylenediaminetetraacetic acid
(EDTA) Titrimetric Method, EDTA
forms a chelated soluble complex when
added to a solution of certain metal
cations. If a small amount of a dye such
as eriochrome black T or calmagite is
added to an aqueous solution containing
calcium and magnesium ions at a pH of
10.0 ± 0.1, the color of the solution
becomes wine red. If EDTA is added as
a titrant, the calcium and magnesium
will be complexed, and when all of the
magnesium and calcium has been
complexed, the solution turns from
wine red to blue, marking the endpoint
of the titration. The volume of titrant
used is proportional to hardness in the
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sample. Magnesium ion must be present
to yield a satisfactory endpoint. To
ensure this, a small amount of
complexometrically neutral magnesium
salt of EDTA is added to the buffer; this
automatically introduces sufficient
magnesium and obviates the need for a
blank correction. The 2011 editorial
revision currently is approved in Table
IB for determination of hardness.
6. Specific Conductance. 2510 B–2021
measures conductance (or resistance) in
the laboratory using a standard
potassium chloride solution and from
the corresponding conductivity, a cell
constant is calculated. Most
conductivity meters do not display the
actual solution conductance, or
resistance, rather, they generally have a
dial that permits the user to adjust the
internal cell constant to match the
conductivity of a standard. Once the cell
constant has been determined, or set,
the conductivity of an unknown
solution is displayed by the meter. The
2011 editorial revision currently is
approved in Table IB for determination
of specific conductance.
7. Residue—Total. In 2540 B–2020 an
aliquot of a well-mixed sample is
evaporated in a pre-weighed
evaporating dish at 103–105 °C to
constant weight in a 103 to 105 °C oven.
The increase compared to the empty
pre-weighed dish weight represents
total solids. The 2015 version of the
method currently is approved in Table
IB for determination of total residue. In
2540 C–2020, Total Dissolved Solids
Dried at 180 °C (Residue—filterable in
Table IB) a measured volume of a wellmixed sample is filtered through a glass
fiber filter with applied vacuum. The
entire exposed surface of the filter is
washed with at least 3 successive
volumes of reagent-grade water with
continued suction until all traces of
water are removed. The total filtrate
(with washings) is then transferred to a
pre-weighed dish and evaporated to
dryness. Successive volumes of sample
are added to the same dish after
evaporation if necessary to yield
between 2.5 and 200 mg of dried
residue. The evaporated residue is then
dried for one hour or more in an oven
at 180 °C, cooled in a desiccator to
ambient temperature, and weighed until
the weight change is less than 0.5 mg.
The 2015 version of the method
currently is approved in Table IB for
determination of filterable residue. In
2540 D–2020, Total Suspended Solids
Dried from 103 to 105 °C (Residue—
non-filterable total suspended solids
(TSS) in Table IB) a well-mixed sample
is filtered through a pre-weighed
standard glass-fiber filter. The filter and
the retained residue are then dried to a
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constant weight in a 103 to 105 °C oven.
The increase in filter weight represents
TSS. The 2015 version of the method
currently is approved in Table IB for
determination of non-filterable residue.
In 2540 E–2020, Fixed and Volatile
Solids Ignited at 550 °C (Residue—
volatile in Table IB) the residue
obtained from the determination of total
(Method 2540 B), filterable (Method
2540 C), or non-filterable residue
(Method 2540 D) is ignited at 550 ± 50
°C in a muffle furnace, cooled in a
desiccator to ambient temperature and
weighed. Repeated successive cycles of
drying, cooling, desiccating, and
weighing are performed until the weight
change is less than 0.5 mg. The
remaining solids are fixed total,
dissolved, or suspended solids, while
those lost to ignition are volatile total,
dissolved, or suspended solids. The
2015 version of the method currently is
approved in Table IB for determination
of volatile residue. In 2540 F–2020,
Settleable Solids (aka, Residue—
settleable in Table IB), a well-mixed
sample is used to fill an Imhoff cone or
graduated cylinder to the 1–L mark. The
sample is allowed to settle for 45
minutes, then gently agitated near the
sides of the cone (or graduated cylinder)
with a rod or by spinning. The sample
is then allowed to settle for another 15
minutes and the volume of settleable
solids in the cone (or graduated
cylinder) is recorded as mL/L. When
applicable, the recorded volume is
corrected for interference from pockets
of liquid volume. The 2015 version of
the method currently is approved in
Table IB for determination of settleable
residue.
8. Multiple metals by flame atomic
absorption spectrometry.
a. 3111 B–2019, Direct Air-Acetylene
Flame Method. The 2011 editorial
revision currently is approved in Table
IB for determination of antimony,
cadmium, calcium, chromium, cobalt,
copper, gold, iridium, iron, lead,
magnesium, manganese, nickel,
palladium, platinum, potassium,
rhodium, ruthenium, silver, sodium,
thallium, tin, and zinc. A sample is
aspirated into a flame and the metals are
atomized. A light beam is directed
through the flame, into a
monochromator, and onto a detector
that measures the amount of light
absorbed by the atomized metal in the
flame. Because each metal has its own
characteristic absorption wavelength, a
source lamp composed of that element
is used. The amount of energy at the
characteristic wavelength absorbed in
the flame is proportional to the
concentration of the element in the
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sample over a limited concentration
range.
b. 3111 C–2019, Extraction and AirAcetylene Flame Method consists of
chelation with ammonium pyrrolidine
dithiocarbamate (APDC) and extraction
into methyl isobutyl ketone (MIBK),
followed by aspiration into an airacetylene flame and is suitable for the
determination of low concentrations of
cadmium, chromium, cobalt, copper,
iron, lead, manganese, nickel, silver,
and zinc. The 2011 editorial revision
currently is approved in Table IB for
determination of cadmium, chromium,
cobalt, copper, iron, lead, nickel, silver,
and zinc.
EPA proposes to approve method
3111 C for manganese. This parameter
was inadvertently left off in an earlier
rulemaking approving method 3111 C.
c. 3111 D–2019, Direct Nitrous OxideAcetylene Flame Method. A sample is
aspirated into a flame produced using a
mixture of nitrous oxide and acetylene
and the metals are atomized. A light
beam is directed through the flame, into
a monochromator, and onto a detector
that measures the amount of light
absorbed by the atomized metal in the
flame. The 2011 editorial revision
currently is approved in Table IB for
determination of aluminum, barium,
beryllium, molybdenum, osmium,
titanium, and vanadium. In addition,
EPA proposes to approve method 3111
D for calcium. This parameter was
inadvertently left off in an earlier
rulemaking approving method 3111 D.
d. 3111 E–2019, Extraction and
Nitrous Oxide-Acetylene Flame Method.
The method consists of chelation with
8-hydroxyquinoline, extraction with
MIBK, and aspiration into a nitrous
oxide-acetylene flame and is suitable for
the determination of aluminum at
concentrations less than 900 mg/L and
beryllium at concentrations less than 30
mg/L. The 2011 editorial revision
currently is approved in Table IB for
determination of aluminum, and
beryllium.
9. Mercury—Total. 3112 B–2020,
Metals by Cold-Vapor Atomic
Absorption Spectrometric Method is a
flameless AA procedure based on the
absorption of radiation at 253.7 nm by
mercury vapor. The mercury in a
sample is reduced to the elemental state
and aerated from solution in a closed
system. The mercury vapor passes
through a cell positioned in the light
path of an atomic absorption
spectrophotometer. Absorbance is
measured as a function of mercury
concentration. The 2011 editorial
revision currently is approved in Table
IB for determination of mercury.
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10. Metals by AA Furnace. In 3113 B–
2020, Electrothermal Atomic Absorption
Spectrometric Method, a discrete
sample volume is dispensed into the
graphite sample tube (or cup).
Typically, determinations are made by
heating the sample in three or more
stages. First, a low current heats the
tube to dry the sample. The second, or
charring, stage destroys organic matter
and volatilizes other matrix components
at an intermediate temperature. Finally,
a high current heats the tube to
incandescence and, in an inert
atmosphere, atomizes the element being
determined. Additional stages
frequently are added to aid in drying
and charring, and to clean and cool the
tube between samples. The resultant
ground-state atomic vapor absorbs
monochromatic radiation from the
source. A photoelectric detector
measures the intensity of transmitted
radiation. The inverse of the
transmittance is related logarithmically
to the absorbance, which is directly
proportional to the number density of
vaporized ground-state atoms (the BeerLambert law) over a limited
concentration range. The 2010 version
of the method currently is approved in
Table IB for determination of aluminum,
antimony, arsenic, barium, beryllium,
cadmium, chromium, cobalt, copper,
iron, lead, manganese, molybdenum,
nickel, selenium, silver, and tin.
Although not specifically listed as target
analytes in 3113 B, the 2010 version of
the method is also approved in Table IB
for determination of gold, thallium, and
vanadium, as these elements may also
be determined using the method.
11. Arsenic and Selenium by AA
Gaseous Hydride. 3114 B–2020, Manual
Hydride Generation/Atomic Absorption
Spectrometric Method is a manual
hydride generation method that is
applicable to the determination of
arsenic and selenium by conversion to
their hydrides by sodium borohydride
reagent and transport into an atomic
absorption atomizer. The 2011 editorial
revision currently is approved in Table
IB for determination of arsenic and
selenium. 3114 C–2020, Continuous
Hydride Generation/Atomic Absorption
Spectrometric Method is a continuousflow hydride generation method that is
applicable to the determination of
arsenic and selenium by conversion to
their hydrides by sodium borohydride
reagent and transport into an atomic
absorption atomizer. The continuous
hydride generator offers the advantages
of simplicity in operation, excellent
reproducibility, low detection limits,
and high sample volume throughput for
selenium analysis following
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preparations as described in 3500–Se B
or 3114 B.4c and d. The 2011 editorial
revision currently is approved in Table
IB for determination of arsenic and
selenium.
12. Multiple Metals by ICP/AES
(Plasma Emission Spectroscopy). In
3120 B–2020, an Inductively Coupled
Plasma (ICP) source consists of a
flowing stream of argon gas ionized by
an applied radio frequency field
typically oscillating at 27.1 MHz. This
field is inductively coupled to the
ionized gas by a water-cooled coil
surrounding a quartz torch that supports
and confines the plasma. A sample
aerosol is generated in an appropriate
nebulizer and spray chamber and is
carried into the plasma through an
injector tube located within the torch.
The sample aerosol is injected directly
into the ICP, subjecting the constituent
atoms to temperatures of about 6000 to
8000 °K. Because this results in almost
complete dissociation of molecules,
significant reduction in chemical
interferences is achieved. The high
temperature of the plasma excites
atomic emission efficiently. Ionization
of a high percentage of atoms produces
ionic emission spectra. The ICP
provides an optically thin source that is
not subject to self-absorption except at
very high concentrations. Total metals
are determined after appropriate
digestion. The 2011 editorial revision
currently is approved in Table IB for
determination of aluminum, antimony,
arsenic, barium, beryllium, boron,
cadmium, calcium, chromium, cobalt,
copper, iron, lead, magnesium,
manganese, molybdenum, nickel,
potassium, selenium, silica, silver,
sodium, thallium, vanadium, and zinc.
Although not specifically listed as a
target analyte in method 3120 B, the
2011 version of the method is also
approved in Table IB for determination
of phosphorus because this element may
also be determined using the method.
13. Multiple Metals by Inductively
Coupled Plasma-Mass Spectrometry. In
this method, 3125 B–2020, Inductively
Coupled Plasma-Mass Spectrometry
(ICP–MS) Method, a sample is
introduced into an argon-based, hightemperature radio-frequency plasma,
usually via pneumatic nebulization. As
energy transfers from the plasma to the
sample stream, the target element
desolvation, atomization, and
ionization. The resulting ions are
extracted from the plasma through a
differential vacuum interface and
separated based on their mass-to-charge
(m/z) ratio by a mass spectrometer.
Typically, either a quadrupole (with or
without collision cell technology or
dynamic reaction cell) or magnetic
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sector (high-resolution) mass
spectrometer is used. An electron
multiplier detector counts the separated
ions, and a computer-based datamanagement system processes the
resulting information. The 2011
editorial revision currently is approved
in Table IB for determination of
aluminum, antimony, arsenic, barium,
beryllium, cadmium, chromium, cobalt,
copper, lead, manganese, molybdenum,
nickel, potassium, selenium, silver,
thallium, vanadium, and zinc. Although
not specifically listed as a target analyte
in method 3125 B, the 2011 version of
the method is also approved in Table IB
for determination of boron, calcium,
gold, iridium, iron, magnesium,
palladium, platinum, potassium,
rhodium, ruthenium, silica, sodium, tin,
and titanium as these elements may also
be determined using the method.
14. 3500 Colorimetric Series for
Multiple Metals.
a. Aluminum. In 3500–Al B–2020,
Eriochrome Cyanine R Method with
Eriochrome cyanine R dye, dilute
aluminum solutions buffered to a pH of
6.0 produce a red to pink complex that
exhibits maximum absorption at 535
nm. The intensity of the developed
color is influenced by the aluminum
concentration, reaction time,
temperature, pH, alkalinity, and
concentration of other ions in the
sample. To compensate for color and
turbidity, the aluminum in one portion
of a sample is complexed with EDTA to
provide a blank. The interference of iron
and manganese, two elements
commonly found in water when
aluminum is present, is eliminated by
adding ascorbic acid. The 2011 editorial
revision currently is approved in Table
IB for determination of aluminum.
b. Arsenic. In 3500–As B–2020, Silver
Diethyldithiocarbamate Method,
arsenite, containing trivalent arsenic, is
reduced selectively by aqueous sodium
borohydride solution to arsine, AsH3, in
an aqueous medium of pH 6. Arsenate,
methylarsonic acid, and dimethylarsinic
acid are not reduced under these
conditions. The generated arsine is
swept by a stream of oxygen-free
nitrogen from the reduction vessel
through a scrubber containing glass
wool or cotton impregnated with lead
acetate solution into an absorber tube
containing silver
diethyldithiocarbamate and morpholine
dissolved in chloroform. The intensity
of the red color that develops is
measured at 520 nm. The 2011 editorial
revision currently is approved in Table
IB for determination of arsenic.
c. Calcium. In 3500–Ca B–2020, EDTA
Titrimetric Method, EDTA is added to
water containing both calcium and
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magnesium, where it combines first
with the calcium. Calcium can be
determined directly, with EDTA, when
the pH is made sufficiently high that the
magnesium is largely precipitated as the
hydroxide and an indicator is used that
combines with calcium only. Several
indicators give a color change when all
the calcium has been complexed by the
EDTA at a pH of 12 to 13. The 2011
editorial revision currently is approved
in Table IB for determination calcium.
d. Chromium. 3500–Cr B–2020,
Colorimetric Method. This procedure
measures only hexavalent chromium,
(chromium VI). The hexavalent
chromium is determined
colorimetrically by reaction with
diphenylcarbazide in acid solution. A
red-violet colored complex of unknown
composition is produced. The 2011
editorial revision currently is approved
in Table IB for determination of
dissolved hexavalent chromium
(chromium VI). 3500–Cr C–2020, Ion
Chromatographic Method. This method
is applicable to determination of
dissolved hexavalent chromium in
drinking water, groundwater, and
industrial wastewater effluents. An
aqueous sample is filtered, and its pH
adjusted to between 9 and 9.5 with a
concentrated buffer. This pH adjustment
reduces the solubility of trivalent
chromium and preserves the hexavalent
chromium oxidation state. The sample
is introduced into the instrument’s
eluent stream of ammonium sulfate and
ammonium hydroxide. Trivalent
chromium in solution is separated from
the hexavalent chromium by the
column. After separation, hexavalent
chromium reacts with an azide dye to
produce a chromogen that is measured
at 530 or 540 nm. Hexavalent chromium
is identified based on retention time.
The 2011 editorial revision currently is
approved in Table IB for determination
of dissolved hexavalent chromium
(chromium VI).
e. Copper Colorimetric. In 3500–Cu
B–2020, Neocuproine Method, the
sample is treated with hydroxylamine
hydrochloride to reduce any cupric ions
(Cu2+) to cuprous ions (Cu+). Sodium
citrate is used to complex metallic ions
that might precipitate when the pH is
raised. The pH is adjusted to between 4
and 6 with ammonium hydroxide
(NH4OH), a solution of neocuproine
(2,9-dimethyl-1,10-phenanthroline) in
methanol is added, and the resultant
complex is extracted into chloroform
(CHCl3). After dilution of the CHCl3 to
an exact volume with methanol
(CH3OH), the absorbance of the solution
is measured at 457 nm. The 2011
editorial revision currently is approved
in Table IB for determination of copper.
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In 3500–Cu C–2020, Bathocuproine
Method, cuprous ion forms a watersoluble orange-colored chelate with
disodium bathocuproine disulfonate
(sodium 4,4′-(2,9-dimethyl-1,10phenanthroline-4,7diyl)dibenzenesulfonate). While the
color forms over the pH range 3.5 to
11.0, the recommended pH range is
between 4 and 5. The sample is buffered
at a pH of about 4.3 and reduced with
hydroxylamine hydrochloride. The
absorbance is measured at 484 nm. The
2011 editorial revision currently is
approved in Table IB for determination
of copper.
f. Potassium. In 3500–K B–2020,
Flame Photometric Method, trace
amounts of potassium can be
determined in either a direct-reading or
internal-standard type of flame
photometer at a wavelength of 766.5
nm. The 2011 editorial revision
currently is approved in Table IB for
determination of potassium. In 3500–K
C–2020, Potassium-Selective Electrode
Method, potassium ions are measured
potentiometrically by using a potassium
ion-selective electrode and a doublejunction, sleeve-type reference
electrode. The analysis is performed
with either a pH meter having an
expanded millivolt scale capable of
being read to the nearest 0.1 mV or a
specific-ion meter having a direct
concentration scale for potassium.
Before measurement, an ionic strength
adjustor reagent is added to both
standards and samples to maintain a
constant ionic strength. The electrode
response is measured in standard
solutions with potassium concentrations
spanning the range of interest using a
calibration line derived either by the
instrument meter or manually. The
electrode response in sample solutions
is measured following the same
procedure and potassium concentration
determined from the calibration line or
instrument direct readout. The 2011
editorial revision currently is approved
in Table IB for determination of
potassium.
g. Manganese. In 3500–Mn B–2020,
Persulfate Method, persulfate oxidation
of soluble manganous compounds to
form permanganate is carried out in the
presence of silver nitrate. The resulting
color is stable for at least 24 hours if
excess persulfate is present and organic
matter is absent. The 2011 editorial
revision currently is approved in Table
IB for determination of manganese.
h. Sodium. In 3500–Na B–2020,
Flame Emission Photometric Method a
sample is nebulized into a gas flame
under carefully controlled, reproducible
excitation conditions. The sodium
resonant spectral line at 589 nm is
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isolated by interference filters or by
light-dispersing devices such as prisms
or gratings. Emission light intensity is
measured by a phototube,
photomultiplier, or photodiode. The
light intensity at 589 nm is
approximately proportional to the
sodium concentration. The 2011
editorial revision currently is approved
in Table IB for determination of sodium.
i. Lead. In 3500–Pb B–2020, Dithizone
Method, an acidified sample containing
microgram quantities of lead is mixed
with ammoniacal citrate-cyanide
reducing solution and extracted with
dithizone in chloroform (CHCl3) to form
a cherry-red lead dithizonate. The color
of the mixed color solution is measured
photometrically. The 2011 editorial
revision currently is approved in Table
IB for determination of lead.
j. Zinc. 3500–Zn B–2020, Zincon
Method. Zinc forms a blue complex
with zincon (2-carboxy-2′-hydroxy-5′sulfoformazyl benzene) in a solution
buffered to pH 9.0. Other heavy metals
likewise form colored complexes with
zincon. Cyanide is added to complex
zinc and heavy metals. Cyclohexanone
is added to selectively free zinc from its
cyanide complex so that it can be
complexed with zincon to form a blue
color which is measured
spectrophotometrically at 620 nm.
Sodium ascorbate reduces manganese
interference. The developed color is
stable except in the presence of copper.
The 2011 editorial revision currently is
approved in Table IB for determination
of zinc.
15. 4110 Series, Ion Chromatography.
a. In 4110 B–2020, Ion
Chromatography with Chemical
Suppression of Eluent Conductivity, is
approved in Table IB for determination
of bromide, chloride, fluoride, nitrate,
nitrite, orthophosphate, and sulfate. A
water sample is injected into a stream of
eluent and passed through a series of
ion exchangers. The anions of interest
are separated based on their relative
affinities for a low-capacity, strongly
basic anion exchanger (guard and
analytical columns). The separated
anions are directed through a
suppressor device that provides
continuous suppression of eluent
conductivity and enhances analyte
response. In the suppressor, the
separated anions are converted to their
highly conductive acid forms while the
conductivity of the eluent is greatly
decreased. The separated anions in their
acid forms are measured by
conductivity. They are identified based
on retention time as compared to
standards. Quantitation is by
measurement of peak area or peak
height. The 2011 editorial revision
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currently is approved in Table IB for
determination of bromide, chloride,
fluoride, nitrate, combined nitratenitrite, nitrite, orthophosphate, and
sulfate.
b. 4110 C–2020, Single-Column Ion
Chromatography with Direct
Conductivity Detection. An aqueous
sample is injected into an ion
chromatograph consisting of an injector
port, analytical column, and
conductivity detector. The sample
merges with the eluent stream and is
pumped through the analytical column
where the anions are separated based on
their affinity for the active sites of the
column packing material.
Concentrations are determined by direct
conductivity detection without
chemical suppression. The 2011
editorial revision currently is approved
in Table IB for determination of
bromide, chloride, fluoride, nitrate,
combined nitrate-nitrite, nitrite,
orthophosphate, and sulfate.
c. 4110 D–2020, Ion Chromatographic
Determination of Oxyhalides and
Bromide. The sample is analyzed in a
manner similar to that in 4110 B–2020.
However, bromate has been shown to be
subject to positive interferences in some
matrices. The interference is noticeable
usually as a flattened peak. It often can
be eliminated by passing the sample
through an H+ off-line solid-phase
extraction (SPE) cartridge, by selection
of a different column-eluent
combination, or by diluting the eluent,
which will increase retention times and
spread the chromatogram. Additionally,
chloride or a nontarget analyte present
in unusually high concentration may
overlap with a target analyte sufficiently
to cause problems in quantitation or
may cause retention-time shifts.
Dilution of the sample may resolve this
problem. The 2011 editorial revision
currently is approved in Table IB for
determination of bromide.
16. Inorganic Anions by CIE/UV
(Capillary Ion Electrophoresis). In 4140
B–2020, Capillary Ion Electrophoresis
with Indirect UV Detection, the sample
is introduced at the cathodic end of the
capillary and anions are separated based
on their differences in mobility in the
electric field as they migrate through the
capillary. Cations migrate in the
opposite direction and are not detected.
Water and neutral organics are not
attracted toward the anode. They
migrate after the anions and thus do not
interfere with anion analysis. Anions
are detected as they displace charge-forcharge the UV-absorbing electrolyte
anion (chromate), causing a net decrease
in UV absorbance in the analyte anion
zone compared to the background
electrolyte. Detector polarity is reversed
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to provide positive millivolt response to
the data system. As in chromatography,
the analytes are identified by their
migration time and quantitated by using
time-corrected peak area relative to
standards. The 2011 editorial revision
currently is approved in Table IB for
determination of bromide, chloride,
fluoride, nitrate, combined nitratenitrite, nitrite, orthophosphate, and
sulfate.
17. 4500 Series, Chloride.
a. 4500–Cl¥ B–2021, Titrimetric
Method. In a neutral or slightly alkaline
solution, potassium chromate can
indicate the endpoint of the silver
nitrate titration of chloride. Silver
chloride is precipitated quantitatively
before red silver chromate is formed. In
this version of the method approved by
the Standard Methods Committee in
2021, additional information regarding
removal of interferences caused by
sulfide, thiosulfate, and sulfite ions by
digestion of the sample with hydrogen
peroxide prior to titration has been
added to the sample preparation
procedures. A tighter pH range of 8–10,
as opposed to 7–10, is specified for
adjustment of the pH of the sample prior
to titration. A reference has been added
for the 2021 Standard Methods Joint
Task Group validation report titled:
‘‘Interlaboratory validation study for the
use of H2O2 with boiling for determining
Cl¥.’’ The 2011 editorial revision
currently is approved in Table IB for
determination of chloride.
b. 4500–Cl¥ C–2021, Mercuric Nitrate
Method. Chloride can be titrated with
mercuric nitrate, Hg(NO3)2, because of
the formation of soluble, slightly
dissociated mercuric chloride. In the pH
range 2.3 to 2.8, diphenylcarbazone
indicates the titration endpoint by
formation of a purple complex with the
excess mercuric ions. Xylene cyanol FF
serves as a pH indicator and endpoint
enhancer. Increasing the strength of the
titrant and modifying the indicator
mixtures extend the range of measurable
chloride concentrations. The 2011
editorial revision currently is approved
in Table IB for determination of
chloride.
c. 4500–Cl¥ D–2021, Potentiometric
Method. Chloride is determined by
potentiometric titration with silver
nitrate solution with a glass and silversilver chloride electrode system. During
titration, an electronic voltmeter is used
to detect the change in potential
between the two electrodes. The
endpoint of the titration is that
instrument reading at which the greatest
change in voltage has occurred for a
small and constant increment of silver
nitrate added. The 2011 editorial
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revision currently is approved in Table
IB for determination of chloride.
d. 4500–Cl¥ E–2021, Automated
Ferricyanide Method. Thiocyanate ion is
liberated from mercuric thiocyanate by
the formation of soluble mercuric
chloride. In the presence of ferric ion,
free thiocyanate ion forms a highly
colored ferric thiocyanate, of which the
intensity is proportional to the chloride
concentration. The 2011 editorial
revision currently is approved in Table
IB for determination of chloride.
18. 4500 Series Cyanide Total or
Available.
a. 4500–CN¥ B–2021, Manual
Distillation (as Preliminary Treatment of
Samples). Total cyanides are measured
after preliminary treatment of samples
for preservation and to remove
interferences. The preliminary treatment
required depends on which interfering
substances the samples contain.
Distillation removes many interfering
substances, but other pretreatment
procedures will be needed for sample
containing sulfides, fatty acids,
oxidizing agents, nitrites, and nitrates.
The 2016 version of the method
currently is approved in Table IB for
preliminary treatment of samples to be
used for determination of cyanide.
b. 4500–CN¥ C–2021, Total Cyanide
after Distillation. Hydrogen cyanide
(HCN) is liberated from an acidified
sample by distillation and purging with
air, with the HCN gas collected in a
NaOH scrubbing solution. The cyanide
concentration in the scrubbing solution
is determined via titrimetric,
colorimetric, or potentiometric
procedures. The 2016 version of the
method currently is approved in Table
IB for preliminary treatment of samples
to be used for determination of cyanide.
c. 4500–CN¥ D–2021, Titrimetric
Method. CN¥ in the alkaline distillate
from the preliminary treatment
procedures (4500–CN¥ B and C) is
titrated with standard silver nitrate
(AgNO3) to form the soluble cyanide
complex Ag(CN)2¥. As soon as all CN¥
has been complexed and a small excess
of Ag+ has been added, the silversensitive indicator, pdimethylaminobenzalrhodanine, detects
the excess Ag+ and immediately changes
color from yellow to salmon. The 2016
version of the method currently is
approved in Table IB for determination
of cyanide.
d. 4500–CN¥ E–2021,
Spectrophotometric Method. Total CN¥
in the alkaline distillate from the
preliminary treatment procedures
(4500–CN¥ B and C) is converted to
cyanogen chloride (CNCl) by reaction
with chloramine-T at pH <8 without
hydrolyzing to cyanate (CNO¥). After
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the reaction is complete, adding a
pyridine-barbituric acid reagent turns
CNCl a red-blue color. Maximum color
absorbance in aqueous solution is
between 575 and 582 nm. The 2016
version of the method currently is
approved in Table IB for determination
of cyanide.
e. 4500–CN¥ F–2021, Ion Selective
Electrode Method. Total CN¥ in the
alkaline distillate from the preliminary
treatment procedures (4500–CN¥ B and
C) is determined potentiometrically by
using a CN¥-ion selective electrode.
The 2016 version of the method
currently is approved in Table IB for
determination of cyanide.
f. 4500–CN¥ G–2021, Cyanides
Amenable to Chlorination after
Distillation. Available cyanide, or
cyanide amenable to chlorination
(CATC), can be determined when a
portion of the sample is chlorinated at
high pH and cyanide levels in the
chlorinated sample are determined after
manual distillation followed by
titrimetric or spectrophotometric
measurement. CATC is calculated by the
difference between the results for
cyanide in the unchlorinated sample
and the results for the chlorinated
sample. The 2016 version of the method
currently is approved in Table IB for
preliminary treatment of samples to be
used for determination of available
cyanide.
g. 4500–CN¥ N–2021, Total Cyanide
after Distillation by Flow Injection
Analysis. Total cyanides are digested
and steam-distilled from the sample
(4500–CN¥ C), The cyanide in this
distillate is converted to CNCl by
reaction with chloramine-T at pH <8.
The CNCl then forms a red-blue dye by
reacting with pyridine-barbituric acid
reagent. The absorbance of this red dye
is measured at 570 nm and is
proportional to the total or weak acid
dissociable cyanide in the sample. The
2016 version of the method currently is
approved in Table IB for determination
of cyanide.
19. 4500 Total Fluoride Series.
a. 4500–F¥ B–2021, Preliminary
Distillation Step. Fluoride is separated
from other nonvolatile constituents in
water by conversion to hydrofluoric or
fluosilicic acid and subsequent
distillation. The conversion is
accomplished by using a strong, highboiling acid. To protect against
glassware etching, hydrofluoric acid is
converted to fluosilicic acid by using
soft glass beads. Quantitative fluoride
recovery is accomplished by using a
relatively large sample. Acid and sulfate
carryover are minimized by distilling
over a controlled temperature range.
The 2011 editorial revision currently is
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approved in Table IB for preliminary
treatment of samples to be used for
determination of fluoride.
b. 4500–F¥ C–2021, Ion-Selective
Electrode Method. The fluoride
electrode is an ion-selective sensor that
measures the ion activity of fluoride in
solution rather than concentration. The
key element in the fluoride electrode is
the laser-type doped lanthanum fluoride
crystal across which a potential is
established by fluoride solutions of
different concentrations. The crystal
contacts the sample solution at one face
and an internal reference solution at the
other. Fluoride ion activity depends on
the solution total ionic strength and pH,
and on fluoride complexing species.
Adding an appropriate buffer provides a
nearly uniform ionic strength
background, adjusts pH, and breaks up
complexes. In effect, the electrode
measures concentration. The 2011
editorial revision currently is approved
in Table IB for determination of
fluoride.
c. 4500–F¥ D–2021, SPADNS Method.
The SPADNS colorimetric method is
based on the reaction between fluoride
and a ‘‘lake’’ of zirconium-dye. Fluoride
reacts with the dye lake, dissociating a
portion of it into a colorless complex
anion (ZrF62¥) and the dye. As the
amount of fluoride increases, the color
produced becomes progressively lighter
and absorbance is measured
colorimetrically at 570 nm. The 2011
editorial revision currently is approved
in Table IB for determination of
fluoride.
d. 4500–F¥ E–2021, Complexone
Method. The sample is distilled in the
automated system, and the distillate is
reacted with alizarin fluorine bluelanthanum reagent to form a blue
complex that is measured
colorimetrically at 620 nm. The 2011
editorial revision currently is approved
in Table IB for determination of
fluoride.
20. 4500 Hydrogen ion (pH). 4500–H+
B–2021, Electrometric Method. The
basic principle of electrometric pH
measurement is determination of the
activity of the hydrogen ions by
potentiometric measurement using a
standard hydrogen electrode and a
reference electrode. The hydrogen
electrode consists of a platinum
electrode across which hydrogen gas is
bubbled at a pressure of 101 kilopascal.
Because of difficulty in its use and the
potential for poisoning the hydrogen
electrode, the glass electrode commonly
is used. The electromotive force (emf)
produced in the glass electrode system
varies linearly with pH. This linear
relationship is described by plotting the
measured emf against the pH of
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different buffers. A sample’s pH is
determined by extrapolation. This
version of the method adds information
to Section 2—Apparatus, regarding
equipment that may be used for manual
or automatic temperature compensation.
The 2011 editorial revision currently is
approved in Table IB for determination
of pH.
21. 4500 Kjeldahl Nitrogen (TKN)
Series.
a. 4500–Norg B–2021, Macro-Kjeldahl
Method. In the presence of sulfuric acid
(H2SO4), potassium sulfate (K2SO4), and
a cupric sulfate (CuSO4) catalyst, amino
nitrogen of many organic materials is
converted to ammonium. Free ammonia
also is converted to ammonium. After
the addition of base, the ammonia is
distilled from an alkaline medium and
absorbed in boric or sulfuric acid. The
ammonia may be determined
colorimetrically, by ammonia-selective
electrode, or by titration with a standard
mineral acid. The 2011 editorial
revision currently is approved in Table
IB for preliminary treatment of samples
to be used for determination of total
Kjeldahl nitrogen (TKN).
b. 4500–Norg C–2021, Semi-MicroKjeldahl Method. This is a reducedvolume version of 4500 Norg B that
specifies use of Kjeldahl flasks with a
capacity of 100 mL in a semi-microKjeldahl digestion apparatus equipped
with heating elements to accommodate
Kjeldahl flasks and a suction outlet to
vent fumes. The 2011 editorial revision
currently is approved in Table IB for
preliminary treatment of samples to be
used for determination of total Kjeldahl
nitrogen (TKN).
c. 4500–Norg D–2021, Block Digestion
and Flow Injection Analysis. Samples
are digested in a block digestor with
sulfuric acid and copper sulfate as a
catalyst. The digested sample is injected
onto the FIA manifold, where its pH is
controlled by raising it to a known,
basic pH by neutralization with a
concentrated buffer. This in-line
neutralization converts the ammonium
cation to ammonia, and also prevents
undue influence of the sulfuric acid
matrix on the pH-sensitive color
reaction that follows. The ammonia thus
produced is heated with salicylate and
hypochlorite to produce a blue color
that is proportional to the ammonia
concentration. The color is intensified
by adding sodium nitroprusside. The
presence of EDTA in the buffer prevents
the precipitation of calcium and
magnesium. The resulting peak’s
absorbance is measured at 660 nm. The
peak area is proportional to the
concentration of total Kjeldahl nitrogen
in the original sample. The 2011
editorial revision currently is approved
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in Table IB for determination of total
Kjeldahl nitrogen.
22. 4500–NH3 Nitrogen (Ammonia as
nitrogen) Series.
a. 4500–NH3 B–2021, Preliminary
Manual Distillation Step. The sample is
buffered at pH 9.5 with a borate buffer
to decrease hydrolysis of cyanates and
organic nitrogen compounds. It is
distilled into a solution of boric acid
when titration is to be used, or into
H2SO4, when the phenate method is
used as the determinative step. The
ammonia in the distillate can be
determined either colorimetrically by
the phenate method or titrimetrically
with standard H2SO4 and a mixed
indicator or a pH meter. Ammonia in
the distillate also can be determined by
the ammonia-selective electrode
method, using 0.04 N H2SO4 to trap the
ammonia. This revision replaces
instructions for storage of ammonia-free
water with instructions for preparation
of ammonia-free water using an ion
exchange resin and simply says that if
high blank values are produced, the
analyst should prepare fresh ammoniafree water. The 2011 editorial revision
currently is approved in Table IB for
preliminary treatment of samples to be
used for determination of ammonia.
b. 4500–NH3 C–2021, Titration
Method. The titrimetric method is used
only on samples that have been carried
through preliminary distillation.
Ammonia is titrated with a standardized
sulfuric acid titrant using a mixed
indicator of methyl red and methylene
blue. The 2011 editorial revision
currently is approved in Table IB for
determination of ammonia as well as for
determination of total Kjeldahl nitrogen
after appropriate digestion/distillation
of the sample.
c. 4500–NH3 D–2021, Electrode
Method. The ammonia-selective
electrode uses a hydrophobic gaspermeable membrane to separate the
sample solution from an electrode
internal solution of ammonium
chloride. Dissolved ammonia (NH3(aq)
and NH4∂) is converted to NH3(aq) by
raising the pH to above 11 with a strong
base. NH3(aq) diffuses through the
membrane and changes the internal
solution pH that is sensed by a pH
electrode. The fixed level of chloride in
the internal solution is sensed by a
chloride ion-selective electrode that
serves as the reference electrode of the
sample. Potentiometric measurements
are made with a pH meter having an
expanded millivolt scale or with a
specific ion meter. The 2011 editorial
revision currently is approved in Table
IB for determination of ammonia, as
well as for determination of total
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Kjeldahl nitrogen after appropriate
digestion/distillation of the sample.
d. 4500–NH3 E–2021, Electrode
Method. Ammonia is determined using
an ammonia-selective electrode. When a
linear relationship exists between
concentration and response, known
addition is convenient for measuring
occasional samples because no
calibration is needed. Because an
accurate measurement requires that the
concentration at least double as a result
of the addition, sample concentration
must be known within a factor of three.
The total concentration of ammonia can
be measured in the absence of
complexing agents down to 0.8 mg/L
NH3-N or in the presence of a large
excess (50 to 100 times) of complexing
agent. The 2011 editorial revision
currently is approved in Table IB for
determination of ammonia, as well as
for determination of total Kjeldahl
nitrogen after appropriate digestion/
distillation of the sample.
e. 4500–NH3 F–2021, Phenate Method.
An intensely blue compound,
indophenol, is formed by the reaction of
ammonia, hypochlorite, and phenol
catalyzed by sodium nitroprusside. The
color is measured
spectrophotometrically at 640 nm. The
2011 editorial revision currently is
approved in Table IB for determination
of ammonia, as well as for
determination of total Kjeldahl nitrogen
after appropriate digestion/distillation
of the sample.
f. 4500–NH3 G–2021, Semi-Automated
Phenate Method. Alkaline phenol and
hypochlorite react with ammonia to
form indophenol blue that is
proportional to the ammonia
concentration. The blue color formed is
intensified with sodium nitroprusside.
The color is measured
spectrophotometrically at 630 to 660
nm. The 2011 editorial revision
currently is approved in Table IB for
determination of ammonia, as well as
for determination of total Kjeldahl
nitrogen after appropriate digestion/
distillation of the sample.
g. 4500–NH3 H–2021, SemiAutomated Phenate Method. A water
sample containing ammonia or
ammonium cation is injected into an
FIA carrier stream to which a
complexing buffer (alkaline phenol) and
hypochlorite are added. This reaction,
the Berthelot reaction, produces the
blue indophenol dye. The blue color is
intensified by the addition of
nitroferricyanide. The resulting peak’s
absorbance is measured at 630 nm. The
peak area is proportional to the
concentration of ammonia in the
original sample. The 2011 editorial
revision currently is approved in Table
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IB for determination of ammonia, as
well as for determination of total
Kjeldahl nitrogen after appropriate
digestion/distillation of the sample.
23. 4500–NO2¥ Nitrite as Nitrogen.
4500–NO2¥ B–2021,
Spectrophotometric Method. Nitrite
(NO2¥) in a sample is determined
through formation of a reddish-purple
azo dye produced at pH 2.0 to 2.5 by
coupling diazotized sulfanilamide with
N-(1-naphthyl)-ethylenediamine
dihydrochloride (NED) and absorbance
is measured spectrophotometrically at
543 nm. The 2011 editorial revision
currently is approved in Table IB for
determination of nitrite.
24. 4500–NO3¥ Nitrogen (Nitrite/
Nitrate as Nitrogen Series).
a. 4500–NO3¥ D–2019, Nitrate
Electrode Method. Nitrate is measured
using an ion-selective electrode that
develops a potential across a thin, inert
membrane holding in place a waterimmiscible liquid ion exchanger. The
2016 version of the method currently is
approved in Table IB for determination
of nitrate.
b. 4500–NO3¥ E–2019, Cadmium
Reduction Method. Nitrate (NO3–) is
reduced almost quantitatively to nitrite
(NO2–) in the presence of cadmium (Cd).
This method uses commercially
available Cd granules treated with
copper sulfate (CuSO4) and packed in a
glass column. The NO2– is then
diazotized with sulfanilamide and
coupled with NED to form a highly
colored azo dye that is measured
spectrophotometrically. To correct for
any NO2– present in the sample before
NO3– reduction, samples also must be
analyzed without the reduction step.
The 2016 version of the method
currently is approved in Table IB for
determination of nitrate (by
subtraction), as well as for
determination of combined nitrate +
nitrite, and for determination of nitrite
singly when bypassing the reduction
step.
c. 4500–NO3¥ F–2019, Automated
Cadmium Reduction Method. This is an
automated version of the cadmium
reduction method 4500 NO3– E. Nitrate
in a sample is reduced to nitrite using
cadmium reduction and then diazotized
with sulfanilamide and coupled with
NED to form a highly colored azo dye
that is measured
spectrophotometrically. To correct for
any NO2– present in the sample before
NO3– reduction, samples also must be
analyzed without the reduction step.
The 2016 version of the method
currently is approved in Table IB for
determination of nitrate (by
subtraction), as well as for
determination of combined nitrate +
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nitrite, and for determination of nitrite
singly when bypassing the reduction
step.
d. 4500–NO3¥ H–2019, Automated
Hydrazine Reduction Method. Nitrate in
a sample is reduced to nitrite using
hydrazine sulfate then diazotized with
sulfanilamide and coupled with NED to
form a highly colored azo dye that is
measured spectrophotometrically. The
2016 version of the method currently is
approved in Table IB for determination
of combined nitrate and nitrite.
e. 4500–NO3¥ I–2019, Cadmium
Reduction Flow Injection Method. A
sample is passed through a copperized
cadmium column to quantitatively
reduce its nitrate content to nitrite. The
nitrite is diazotized with sulfanilamide
and coupled with NED to yield a watersoluble dye with a magenta color whose
absorbance at 540 nm is proportional to
the nitrate + nitrite in the sample.
Nitrite concentrations may be
determined by bypassing the cadmium
column and nitrate concentration may
be calculated by subtraction of the result
for the nitrite concentration from the
result for the combined nitrate + nitrite
concentration. The 2016 version of the
method currently is approved in Table
IB for determination of nitrate, as well
as for determination of combined nitrate
+ nitrite, and for determination of nitrite
singly by bypassing the reduction step.
25. 4500–O Oxygen (Dissolved) Series.
a. 4500–O B–2021, Iodometric
Methods. A divalent manganese
solution is added and then a strong
alkali is added to a sample in a glassstoppered bottle and dissolved oxygen
(DO) rapidly oxidizes an equivalent
amount of the dispersed divalent
manganous hydroxide precipitate into
higher-valency hydroxides. Oxidized
manganese reverts to the divalent state
in the presence of iodide ions in an
acidic solution, liberating an amount of
iodine equivalent to the original DO
content. The iodine is then titrated with
a standard thiosulfate solution. The
2016 version of the method currently is
approved in Table IB for determination
of dissolved oxygen.
b. 4500–O C–2021, Azide
Modification. The sample is treated with
manganous sulfate, potassium
hydroxide, and potassium iodide (the
latter two reagents combined in one
solution) and finally sulfuric acid. The
initial precipitate of manganous
hydroxide, Mn(OH)2, combines with the
dissolved oxygen in the sample to form
a brown precipitate, manganic
hydroxide, MnO(OH)2. Upon
acidification, the manganic hydroxide
forms manganic sulfate, which acts as
an oxidizing agent to release free iodine
from the potassium iodide. The iodine,
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which is stoichiometrically equivalent
to the dissolved oxygen in the sample,
is then titrated with sodium thiosulfate
or phenylarsine oxide (PAO). The azide
modification effectively removes nitrite
interference, which is the most common
interference in biologically treated
effluents and incubated biochemical
oxygen demand (BOD) samples. The
2016 version of the method currently is
approved in Table IB for determination
of dissolved oxygen.
c. 4500–O D–2021, Permanganate
Modification. The permanganate
modification is used only on samples
containing Fe(II) (e.g., acid mine water).
Concentrated sulfuric acid, potassium
permanganate in solution and
potassium fluoride in solution are
added to the sample. Enough KMnO4
solution is added to obtain a violet tinge
that persists for 5 minutes. 0.5 to 1.0 mL
potassium oxalate solution is then
added only until permanganate color is
removed completely. From this point,
the procedure closely parallels that in
4500–O C. The 2016 version of the
method currently is approved in Table
IB for determination of dissolved
oxygen.
d. 4500–O E–2021, Alum Flocculation
Modification. Samples high in
suspended solids may consume
appreciable quantities of iodine in acid
solution. The interference due to solids
may be removed by alum flocculation.
Concentrated ammonium hydroxide and
aluminum potassium sulfate solution
are added to a sample. The sample is
allowed to settle for about 10 min and
the clear supernatant is siphoned into a
250- to 300-mL DO bottle until it
overflows. From this point, the
procedure closely parallels that in
4500–O C. The 2016 version of the
method currently is approved in Table
IB for determination of dissolved
oxygen.
e. 4500–O F–2021, Copper SulfateSulfamic Acid Flocculation
Modification. This modification is used
for biological flocs (e.g., activated sludge
mixtures), which have high oxygen
utilization rates. A copper sulfatesulfamic acid inhibitor solution is
added to the sample. The suspended
solids are allowed to settle, and the
relatively clear supernatant liquor is
siphoned into a 250- to 300-mL DO
bottle. From this point, the procedure
closely parallels that in 4500–O C. The
2016 version of the method currently is
approved in Table IB for determination
of dissolved oxygen.
f. 4500–O G–2021, Electrode Method.
Oxygen-sensitive polarographic or
galvanic membrane electrodes are
composed of two solid metal electrodes
in contact with supporting electrolyte
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separated from the test solution by a
selective membrane. Polyethylene and
fluorocarbon membranes are commonly
used because they are permeable to
molecular oxygen and are relatively
rugged. The diffusion current is linearly
proportional to the molecular-oxygen
concentration. The measured current
can be converted easily to concentration
units (e.g., mg/L) by a number of
calibration procedures. The 2016
version of the method currently is
approved in Table IB for determination
of dissolved oxygen.
g. 4500–O H–2021, Luminescencebased Method. The optical probe uses
luminescence-based oxygen sensors to
measure the light-emission
characteristics of a luminescent
reaction; oxygen quantitatively
quenches the luminescence. The change
in the luminescence signal’s lifetime
correlates to the DO concentration. The
2016 version of the method currently is
approved in Table IB for determination
of dissolved oxygen.
26. 4500–P Phosphorus Total and
Ortho Phosphorus Series.
a. 4500–P B–2021, Digestion Sample
Preparation. Because phosphorus may
occur in combination with organic
matter, a digestion method to determine
total phosphorus must be able to oxidize
organic matter effectively to release
phosphorus as orthophosphate. Three
digestion methods are given in 4500–P
B.3, 4, and 5. The perchloric acid
method in B.5 is the most vigorous and
time-consuming method, and is
recommended for particularly difficult
samples, such as sediments. The nitric
acid-sulfuric acid method is
recommended for most samples. The
simplest digestion method that may be
used for determination of total
phosphorus is the persulfate oxidation
technique in which 50 mL of an
unfiltered sample is boiled with sulfuric
acid and either ammonium persulfate or
potassium persulfate for approximately
30–40 minutes or until a final volume
of about 10 mL is reached. The 2011
editorial revision is currently approved
in Table IB for preliminary treatment of
samples to be used for determination of
total phosphorus as orthophosphorus
using manual or automated versions of
the ascorbic acid reduction, colorimetric
methods.
b. 4500–P E–2021, Manual Method.
Ammonium molybdate and antimony
potassium tartrate react in an acid
medium with orthophosphate to form
phosphomolybdic acid, a heteropoly
acid that is reduced to intensely colored
molybdenum blue by ascorbic acid and
is measured spectrophotometrically.
This revision adds that possible
interference from silicate should be
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evaluated when reporting
concentrations less than 10 mg/L. The
2011 editorial revision currently is
approved in Table IB for determination
of total phosphorus after digestion of the
sample, as well as for determination of
orthophosphorus in a filtered,
undigested sample.
c. 4500–P F–2021, Automated
Ascorbic Acid Reduction Method.
Ammonium molybdate and antimony
potassium tartrate react with
orthophosphate in an acid medium to
form an antimony-phosphomolybdate
complex, which on reduction with
ascorbic acid yields an intense blue
color suitable for photometric
measurement using continuous flow
analytical equipment. The 2011
editorial revision currently is approved
in Table IB for determination of total
phosphorus after digestion of the
sample, as well as for determination of
orthophosphorus in a filtered,
undigested sample.
d. 4500–P G–2021, Automated.
Ammonium molybdate and antimony
potassium tartrate react with
orthophosphate in an acid medium to
form an antimony-phosphomolybdate
complex, which on reduction with
ascorbic acid yields an intense blue
color suitable for photometric
measurement using flow injection
analysis. The 2011 editorial revision
currently is approved in Table IB for
determination of total phosphorus after
digestion of the sample as well, as for
determination of orthophosphorus in a
filtered, undigested sample.
e. 4500–P H–2021, Automated Total
Phosphorus. Samples are manually
digested using the approved procedure
for preliminary treatment of samples to
be used for determination of total
phosphorus. When the resulting
solution is injected onto the manifold,
the orthophosphate ion reacts with
ammonium molybdate and antimony
potassium tartrate under acidic
conditions to form a complex. This
complex is reduced with ascorbic acid
to form a blue complex suitable for
photometric measurement using flow
injection analysis. The 2011 editorial
revision currently is approved in Table
IB for determination of total
phosphorus.
27. 4500–S2¥ Sulfide Series.
a. 4500–S2¥ B–2021, Sample
Pretreatment. Dissolved sulfide is
measured by first removing insoluble
matter. This is done by adding sodium
hydroxide and aluminum chloride
solutions producing an aluminum
hydroxide floc that is settled, leaving a
clear supernatant for analysis. The 2011
editorial revision currently is approved
in Table IB for preliminary treatment of
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samples to be used for determination of
sulfide.
b. 4500–S2¥ C–2021, Sample
Pretreatment. Interferences due to
sulfite, thiosulfate, iodide, and many
other soluble substances, but not
ferrocyanide, are eliminated by first
precipitating zinc sulfide (ZnS) by
addition of sodium hydroxide and zinc
acetate solutions, removing the
supernatant, and replacing it with
reagent water. The same procedure is
used even when not needed for removal
of interferences, to concentrate sulfide
prior to analysis. The 2011 editorial
revision currently is approved in Table
IB for preliminary treatment of samples
to be used for determination of sulfide.
c. 4500–S2¥ D–2021, Colorimetric
Method. The methylene blue method is
based on the reaction of sulfide, ferric
chloride, and dimethyl-pphenylenediamine to produce
methylene blue. Ammonium phosphate
is added after color development to
remove ferric chloride color, which is
measured photometrically. The
procedure is applicable at sulfide
concentrations between 0.1 and 20.0
mg/L. There are no other procedural
changes. The 2011 editorial revision
currently is approved in Table IB for
determination of sulfide.
d. 4500–S2¥ F–2021, Titrimetric.
Iodine oxidizes sulfide in acid solution.
A titration based on this reaction is an
accurate method for determining sulfide
at concentrations above 1 mg/L if
interferences are absent and if loss of
H2S is avoided. The 2011 editorial
revision currently is approved in Table
IB for determination of sulfide.
e. 4500–S2¥ G–2021, Ion-Selective
Electrode Method. The potential of a
sulfide ion-selective electrode (ISE) is
related to the sulfide ion activity. An
alkaline antioxidant reagent (AAR) is
added to samples and standards to
inhibit oxidation of sulfide by oxygen
and to provide a constant ionic strength
and pH. Use of the AAR allows
calibration in terms of total dissolved
sulfide concentration. All samples and
standards must be at the same
temperature. Sulfide concentrations
between 0.032 mg/L and 100 mg/L can
be measured without preconcentration.
For lower concentrations,
preconcentration is necessary. The 2011
editorial revision currently is approved
in Table IB for determination of sulfide.
28. 4500–SiO2 Silica Series.
a. 4500–SiO2 C–2021, Colorimetric
Method. Ammonium molybdate at pH
approximately 1.2 reacts with silica and
any phosphate present to produce
heteropoly acids. Oxalic acid is added
to destroy the molybdophosphoric acid,
but not the molybdosilicic acid. Even if
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phosphate is known to be absent, the
addition of oxalic acid is highly
desirable and is a mandatory step. The
intensity of the yellow color produced
is proportional to the concentration of
molybdate-reactive silica and is
measured photometrically. The 2011
editorial revision currently is approved
in Table IB for determination of silica.
b. 4500–SiO2 E–2021, Automated
Method for Molybdate-Reactive Silica.
Ammonium molybdate at pH
approximately 1.2 reacts with silica and
any phosphate present to produce
heteropoly acids. Oxalic acid is added
to destroy the molybdophosphoric acid,
but not the molybdosilicic acid. The
yellow molybdosilicic acid is reduced
by means of amino naphthol sulfonic
acid to heteropoly blue. The blue color
is more intense than the yellow color of
4500–SiO2 C and provides increased
sensitivity. The 2011 editorial revision
currently is approved in Table IB for
determination of silica.
c. 4500–SiO2 F–2021, Automated
Method for Molybdate-Reactive Silicate.
Silicate reacts with molybdate under
acidic conditions to form yellow betamolybdosilicic acid. This acid is
subsequently reduced with stannous
chloride to form a heteropoly blue
complex that is measured
photometrically. Oxalic acid is added to
reduce the interference from phosphate.
The 2011 editorial revision currently is
approved in Table IB for determination
of silica.
29. 4500–SO42¥Sulfate Series.
a. 4500–SO42¥C–2021, Gravimetric
Method with Ignition of Residue. Sulfate
is precipitated in a hydrochloric acid
(HCl) solution as barium sulfate (BaSO4)
by the addition of barium chloride
(BaCl2). The precipitation is carried out
near the boiling temperature, and after
a period of digestion, the precipitate is
filtered, washed with water until free of
Cl¥, ignited at 800 °C for an hour and
weighed as BaSO4. The 2011 editorial
revision currently is approved in Table
IB for determination of sulfate.
b. 4500–SO42¥D–2021, Gravimetric
Method with Drying of Residue. Sulfate
is precipitated in a hydrochloric acid
(HCl) solution as barium sulfate (BaSO4)
by the addition of barium chloride
(BaCl2). The precipitation is carried out
near the boiling temperature, and after
a period of digestion the precipitate is
filtered, washed with water until free of
Cl¥, dried to a constant weight in an
oven at 105 °C or higher, and weighed
as BaSO4. The 2011 editorial revision
currently is approved in Table IB for
determination of sulfate.
c. 4500–SO42¥E–2021, Turbidimetric
Method. Sulfate ion (SO42¥) is
precipitated in an acetic acid medium
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with barium chloride (BaCl2) to form
barium sulfate (BaSO4) crystals of
uniform size. Light absorbance of the
BaSO4 suspension is measured by a
photometer and the SO42¥
concentration is determined by
comparison of the reading with a
standard curve. The 2011 editorial
revision currently is approved in Table
IB for determination of sulfate.
d. 4500–SO42¥F–2021, Automated
Colorimetric Method. Barium sulfate is
formed by the reaction of the SO42¥
with barium chloride (BaCl2) at a low
pH. At high pH, excess barium reacts
with methylthymol blue (MTB) to
produce a blue chelate. The
uncomplexed methylthymol blue is
gray. The intensity of gray
(uncomplexed methylthymol blue) is
measured photometrically and is
proportional to concentration of sulfate.
The 2011 editorial revision currently is
approved in Table IB for determination
of sulfate.
e. 4500–SO42¥G–2021, Automated
Colorimetric Method. At pH 13.0,
barium forms a blue complex with MTB.
The sample is injected into a low, but
known, concentration of sulfate. The
sulfate from the sample then reacts with
the ethanolic barium-MTB solution and
displaces the MTB from the barium to
give barium sulfate and uncomplexed
MTB. Uncomplexed MTB has a grayish
color. The pH is raised with NaOH and
the gray color of the uncomplexed MTB
is measured photometrically. The
intensity of the gray color is
proportional to the sulfate
concentration. The 2011 editorial
revision currently is approved in Table
IB for determination of sulfate.
30. Sulfite 4500–SO32¥B–2021,
Titrimetric Iodometric Method. An
acidified sample containing sulfite
(SO32¥) is titrated with a standardized
potassium iodide-iodate titrant. Free
iodine, liberated by the iodide-iodate
reagent, reacts with SO32¥. The titration
endpoint is signaled by the blue color
resulting from the first excess of iodine
reacting with a starch indicator. The
2011 editorial revision currently is
approved in Table IB for determination
of sulfite.
31. 5520 Oil and Grease Series.
a. 5520 B–2021, Liquid-Liquid,
Partition-Gravimetric Method. Dissolved
or emulsified oil and grease is extracted
from water by intimate contact with an
extracting solvent (n-hexane). The
extract is dried over sodium sulfate. The
solvent is then distilled from the extract
and the hexane extractable material is
desiccated and weighed. Some
extractables, especially unsaturated fats
and fatty acids, oxidize readily; hence,
special precautions regarding
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temperature and solvent vapor
displacement are included to minimize
this effect. Organic solvents shaken with
some samples may form an emulsion
that is very difficult to break. This
method includes a means for handling
such emulsions. Recovery of solvents is
discussed. Solvent recovery can reduce
both vapor emissions to the atmosphere
and costs. The 2011 editorial revision
currently is approved in Table IB for
determination of oil and grease (hexane
extractable material or HEM).
b. 5520 F–2021, Hydrocarbons. The
oil and grease extracted by 5520 B is
used for this test. When only
hydrocarbons are of interest, this
procedure is introduced before final
measurement. When hydrocarbons are
to be determined after total oil and
grease has been measured, redissolve
the extracted oil and grease in n-hexane.
Silica gel has the ability to adsorb polar
materials. The solution of extracted
hydrocarbons and fatty materials in nhexane is mixed with silica gel, and the
fatty acids are removed selectively from
solution. The solution is filtered to
remove the silica gel, the solvent is
distilled, and the silica gel treated
hexane extractable material (SGT–HEM)
is weighed. The materials not
eliminated by silica gel adsorption are
designated hydrocarbons by this test.
The 2011 editorial revision currently is
approved in Table IB for determination
of oil and grease (hexane extractable
material or HEM).
32. 5530 Phenols Series.
a. 5530 B–2021, Manual Distillation.
Phenols, defined as hydroxy derivatives
of benzene and its condensed nuclei,
may occur in domestic and industrial
wastewaters, natural waters, and potable
water supplies. Phenols are distilled
from nonvolatile impurities. Because
the volatilization of phenols is gradual,
the distillate volume must ultimately
equal that of the original sample. The
2010 version of the method currently is
approved in Table IB for preliminary
treatment of samples to be used for
determination of phenols.
b. 5530 D–2021, Colorimetric Method.
Steam-distillable phenolic compounds
react with 4-aminoantipyrine at pH 7.9
± 0.1 in the presence of potassium
ferricyanide to form a colored
antipyrine dye. This dye is kept in
aqueous solution and the absorbance is
measured photometrically at 500 nm.
The 2010 version of the method
currently is approved in Table IB for
determination of phenol. Note that for
regulatory compliance monitoring
required under the Clean Water Act, the
colorimetric reaction must be performed
at a pH of 10.0 ± 0.2 as stated in 40 CFR
136.3, Table IB, footnote 27.
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33. 5540 Surfactants.
5540 C–2021. This colorimetric
method comprises three successive
extractions from an acid aqueous
medium containing excess methylene
blue into chloroform (CHCl3), followed
by an aqueous backwash and
measurement of the blue color in the
CHCl3 by spectrophotometry at 652 nm.
The method is applicable at methylene
blue active substances concentrations
down to about 0.025 mg/L. The 2011
editorial revision currently is approved
in Table IB for determination of
surfactants.
34. 6200 Volatile Organic
Compounds Series.
a. In the 6200 B–2020, Purge and Trap
Capillary-Column Gas
Chromatographic/Mass Spectrometric
(GC/MS) Method, volatile organic
compounds are transferred efficiently
from the aqueous to the gaseous phase
by bubbling an inert gas (e.g., helium)
through a water sample contained in a
specially designed purging chamber at
ambient temperature. The vapor is
swept through a sorbent trap that
adsorbs the analytes of interest. After
purging is complete, the trap is heated
and back-flushed with the same inert
gas to desorb the compounds onto a gas
chromatographic column. The gas
chromatograph is temperatureprogrammed to separate the
compounds. The detector is a mass
spectrometer. The 2011 editorial
revision currently is approved in Table
IC for determination of benzene,
bromodichloromethane, bromoform,
bromomethane, carbon tetrachloride,
chlorobenzene, chloroethane,
chloroform, chloromethane,
dibromochloromethane, 1,2dichlorobenzene, 1,3-dichlorobenzene,
1,4-dichlorobenzene,
dichlorodifluoromethane, 1,1dichloroethane, 1,2-dichloroethane, 1,1dichloroethene, trans-1,2dichloroethene, 1,2-dichloropropane,
cis-1,3-dichloropropene, trans-1,3dichloropropene, ethylbenzene,
methylene chloride, 1,1,2,2tetrachloroethane, tetrachloroethene,
toluene, 1,1,1-trichloroethane, 1,1,2trichloroethane, trichloroethene,
trichlorofluoromethane, and vinyl
chloride.
b. 6200 C–2020, Purge and Trap
Capillary-Column Gas Chromatographic
(GC) Method. Volatile organic
compounds are transferred efficiently
from the aqueous to the gaseous phase
by bubbling an inert gas (e.g., helium)
through a water sample contained in a
specially designed purging chamber at
ambient temperature. The vapor is
swept through a sorbent trap that
adsorbs the analytes of interest. After
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purging is complete, the trap is heated
and back-flushed with the same inert
gas to desorb the compounds onto a gas
chromatographic column. The gas
chromatograph is temperatureprogrammed to separate the compounds
and detected using a photoionization
detection and an electrolytic
conductivity detection in series. The
2011 editorial revision currently is
approved in Table IC for determination
of benzene, bromodichloromethane,
bromoform, bromomethane, carbon
tetrachloride, chlorobenzene,
chloroethane, chloroform,
chloromethane, dibromochloromethane,
1,2-dichlorobenzene, 1,3dichlorobenzene, 1,4-dichlorobenzene,
1,1-dichloroethane, 1,2-dichloroethane,
1,1-dichloroethene, trans-1,2dichloroethene, 1,2-dichloropropane,
cis-1,3-dichloropropene, trans-1,3dichloropropene, ethylbenzene,
methylene chloride, 1,1,2,2tetrachloroethane, tetrachloroethene,
toluene, 1,1,1-trichloroethane, 1,1,2trichloroethane, trichloroethene,
trichlorofluoromethane, and vinyl
chloride.
35. 6410 Extractable Base/Neutrals
and Acids.
6410 B–2020, Liquid-Liquid
Extraction Gas Chromatographic/Mass
Spectrometric Method. This method is
applicable to the determination of
organic compounds that are partitioned
into an organic solvent and are
amenable to gas chromatography in
municipal and industrial discharges. A
measured volume of sample is extracted
serially with methylene chloride at a pH
of approximately 2 and again at pH 11.
The extract is dried, concentrated, and
analyzed by GC/MS. Qualitative
compound identification is based on
retention time and relative abundance of
three characteristic masses (m/z).
Quantitative analysis uses internalstandard techniques with a single
characteristic m/z. This revision adds a
note that although the method was
validated extracting base neutrals first
and then acids, performance may be
improved by extracting acids first and
then base neutrals. In addition, EPA
proposes to approve method 6410–B for
endrin aldehyde in Table ID. This
parameter was inadvertently left off the
2000 MUR rulemaking. The 2000
version of the method currently is
approved in Table IC for determination
of acenaphthene, acenaphthylene,
anthracene, benzidine,
benzo(a)anthracene, benzo(a)pyrene,
benzo(b)fluoranthene,
benzo(g,h,i)perylene,
benzo(k)fluoranthene, butyl benzyl
phthalate, bis(2-chloroethoxy) methane,
bis(2-chloroethyl) ether, bis(2-
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ethylhexyl) phthalate,
bromodichloromethane, 4-bromophenyl
phenyl ether, 4-chloro-3-methyl phenol,
2-chloronaphthalene, 2-chlorophenol, 4chlorophenyl phenyl ether, chrysene,
dibenzo(a,h)anthracene, 3,3′dichlorobenzidine, 2,4-dichlorophenol,
diethyl phthalate, 2,4-dimethylphenol,
dimethyl phthalate, di-n-butyl
phthalate, di-n-octyl phthalate, 2,4dinitrophenol, 2,4-dinitrotoluene, 2,6dinitrotoluene, fluoranthene, fluorene,
hexachlorobenzene,
hexachlorobutadiene,
hexachlorocyclopentadiene,
indeno(1,2,3-c,d) pyrene, isophorone, 2methyl-4,6-dinitrophenol, naphthalene,
nitrobenzene, 2-nitrophenol, 4nitrophenol, n-nitrosodi-n-propylamine,
n-nitrosodiphenylamine, PCB–1016,
PCB–1221, PCB–1232, PCB–1242, PCB–
1248, PCB–1254, PCB–1260,
pentachlorophenol, phenanthrene,
phenol, pyrene, 1,2,4-trichlorobenzene,
and 2,4,6-trichlorophenol and in Table
ID for determination of aldrin, a-BHC, bBHC, d-BHC, g-BHC (lindane),
chlordane, 4,4′-DDD, 4,4′-DDE, 4,4′DDT, dieldrin, endosulfan I, endosulfan
II, endosulfan sulfate, endrin,
heptachlor, heptachlor epoxide, and
toxaphene.
36. 6420 Phenols.
6420 B–2020, Liquid-Liquid
Extraction Gas Chromatographic
Method. A measured volume of sample
is acidified and extracted with
methylene chloride. The extract is dried
and exchanged to 2-propanol during
concentration. Target analytes in the
extract are separated by gas
chromatography and are identified by
retention time and measured with a
flame ionization detector, or derivatized
and measured with an electron capture
detector. This revision of the method
replaces distilled, deionized water with
reagent water, adds that the packed
columns used for validation of the
method are no longer available or
recommended, and includes
information on alternative capillary
columns that may be used. The 2000
version of the method currently is
approved in Table IC for determination
of 4-chloro-3-methylphenol, 2chlorophenol, 2,4-dichlorophenol, 2,4dimethylphenol, 2,4-dinitrophenol, 2methyl-4,6-dinitrophenol, 2nitrophenol, 4-nitrophenol,
pentachlorophenol, phenol, and 2,4,6trichlorophenol.
37. 6440 Polynuclear Aromatic
Hydrocarbons.
6440 B–2021, Liquid-Liquid
Extraction Chromatographic Method. A
measured volume of sample is extracted
with methylene chloride. The extract is
dried, concentrated, and separated by
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the high-performance liquid
chromatographic (HPLC) or gas
chromatographic (GC) method.
Ultraviolet (UV) and fluorescence
detectors are used with HPLC to identify
and measure the polynuclear aromatic
hydrocarbons. A flame ionization
detector is used with GC. The 2005
version of the method currently is
approved in Table IC for determination
of acenaphthene, acenaphthylene,
anthracene, benzo(a)anthracene,
benzo(a)pyrene, benzo(b)fluoranthene,
benzo(g,h,i)perylene,
benzo(k)fluoranthene, chrysene,
dibenzo(a,h)anthracene, fluoranthene,
fluorene, indeno(1,2,3-c,d)pyrene,
naphthalene, phenanthrene, and pyrene.
38. 6630 Organochlorine Pesticides
Series.
a. 6630 B–2021, Liquid-Liquid
Extraction Gas Chromatographic
Method I, in this procedure, the
pesticides are extracted with a mixed
solvent, diethyl ether-hexane or
methylene chloride-hexane, by either
liquid-liquid extraction using a
separatory funnel or by continuous
liquid-liquid extraction. The extract is
concentrated by evaporation and, if
necessary, is cleaned up by column
adsorption chromatography. The
individual pesticides then are separated
by gas chromatography and the
compounds are measured with an
electron capture detector (ECD). This
revision of the method adds information
regarding alternative capillary columns
that may be used in place of the packed
columns that were used for validation of
the method, removes information
regarding preparation of packed
columns, replaces information regarding
manual injection technique with use of
an autosampler and states that gas
chromatography/mass spectrometry
(GC/MS) may be used for confirmatory
analyses in place of a second column
and ECD detection. There are no other
procedural changes. The 2007 version of
the method currently is approved in
Table ID for determination of aldrin, aBHC, b-BHC, d-BHC, g-BHC (lindane),
captan, carbophenothion, chlordane,
4,4′-DDD, 4,4′-DDE, 4,4′-DDT, dichloran,
dieldrin, endosulfan I, endosulfan II,
endrin, heptachlor, heptachlor epoxide,
isodrin, malathion, methoxychlor,
mirex, parathion methyl, parathion
ethyl, PCNB, strobane, toxaphene, and
trifluralin.
b. In 6630 C–2021, Liquid-Liquid
Extraction Gas Chromatographic
Method II, a measured volume of
sample is extracted with methylene
chloride either by liquid-liquid
extraction using separatory funnels or
by continuous liquid-liquid extraction.
The extract is dried and exchanged to
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hexane during concentration. The target
analytes are separated by gas
chromatography and the compounds are
measured with an electron capture
detector (ECD). This revision of the
method adds information regarding
alternative capillary columns that may
be used in place of the packed columns
that were used for validation of the
method, and states that gas
chromatography/mass spectrometry
(GC/MS) may be used for confirmatory
analyses in place of a second column
and ECD detection. There are no other
procedural changes. The 2007 version of
the method currently is approved in
Table ID for determination of aldrin, aBHC, b-BHC, d-BHC, g-BHC (lindane),
chlordane, 4,4′-DDD, 4,4′-DDE, 4,4′DDT, dieldrin, endosulfan I, endosulfan
II, endosulfan sulfate, endrin, endrin
aldehyde, heptachlor, heptachlor
epoxide, isodrin, methoxychlor, mirex,
PCNB, strobane, and toxaphene.
39. 6640 Acidic Herbicide
Compounds.
6640 B–2021, Micro Liquid-Liquid
Extraction Gas Chromatographic
Method. A 40-mL sample is adjusted to
pH ≥12 with 4 N sodium hydroxide and
is kept for 1 hour at room temperature
to hydrolyze derivatives. Because the
chlorphenoxy acid herbicides are
formulated as a variety of esters and
salts, the hydrolysis step is required and
may not be skipped. The aqueous
sample then is acidified with sulfuric
acid to pH ≤1 and extracted with 4 mL
of methyl tert-butyl ether (MtBE) that
contains the internal standard. The
chlorinated acids, which have been
partitioned into the MtBE, then are
converted to methyl esters by
derivatization with diazomethane. The
target esters are separated and detected
by capillary column gas
chromatography using an electron
capture detector (GC/ECD). Analytes are
quantified using an internal-standardbased calibration curve. The 2006
editorial revision currently is approved
in Table IC for determination of 2,4–D,
2,4,5–T, and 2,4,5–TP (Silvex).
D. Changes to 40 CFR 136.3 To Include
Alternate Test Procedures in Table IC
To promote method innovation, EPA
maintains a program that allows method
developers to apply for EPA review and
potential approval of an alternative
method to an existing approved method.
This alternate test procedure (ATP)
program is described for CWA
applications at 40 CFR 136.4 and 136.5.
EPA is proposing two ATPs for
nationwide use. Based on EPA’s review,
the performance of these ATPs is
equally effective as other methods
already approved for measurement of
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2,3,7,8-substituted tetra- through octachlorinated dibenzo-p-dioxins and
dibenzofurans (PCDDs/PCDFs) in
wastewater. The ATP applicants
supplied EPA with study reports that
contain the data from their validation
studies. These study reports, the final
methods, and the letters documenting
EPA’s review are included as supporting
documents in the docket for this
proposed rule.
These proposed new methods are:
SGS AXYS Method ATM 16130,
‘‘Determination of 2,3,7,8-Substituted
Tetra- through Octa-Chlorinated
Dibenzo-p-Dioxins and Dibenzofurans
(CDDs/CDFs) Using Waters and Agilent
Gas Chromatography-Tandem-Mass
Spectrometry (GC/MS/MS), Revision 1.0
and Pace Analytical Method PAM–
16130–SSI, ‘‘Determination of 2,3,7,8Substituted Tetra- through OctaChlorinated Dibenzo-p-Dioxins and
Dibenzofurans (CDDs/CDFs) Using
Shimadzu Gas Chromatography Mass
Spectrometry (GC–MS/MS), Revision
1.1.’’ These ATPs are the results of
separate collaborative efforts between
SGS AXYS Analytical Services Ltd, and
the instrument manufacturers Waters
Corporation, Agilent Technologies, and
between Pace Analytical Services LLC
and the instrument manufacturer
Shimadzu Scientific Instruments, Inc.
These final methods are heavily adapted
from Method 1613B. Neither ATP makes
changes to the extraction or cleanup
procedures specified in Method 1613B.
All required quality control tests (or
analogous tests) and associated QC
acceptance criteria have been included
in both SGS AXYS 16130 and PAM–
16130–SSI.
To minimize costs to both the
applicants and the Agency where
possible, SGS AXYS, Pace Analytical,
and the instrument manufacturers who
collaborated on these methods worked
closely with EPA’s CWA ATP
Coordinator to design single-laboratory
validation studies for these methods.
The goal of these validation studies was
to demonstrate that all of the
performance criteria specified in
Method 1613B could be met and that
comparable performance could be
achieved when using GC–MS/MS
instrumentation for determination of
PCDDs/PCDFs in extracts from realworld samples.
EPA Method 1613B was promulgated
at 40 CFR 136 in 1995 and remains the
only approved method for dioxins and
furans at NPDES permit levels (Methods
613 and 625.1 may only be used for
screening). Method 1613B is also the
only method approved at 40 CFR part
136 that relies on gas chromatographyhigh resolution mass spectrometry (GC/
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HRMS) as the determinative technique.
As a result, the need for GC/HRMS
instruments is somewhat limited, and
market forces have led some instrument
vendors to move away from supporting
new GC/HRMS instrumentation. In
addition, in the last 30 years, there has
been substantial consolidation of
manufacturers, with the disappearance
of many of the vendors whose
instruments were used to develop and
validate Method 1613B.
In these two methods, referred to in
the rule as ATM 16130 and PAM
16130–SSI, each sample is spiked with
the same suite of carbon-13 labeled
standards prior to extraction and those
standards are used for isotope dilution
quantitation in the same way as is done
in EPA Method 1613B. All of the
relevant QC acceptance criteria are the
same in the methods as well. The
difference between these methods and
the approved EPA method is the use of
an MS/MS detector system that uses
Multiple Reaction Monitoring (MRM) in
place of a high resolution mass
spectrometer (HRMS) detector system.
The GC portions of the methods did not
change.
E. Corrections or Amendments to the
Text and Tables of 40 CFR Part 136
In addition to the method revisions
discussed in Section II.C of this
preamble, Standard Methods has
revised certain of their general quality
control sections (2020, 3020, 4020 and
5020). EPA is proposing to update the
year of the current references to these
sections in 136.3 Table IB footnote 85,
as well as add a reference to an
additional Standard Methods Quality
Control Section: Part 6000 Individual
Organic Compounds, 6020, based on
EPA’s review of these sections. These
Quality Control Standards are available
for download at
www.standardmethods.org at no charge.
Further, during the preparation of this
proposed rulemaking, EPA identified
several minor errors or inconsistencies
in the tables of approved methods.
Therefore, EPA is proposing the
following changes to 40 CFR 136.3,
Tables IA, IB, IC or ID:
1. Table IA. Removing the units of
‘‘number per 100 mL’’ under parameter
1. Coliform (fecal), because parameter 1
is specifically for biosolids that are
reported as ‘‘number per gram dry
weight’’.
2. Table IA. Moving USGS Method
‘‘B–0050–85’’ from parameter 1.
Coliform (fecal) number per gram dry
weight to parameter 2. Coliform (fecal)
number per 100 mL, to address an error
from the previous rulemaking when
Parameter 1 Coliform (fecal) was split
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into two parameters to eliminate
confusion as to which methods were
approved for biosolids.
3. Table IA. Moving the phrase ‘‘twostep’’ in parameter 3, in the ‘‘Method’’
column from the second to the third line
which returns the phrase to the proper
line after having been inadvertently
moved.
4. Table IB. Revising footnote 85 to
remove bullet formatting.
5. Table IB. EPA proposes adding
footnote 86 to Method 419D, listed as an
approved method for determination
nitrate using Colorimetric (Brucine
sulfate) methodology. This addition
corrects a long-standing typographical
error regarding the appropriate footnote
for this method in Table IB.
6. Table IB. Correcting an inadvertent
error to footnote 57. The reference
number was incorrectly changed to
335.4–1. The correct number is 335.4.
7. Tables IC and ID. Proposes adding
footnote 15 to the Standard Method
Column header and adding footnote 15
to refer to Quality Control Section: Part
6000 Individual Organic Compounds,
6020 (2019).
8. Table IC. The parameter 39,
dichlorodifluoromethane, should refer
to Method 6200 B rather than 6200 C for
the GC/MS method.
9. Table IC. Parameters 66–72, 95, 96
and 97. These parameters are missing
the footnote 10 that was inadvertently
dropped in an earlier rulemaking.
Footnote 10 to table IC applies to all of
the 17 dioxin and furan congeners.
10. Table IH. Parameter 2 has method
B–0025–85 is moved down one row
because it was inadvertently moved.
This method is a one-step membrane
filtration (MF) method rather than a
most probable number (MPN) method.
11. Footnote 5 to Table II for the
preservation and holding time
requirements for cyanide to add the year
(2015) of the ASTM method D7365–09a
(15). This practice is applicable for the
collection and preservation of water
samples for the analysis of cyanide.
Samples are collected in appropriate
containers and mitigated for known
interferences either in the field during
sample collection or in the laboratory
prior to analysis. The sampling,
preservation and mitigation of
interference procedures described in
this practice are recommended for the
analysis of total cyanide, available
cyanide, weak acid dissociable cyanide,
and free cyanide by ASTM Methods
D2036, D4282, D4374, D6888, D6994,
D7237, D7284, and D7511.
The recommended sampling and
preservation procedures in the ASTM
method have not changed since 2009,
but the change to footnote 5 will
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19:11 Feb 17, 2023
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simplify identification of the current
method that is available from ASTM
International. The 2015 reapproval date
was already updated in footnote 6 to
Table II in the 2021 methods update
rule; however, adding the reapproval
date was overlooked in the IBR section
and in footnote 5 to Table II.
F. Changes to 40 CFR 136.3 To Include
New Standard Methods Committee
Methods Based on Previously Approved
Technologies
EPA is proposing adding five new
methods in furtherance of the National
Technology Transfer and Advancement
Act of 1995 (NTTAA), Public Law 104–
113, that provides that Federal agencies
and departments shall use technical
standards developed or adopted by the
VCSBs if compliance would not be
inconsistent with applicable law or
otherwise impracticable. These methods
were submitted by Standard Methods
and are consistent with other already
approved methods. EPA is adding 4500–
CN– P–2021, 4500–CN– Q–2021, 4500
CN– R–2021, 4500–F¥ G–2021 to Table
IB for cyanide and fluoride and is
adding 5520 G–2021 to Table IB for oil
and grease, based on the following
reasons:
1. Cyanide. Although method 4500–
CN– P–2021, Total Cyanide by
Segmented Flow Injection, UVIrradiation with Gas Diffusion, and
Amperometric Measurement is new to
Standard Methods for the Examination
of Water and Wastewater, it is based on
ASTM D7511–12(17), which is
approved in Table IB for determination
of total cyanide and relies on the same
underlying chemistry and determinative
technique to determine total cyanide.
Total cyanide consists of dissolved
HCN, sodium cyanide (NaCN), and
various metal-cyanide complexes,
which a continuous flow analyzer
converts to aqueous HCN by mixing it
with sulfuric acid, irradiating with UV
light, and precipitating potentially
interfering sulfides with bismuth ion.
The aqueous HCN is captured in a
donor stream that is passed across a
hydrophobic gas-permeable membrane,
which selectively diffuses the gaseous
HCN into a parallel acceptor stream of
dilute sodium hydroxide forming
dissolved CN–. The cyanide ion in this
acceptor stream is measured using an
amperometric detector, where the
cyanide ion dissolves the silver
electrode, resulting in a proportional
current.
2. 4500–CN¥ Q–2021, Weak and
Dissociable Cyanide by Flow Injection,
Gas Diffusion, and Amperometric
Measurement. Weak and dissociable
cyanide consists of dissolved HCN,
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10739
NaCN, and various metal-cyanide
complexes and includes the same forms
of cyanide as those measured using
other methods approved in Table IB for
determination of available cyanide.
Analysts pretreat for weak and
dissociable cyanide by mixing a sample
with ligand reagents. They then inject
the sample into a sulfuric acid and
bismuth nitrate solution to produce a
donor stream containing aqueous
dissolved HCN and precipitated sulfide,
if sulfide is present. The donor stream
is passed across a hydrophobic gaspermeable membrane, which selectively
diffuses gaseous HCN into a parallel
acceptor stream of dilute sodium
hydroxide, forming dissolved CN¥. The
cyanide ion in this acceptor stream is
measured using an amperometric
detector, where the cyanide ion
dissolves the silver electrode, resulting
in a proportional current. Although this
method is new to Standard Methods for
the Examination of Water and
Wastewater, it is based on ASTM
D6888–16, which is approved in Table
IB for determination of available
cyanide and relies on the same
underlying chemistry and determinative
technique to determine available
cyanide.
3. 4500–CN¥ R–2021, Free Cyanide by
Flow Injection, Gas Diffusion, and
Amperometric Measurement. Free
cyanide (FCN) consists of dissolved
HCN, NaCN, and the soluble fraction of
various metal-cyanide complexes. To
determine FCN, analysts pretreat a
sample by mixing it with a buffered
solution in the pH range of 6 to 8 that
simulates the receiving water resulting
in a donor stream containing aqueous
dissolved HCN in equilibrium with the
cyanide anion. The donor stream is
passed across a hydrophobic gaspermeable membrane, which selectively
diffuses gaseous HCN into a parallel
acceptor stream that consists of dilute
sodium hydroxide, forming dissolved
CN¥. The cyanide ions in this acceptor
stream are measured when it is passed
through an amperometric detector,
where the cyanide ion dissolves the
silver electrode, resulting in a
proportional current. Although this
method is new to Standard Methods for
the Examination of Water and
Wastewater, it is based on ASTM
D7237–15, which is approved in Table
IB for determination of free cyanide and
relies on the same underlying chemistry
and determinative technique to
determine free cyanide.
4. Fluoride. 4500–F¥ G–2021, IonSelective Electrode Flow Injection
Analysis is an automated version of
method 4500–F¥ C and relies on the
same underlying chemistry and
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
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determinative technique as USGS
Method I–4237–85, which currently is
approved in Table IB for determination
of fluoride. Fluoride is determined
potentiometrically by using a
combination fluoride ion selective
electrode (ISE) in a flow cell. The
fluoride electrode consists of a
lanthanum fluoride crystal across which
a potential is developed by fluoride
ions.
5. Oil and Grease. In 5520 G–2021,
Solid-Phase, Partition-Gravimetric
Method, dissolved or emulsified oil and
grease is extracted from water by
passing a sample through a solid-phase
extraction (SPE) disk where the oil and
grease are adsorbed by the disk and
subsequently eluted with n-hexane. SPE
is a modification allowed under EPA
Methods 1664 A and B and relies on the
same underlying chemistry and
determinative technique as Methods
1664 A and B. Some extractables,
especially unsaturated fats and fatty
acids, oxidize readily; hence, special
precautions regarding temperature and
solvent vapor displacement are
provided. This method is not applicable
to materials that volatilize at
temperatures below 85 °C, or crude and
heavy fuel oils containing a significant
percentage of material not soluble in nhexane. This method may be a
satisfactory alternative to liquid-liquid
extraction techniques, especially for
samples that tend to form difficult
emulsions during the extraction step.
IV. Incorporation by Reference
Currently, hundreds of methods and
ATPs are incorporated by reference
within 40 CFR part 136. In most cases,
40 CFR part 136 contains multiple
approved methods for a single
parameter (or pollutant) and regulated
entities often have a choice in selecting
a method. The proposed rule contains
revisions to VCSB methods that are
currently incorporated by reference (see
Sections III.B, III.C, and III.F of this
preamble). Two VCSBs have made such
revisions, Standard Methods and
ASTM. The proposed VCSB methods
are consistent with the requirements of
the National Technology Transfer and
Advancement Act (NTTAA), under
which Federal agencies use technical
standards developed or adopted by the
VCSBs if compliance would not be
inconsistent with applicable law or
otherwise impracticable (see Section V.I
of this preamble). The proposed
copyrighted VCSB methods are
available on their respective websites
(standardmethods.org and astm.org) to
everyone at a cost determined by the
VCSB, generally from $60 to $80. Both
organizations also offer memberships or
VerDate Sep<11>2014
19:11 Feb 17, 2023
Jkt 259001
subscriptions that allow unlimited
access to their methods. The cost of
obtaining these methods is not a
significant financial burden for a
discharger or environmental laboratory,
making the methods reasonably
available.
This proposal also includes two
vendor ATPs (see Section III.D of this
preamble) and four revised EPA
methods (see Section III.A of this
preamble) which EPA proposes to
incorporate by reference. The ATPs and
EPA methods are available free of
charge on their respective websites
(sgsaxys.com/wp-content/uploads/2022/
09/SGS-AXYS-Method-16130-Rev1.0.pdf, pacelabs.com and epa.gov/cwamethods/approved-cwa-chemical-testmethods), therefore the ATPs and EPA
methods incorporated by reference are
reasonably available.
alternatives to currently approved
methods for a particular analyte (e.g.,
ASTM Method D7511). Because these
methods would be alternatives rather
than requirements, there are no direct
costs associated with this proposal. EPA
proposes methods that would be
incorporated by reference. If a permittee
elected to use these methods, they could
incur a small cost associated with
obtaining these methods from the listed
sources. See Section IV of this preamble.
V. Statutory and Executive Order
Reviews
E. Executive Order 13132: Federalism
A. Executive Order 12866: Regulatory
Planning and Review Executive Order
13563: Improving Regulation and
Regulatory Review
This action is not a significant
regulatory action and was therefore not
submitted to the Office of Management
and Budget (OMB) for review.
B. Paperwork Reduction Act
This action does not impose an
information collection burden under the
Paperwork Reduction Act. This rule
does not impose any information
collection, reporting, or recordkeeping
requirements. This proposal would
merely add or revise CWA test
procedures.
C. Regulatory Flexibility Act
The Agency certifies that this action
would not have a significant economic
impact on a substantial number of small
entities under the Regulatory Flexibility
Act. This action would not impose any
requirements on small entities. This
action would approve new and revised
versions of CWA testing procedures.
Generally, these changes would have a
positive impact on small entities by
increasing method flexibility, thereby
allowing entities to reduce costs by
choosing more cost-effective methods.
In general, EPA expects the proposed
revisions would lead to few, if any,
increased costs. The proposed changes
clarify or improve the instructions in
the method, update the technology used
in the method, improve the QC
instructions, make editorial corrections,
or reflect the most recent approval year
of an already approved method. In some
cases, the proposal would add
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D. Unfunded Mandates Reform Act
This action does not contain any
unfunded mandate as described in the
Unfunded Mandates Reform Act, 2
U.S.C. 1531–1538, and does not
significantly or uniquely affect small
governments. The action imposes no
enforceable duty on any state, local or
tribal governments or the private sector.
This proposed rule does not have
federalism implications. It would 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.
F. Executive Order 13175: Consultation
and Coordination With Indian Tribal
Governments
This proposed rule does not have
tribal implications as specified in
Executive Order 13175. This rule would
merely approve new and revised
versions of test procedures. EPA does
not expect the proposal would lead to
any costs to any tribal governments, and
if incurred, EPA projects they would be
minimal. Thus, Executive Order 13175
does not apply to this action.
G. Executive Order 13045: Protection of
Children From Environmental Health
Risks and Safety Risks
EPA interprets Executive Order 13045
as applying only to those regulatory
actions that concern environmental
health or safety risks that EPA has
reason to believe may
disproportionately affect children, per
the definition of ‘‘covered regulatory
action’’ in section 2–202 of the
Executive Order. This action is not
subject to Executive Order 13045
because it does not concern an
environmental health risk or safety risk.
H. Executive Order 13211: Actions That
Significantly Affect Energy Supply,
Distribution, or Use
This action is not subject to Executive
Order 13211 because it is not a
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
significant regulatory action under
Executive Order 12866.
I. National Technology Transfer and
Advancement Act of 1995
This action involves technical
standards. EPA proposes to approve the
use of technical standards developed
and recommended by the Standard
Methods Committee and ASTM
International for use in compliance
monitoring where EPA determined that
those standards meet the needs of CWA
programs. As described above, this
proposal is consistent with the NTTAA.
J. Executive Order 12898: Federal
Actions To Address Environmental
Justice in Minority Populations and
Low-Income Populations
Executive Order 12898 (59 FR 7629,
February 16, 1994) directs Federal
agencies, to the greatest extent
practicable and permitted by law, to
make environmental justice part of their
mission by identifying and addressing,
as appropriate, disproportionately high
and adverse human health or
environmental effects of their programs,
policies, and activities on minority
populations (people of color) and lowincome populations.
EPA believes that this type of action
does not concern human health or
environmental conditions and therefore
cannot be evaluated with respect to
potentially disproportionate and
adverse effects on people of color, lowincome populations and/or indigenous
peoples. This action has no effect on
human health or the environment
because this action would approve new
and revised versions of CWA testing
procedures. The proposed changes
clarify or improve the instructions in
the method, update the technology used
in the method, improve the QC
instructions, make editorial corrections,
or reflect the most recent approval year
of an already approved method. These
proposed changes would provide
increased flexibility for the regulated
community in meeting monitoring
requirements while improving data
quality. In addition, this proposed
update to the CWA methods would
incorporate technological advances in
analytical technology.
List of Subjects in 40 CFR Part 136
Environmental protection,
Incorporation by reference, Reporting
and recordkeeping requirements, Test
procedures, Water pollution control.
Michael S. Regan,
Administrator.
For the reasons set out in the
preamble, the EPA proposes to amend
40 CFR part 136 as follows:
10741
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. Amend § 136.3 as follows:
a. Revise tables IA, IB, IC, ID, and IH
in paragraph (a);
■ b. Revise the introductory text to
paragraph (b) and paragraphs (b)(8)(ii)
through (v), (b)(10)(i), (viii) through
(xiv), (xvi) through (xxvi), (xxviii)
through (xxxv), (xxxvii), (xxxix) through
(li), (lv) through (lxiii), and (lxvii),
(b)(15)(xi), (xx), (xxx), (xxxii), (lix), (lxv)
through (lxvii), and (lxix);
■ c. Redesignate paragraphs (b)(33)
through (39) as paragraphs (b)(35)
through (41);
■ d. Add new paragraphs (b)(33) and
(34); and
■ e. In paragraph (e), table II, revise
Footnote ‘‘5’’.
The revisions and additions read as
follows:
■
■
§ 136.3
*
Identification of test procedures.
*
*
*
*
TABLE IA—LIST OF APPROVED BIOLOGICAL METHODS FOR WASTEWATER AND SEWAGE SLUDGE
Method 1
Parameter and units
EPA
AOAC, ASTM,
USGS
Standard methods
Other
Bacteria
1. Coliform (fecal),
number per gram dry
weight.
2. Coliform (fecal),
number per 100 mL.
3. Coliform (total), number per 100 mL.
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4. E. coli, number per
100 mL.
5. Fecal streptococci,
number per 100 mL.
6. Enterococci, number
per 100 mL.
VerDate Sep<11>2014
Most Probable Number
(MPN), 5 tube, 3 dilution, or
Membrane filter
(MF),2 5 single step.
MPN, 5 tube, 3 dilution, or.
Multiple tube/multiple
well, or.
MF,2 5 single step 5 ......
MPN, 5 tube, 3 dilution, or.
MF,2 5 single step or ...
MF,2 5 two step with
enrichment.
MPN 6 8 16 multiple
tube, or.
multiple tube/multiple
well, or.
MF,2 5 6 7 8 two step, or
Single step ..................
MPN, 5 tube, 3 dilution, or.
MF,2 or ........................
Plate count ..................
MPN, 5 tube, 3 dilution, or.
19:11 Feb 17, 2023
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p. 132; 3 1680; 11 15
1681 11 20.
9221 E–2014.
p. 124 3 ........................
9222 D–2015 29.
p. 132 3 ........................
.....................................
9221 E–2014; 9221 F–
2014 33.
.....................................
p. 124 3 ........................
p. 114 3 ........................
9222 D–2015 29 ..........
9221 B–2014.
B–0050–85 4.
p. 108 3 ........................
p. 111 3 ........................
9222 B–2015 30 ...........
9222 B–2015 30.
B–0025–85 4.
.....................................
9221 B2014/9221 F–
2014 12 14 33.
9223 B–2016 13 ...........
.....................................
.....................................
1603.1 21 ......................
p. 139 3 ........................
p. 136 3 ........................
p. 143 3.
p. 139 3 ........................
Frm 00019
Fmt 4701
...........................
991.15 10 ...........
Colilert®.13 18
Colilert-18®.13 17 18
...........................
m-ColiBlue24®.19
9222 B–2015/9222 I–
2015 31.
.....................................
9230 B–2013.
9230 C–2013 32 ...........
B–0055–85 4.
9230 B–2013.
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE IA—LIST OF APPROVED BIOLOGICAL METHODS FOR WASTEWATER AND SEWAGE SLUDGE—Continued
Method 1
EPA
Standard methods
AOAC, ASTM,
USGS
MPN,6 8 multiple tube/
multiple well, or.
MF 2 5 6 7 8 single step
or.
Plate count ..................
MPN multiple tube ......
.....................................
9230 D–2013 ..............
D6503–99 9 .......
1600.1 24 ......................
9230 C–2013 32.
Parameter and units
7. Salmonella, number
per gram dry
weight 11.
p. 143 3.
1682 22.
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Aquatic Toxicity
8. Toxicity, acute, fresh Water flea,
water organisms,
Cladoceran,
LC50, percent effluent.
Ceriodaphnia dubia
acute.
Water fleas,
Cladocerans,
Daphnia pulex and
Daphnia magna
acute.
Fish, Fathead minnow,
Pimephales
promelas, and
Bannerfin shiner,
Cyprinella leedsi,
acute.
Fish, Rainbow trout,
Oncorhynchus
mykiss, and brook
trout, Salvelinus
fontinalis, acute.
9. Toxicity, acute, estu- Mysid, Mysidopsis
arine and marine orbahia, acute.
ganisms of the Atlan- Fish, Sheepshead mintic Ocean and Gulf of
now, Cyprinodon
Mexico, LC50, pervariegatus, acute.
cent effluent.
Fish, Silverside,
Menidia beryllina,
Menidia menidia,
and Menidia
peninsulae, acute.
Fish, Fathead minnow,
10. Toxicity, chronic,
Pimephales
fresh water orgapromelas, larval surnisms, NOEC or
vival and growth.
IC25, percent effluent.
Fish, Fathead minnow,
Pimephales
promelas, embryolarval survival and
teratogenicity.
Water flea,
Cladoceran,
Ceriodaphnia dubia,
survival and reproduction.
Green alga,
Selenastrum
capricornutum,
growth.
11. Toxicity, chronic,
Fish, Sheepshead minestuarine and marine
now, Cyprinodon
organisms of the Atvariegatus, larval
lantic Ocean and
survival and growth.
Gulf of Mexico,
NOEC or IC25, percent effluent.
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19:11 Feb 17, 2023
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2002.0 25.
2021.0 25.
2000.0 25.
2019.0 25.
2007.0 25.
2004.0 25.
2006.0 25.
1000.0 26.
1001.0 26.
1002.0 26.
1003.0 26.
1004.0 27.
Frm 00020
Fmt 4701
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Enterolert®.13 23
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10743
TABLE IA—LIST OF APPROVED BIOLOGICAL METHODS FOR WASTEWATER AND SEWAGE SLUDGE—Continued
Method 1
Parameter and units
EPA
lotter on DSK11XQN23PROD with PROPOSALS2
Fish, Sheepshead minnow, Cyprinodon
variegatus, embryolarval survival and
teratogenicity.
Fish, Inland silverside,
Menidia beryllina,
larval survival and
growth.
Mysid, Mysidopsis
bahia, survival,
growth, and fecundity.
Sea urchin, Arbacia
punctulata, fertilization.
Standard methods
AOAC, ASTM,
USGS
Other
1005.0 27.
1006.0 27.
1007.0 27.
1008.0 27.
Table IA notes:
1 The method must be specified when results are reported.
2 A 0.45-μm 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 Microbiological Methods for Monitoring the Environment, Water and Wastes, EPA/600/8–78/017. 1978. U.S. EPA.
4 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. 1989. USGS.
5 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.
6 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.
7 When the MF method has been used previously to test waters with high turbidity, large numbers 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.
8 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.
9 Annual Book of ASTM Standards-Water and Environmental Technology, Section 11.02. 2000, 1999, 1996. ASTM International.
10 Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998. AOAC International.
11 Recommended for enumeration of target organism in sewage sludge.
12 The multiple-tube fermentation test is used in 9221B.2–2014. 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.
14 After prior enrichment in a presumptive medium for total coliform using 9221B.2–2014, 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–2014. Commercially available EC–MUG media or EC media
supplemented in the laboratory with 50 μg/mL of MUG may be used.
15 Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using Lauryl-Tryptose Broth (LTB) and EC Medium, EPA–821–R–14–009. September 2014. U.S. EPA.
16 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® may be enumerated with the multiple-well procedures, Quanti-Tray® or Quanti-Tray®/2000 and the MPN calculated from the table provided by the manufacturer.
17 Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms and E. coli that provides results within 18 h of
incubation at 35°C rather than the 24 h required for the Colilert® test and is recommended for marine water samples.
18 Descriptions of the Colilert®, Colilert-18®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories, Inc.
19 A description of the mColiBlue24® test is available from Hach Company.
20 Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using A–1 Medium, EPA–821–R–06–013. July
2006. U.S. EPA.
21 Method 1603.1: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified Membrane-Thermotolerant Escherichia coli Agar
(modified mTEC), [in draft as of 2023]. U.S. EPA.
22 Method 1682: Salmonella in Sewage Sludge (Biosolids) by Modified Semisolid Rappaport-Vassiliadis (MSRV) Medium, EPA–821–R–14–012.
September 2014. U.S. EPA.
23 A description of the Enterolert® test may be obtained from IDEXX Laboratories Inc.
24 Method 1600.1: Enterococci in Water by Membrane Filtration Using Membrane-Enterococcus Indoxyl-b-D-Glucoside Agar (mEI), [in draft as
of 2023]. U.S. EPA.
25 Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms, EPA–821–R–02–012.
Fifth Edition, October 2002. U.S. EPA; and U.S. EPA Whole Effluent Toxicity Methods Errata Sheet, EPA 821–R–02–012–ES. December 2016.
26 Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms, EPA–821–R–02–013.
Fourth Edition, October 2002. U.S. EPA; and U.S. EPA Whole Effluent Toxicity Methods Errata Sheet, EPA 821–R–02–012–ES. December
2016.
27 Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms, EPA–821–R–
02–014. Third Edition, October 2002. U.S. EPA; and U.S. EPA Whole Effluent Toxicity Methods Errata Sheet, EPA 821–R–02–012–ES. December 2016.
28 To use Colilert-18® to assay for fecal coliforms, the incubation temperature is 44.5 ± 0.2 °C, and a water bath incubator is used.
29 On a monthly basis, at least ten blue colonies from positive samples must be verified using Lauryl Tryptose Broth and EC broth, followed by
count adjustment based on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible,
verifications should be done from randomized sample sources.
30 On a monthly basis, at least ten sheen colonies from positive samples must be verified using lauryl tryptose broth and brilliant green lactose
bile broth, followed by count adjustment based on these results; and representative non-sheen colonies should be verified using lauryl tryptose
broth. Where possible, verifications should be done from randomized sample sources.
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
31 Subject
coliform positive samples determined by 9222 B–2015 or other membrane filter procedure to 9222 I–2015 using NA–MUG media.
of colonies by incubation of BHI agar at 10 ± 0.5 °C for 48 ± 3 h is optional. As per the Errata to the 23rd Edition of Standard
Methods for the Examination of Water and Wastewater ‘‘Growth on a BHI agar plate incubated at 10 ± 0.5 °C for 48 ± 3 h is further verification
that the colony belongs to the genus Enterococcus.’’
33 9221F. 2–2014 allows for simultaneous detection of E. coli and thermotolerant fecal coliforms by adding inverted vials to EC–MUG; the inverted vials collect gas produced by thermotolerant fecal coliforms.
32 Verification
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES
Parameter
1. Acidity, as CaCO3,
mg/L.
2. Alkalinity, as
CaCO3, mg/L.
3. Aluminum—Total, 4
mg/L.
Methodology 58
EPA 52
Standard methods 84
ASTM
Electrometric endpoint or phenolphthalein endpoint.
Electrometric or Colorimetric titration to
pH 4.5, Manual.
Automatic ..................
Digestion,4 followed
by any of the following:
AA direct aspiration 36
...................................
2310 B–2020 ............
D1067–16 .................
I–1020–85.2
...................................
2320 B–2021 ............
D1067–16 .................
973.43,3 I–1030–85.2
310.2 (Rev. 1974) 1 ...
...................................
...................................
I–2030–85.2
...................................
3111 D–2019 or 3111
E–2019.
3113 B–2020.
...................................
I–3051–85.2
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
...................................
D4190–15 .................
993.14,3 I–4472–
97.81
See footnote.34
AA furnace ................
STGFAA ....................
ICP/AES 36 ................
ICP/MS ......................
lotter on DSK11XQN23PROD with PROPOSALS2
4. Ammonia (as N),
mg/L.
5. Antimony—Total, 4
mg/L.
VerDate Sep<11>2014
Direct Current Plasma (DCP) 36.
Colorimetric
(Eriochrome
cyanine R).
Manual distillation 6 or
gas diffusion (pH >
11), followed by
any of the following:
Nesslerization ...........
Titration .....................
Electrode ...................
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev 4.2
(2003),68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
3500–Al B–2020.
350.1, Rev. 2.0
(1993).
4500–NH3 B–2021 ....
...................................
973.49.3
...................................
...................................
...................................
...................................
4500–NH3 C–2021.
4500–NH3 D–2021 or
E–2021.
4500–NH3 F–2021 ....
D1426–15 (A) ...........
973.49,3 I–3520–85.2
Manual phenate, sa...................................
licylate, or other
substituted phenols
in Berthelot reaction-based methods.
Automated phenate,
350.1,30 Rev. 2.0
salicylate, or other
(1993).
substituted phenols
in Berthelot reaction-based methods.
Automated electrode
...................................
Ion Chromatography
...................................
Automated gas diffu...................................
sion, followed by
conductivity cell
analysis.
Automated gas diffu...................................
sion followed by
fluorescence detector analysis.
Digestion,4 followed
by any of the following:
AA direct aspiration 36 ...................................
AA furnace ................ ...................................
STGFAA .................... 200.9, Rev. 2.2
(1994).
ICP/AES 36 ................ 200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
19:11 Feb 17, 2023
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USGS/AOAC/other
PO 00000
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Fmt 4701
D1426–15 (B).
...................................
See footnote.60
4500–NH3 G–2021
4500–NH3 H–2021.
...................................
I–4523–85,2 I–2522–
90.80
...................................
...................................
...................................
...................................
D6919–17.
...................................
See footnote.7
...................................
...................................
3111 B–2019.
3113 B–2020.
3120 B–2020 ............
Sfmt 4702
D1976–20.
E:\FR\FM\21FEP2.SGM
21FEP2
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FIAlab100.82
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10745
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
6. Arsenic—Total,4
mg/L.
Methodology 58
EPA 52
Standard methods 84
ASTM
ICP/MS ......................
200.8, Rev. 5.4
(1994).
206.5 (Issued 1978) 1.
3125 B–2020 ............
D5673–16 .................
993.14,3 I–4472–
97.81
...................................
3114 B–2020 or 3114
C–2020.
3113 B–2020 ............
D2972–15 (B) ...........
I–3062–85.2
D2972–15 (C) ...........
I–4063–98.49
3120 B–2020 ............
D1976–20.
3125 B–2020 ............
D5673–16 .................
3500–As B–2020 ......
D2972–15 (A) ...........
...................................
...................................
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
3111 D–2019 ............
3113 B–2020 ............
3120 B–2020 ............
...................................
D4382–18.
...................................
3125 B–2020 ............
D5673–16 .................
...................................
...................................
993.14,3 I–4472–
97.81
See footnote.34
...................................
3111 D–2019 or 3111
E–2019.
3113 B–2020 ............
D3645–15 (A) ...........
I–3095–85.2
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
993.14,3 I–4472–
97.81
See footnote.34
Digestion,4 followed
by any of the following:
AA gaseous hydride
AA furnace ................
STGFAA ....................
ICP/AES 36 ................
ICP/MS ......................
7. Barium—Total,4 mg/
L.
Colorimetric (SDDC)
Digestion,4 followed
by any of the following:
AA direct aspiration 36
AA furnace ................
ICP/AES 36 ................
ICP/MS ......................
8. Beryllium—Total,4
mg/L.
DCP 36 .......................
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
STGFAA ....................
ICP/AES ....................
ICP/MS ......................
9. Biochemical oxygen
demand (BOD5),
mg/L.
10. Boron—Total,37
mg/L.
DCP ..........................
Colorimetric
(aluminon).
Dissolved Oxygen
Depletion.
Colorimetric (curcumin).
ICP/AES ....................
ICP/MS ......................
11. Bromide, mg/L ......
lotter on DSK11XQN23PROD with PROPOSALS2
12. Cadmium—Total,4
mg/L.
DCP ..........................
Electrode ...................
Ion Chromatography
CIE/UV ......................
Digestion,4 followed
by any of the following:
AA direct aspiration 36
AA furnace ................
STGFAA ....................
ICP/AES 36 ................
VerDate Sep<11>2014
19:11 Feb 17, 2023
Jkt 259001
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
USGS/AOAC/other
993.14,3 I–4020–
05.70
I–3060–85.2
I–3084–85.2
I–4471–97.50
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
3125 B–2020 ............
D5673–16 .................
...................................
See footnote.61.
D4190–15 .................
...................................
5210 B–2016 85 .........
...................................
...................................
4500–B B–2011 ........
...................................
973.44,3 p. 17,9 I–
1578–78,8 See
footnote.10 63
I–3112–85.2
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
300.0, Rev 2.1 (1993)
and 300.1, Rev 1.0
(1997).
...................................
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
993.14.3
...................................
...................................
4110 B–2020, C–
2020 or D–2020.
D4190–15 .................
D1246–16 .................
D4327–17 .................
See footnote.34
I–1125–85.2
993.30,3 I–2057–
85.79
4140 B–2020 ............
D6508–15 .................
D6508, Rev. 2.54
...................................
3111 B–2019 or 3111
C–2019.
D3557–17 (A or B) ...
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
3113 B–2020 ............
D3557–17 (D) ...........
974.27,3 p. 37,9 I–
3135–85 2 or I–
3136–85.2
I–4138–89.51
3120 B–2020 ............
D1976–20 .................
PO 00000
Frm 00023
Fmt 4701
Sfmt 4702
D3645–15 (B).
E:\FR\FM\21FEP2.SGM
21FEP2
I–1472–85 2 or I–
4471–97.50
10746
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
13. Calcium—Total,4
mg/L.
Methodology 58
EPA 52
Standard methods 84
ASTM
ICP/MS ......................
200.8, Rev. 5.4
(1994).
...................................
...................................
...................................
3125 B–2020 ............
D5673–16 .................
...................................
...................................
3500–Cd–D–1990.
D4190–15 .................
D3557–17 (C).
3111 B–2019 or 3111
D–2019.
3120 B–2020 ............
D511–14 (B) .............
I–3152–85.2
...................................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
993.14.3
...................................
3500–Ca B–2020 ......
...................................
5210 B–2016 85 .........
...................................
D511–14 (A).
D6919–17.
...................................
See footnote.34
DCP 36 .......................
Voltammetry 11 ..........
Colorimetric (Dithizone).
Digestion,4 followed
by any of the following:
AA direct aspiration ..
ICP/AES ....................
ICP/MS ......................
14. Carbonaceous biochemical oxygen demand (CBOD5), mg/
L 12.
15. Chemical oxygen
demand (COD), mg/
L.
16. Chloride, mg/L ......
17. Chlorine—Total residual, mg/L.
lotter on DSK11XQN23PROD with PROPOSALS2
17A. Chlorine-Free
Available, mg/L.
18. Chromium VI dissolved, mg/L.
DCP ..........................
Titrimetric (EDTA) .....
Ion Chromatography
Dissolved Oxygen
Depletion with nitrification inhibitor.
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
...................................
...................................
993.14,3 I–4472–
97.81
See footnote.34
See footnote.35 63
Titrimetric ..................
410.3 (Rev. 1978) 1 ...
5220 B–2011 or C–
2011.
D1252–06(12) (A) .....
973.46,3 p. 17,9 I–
3560–85.2
Spectrophotometric,
manual or automatic.
Titrimetric: (silver nitrate).
(Mercuric nitrate) .......
Colorimetric: manual
Automated (ferricyanide).
Potentiometric Titration.
Ion Selective Electrode.
Ion Chromatography
410.4, Rev. 2.0
(1993).
5220 D–2011 ............
D1252–06(12) (B) .....
See footnotes,13 14 83
I–3561–85.2
...................................
4500–Cl¥ B–2021 ....
D512–12 (B) .............
I–1183–85.2
...................................
...................................
...................................
4500–Cl¥ C–2021 ....
...................................
4500–Cl¥ E–2021 ....
D512–12 (A) .............
...................................
...................................
973.51,3 I–1184–85.2
I–1187–85.2
I–2187–85.2
...................................
4500–Cl¥ D–2021.
...................................
...................................
D512–12 (C).
300.0, Rev 2.1 (1993)
and 300.1, Rev 1.0
(1997).
...................................
...................................
4110 B–2020 or 4110
C–2020.
D4327–17 .................
993.30,3 I–2057–
90.51
4140 B–2020 ............
4500–Cl D–2011 .......
D6508–15 .................
D1253–14.
D6508, Rev. 2.54
Amperometric direct
(low level).
Iodometric direct .......
Back titration ether
end-point 15.
DPD–FAS .................
Spectrophotometric,
DPD.
Electrode ...................
Amperometric direct ..
...................................
4500–Cl E–2011.
...................................
...................................
4500–Cl B–2011.
4500–Cl C–2011.
...................................
...................................
4500 Cl F–2011.
4500–Cl G–2011.
...................................
...................................
...................................
4500–Cl D–2011 .......
...................................
D1253–14.
See footnote.16
Amperometric direct
(low level).
DPD–FAS .................
Spectrophotometric,
DPD.
0.45-micron filtration
followed by any of
the following:
AA chelation-extraction.
Ion Chromatography
...................................
4500–Cl E–2011.
...................................
...................................
4500–Cl F–2011.
4500–Cl G–2011.
...................................
3111 C–2019 ............
...................................
I–1232–85.2
218.6, Rev. 3.3
(1994).
...................................
3500–Cr C–2020 ......
D5257–17 .................
993.23.3
3500–Cr B–2020 .......
D1687–17 (A) ...........
I–1230–85.2
CIE/UV ......................
Amperometric direct ..
Colorimetric (diphenyl-carbazide).
VerDate Sep<11>2014
...................................
USGS/AOAC/other
19:11 Feb 17, 2023
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10747
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
Methodology 58
EPA 52
Standard methods 84
ASTM
USGS/AOAC/other
19. Chromium—Total,4
mg/L.
Digestion,4 followed
by any of the following:
AA direct aspiration 36
AA chelation-extraction.
AA furnace ................
STGFAA ....................
...................................
...................................
3111 B–2019 ............
3111 C–2019.
D1687–17 (B) ...........
974.27,3 I–3236–85.2
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev 4.2
(2003),68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
3113 B–2020 ............
D1687–17 (C) ...........
I–3233–93.46
3120 B–2020 ............
D1976–20.
3125 B–2020 ............
D5673–16 .................
...................................
3500–Cr B–2020.
D4190–15 .................
993.14,3 I–4020–05 70
I–4472–97.81
See footnote.34
3111 B–2019 or 3111
C–2019.
3113 B–2020 ............
D3558–15 (A or B) ...
p. 37,9 I–3239–85.2
D3558–15 (C) ...........
I–4243–89.51
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
...................................
2120 F–2021 78.
D4190–15 .................
993.14,3 I–4020–05 70
I–4472–97.81
See footnote.34
ICP/AES 36 ................
ICP/MS ......................
20. Cobalt—Total,4
mg/L.
DCP 36 .......................
Colorimetric (diphenyl-carbazide).
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
STGFAA ....................
ICP/AES ....................
ICP/MS ......................
21. Color, platinum cobalt units or dominant wavelength,
hue, luminance purity.
22. Copper—Total,4
mg/L.
DCP ..........................
Colorimetric (ADMI) ..
...................................
2120 B–2021 ............
...................................
I–1250–85.2
...................................
...................................
...................................
See footnote.18
...................................
3111 B–2019 or 3111
C–2019.
D1688–17 (A or B) ...
AA furnace ................
STGFAA ....................
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
3113 B–2020 ............
D1688–17 (C) ...........
974.27,3 p. 37,9 I–
3270–85 2 or I–
3271–85.2
I–4274–89.51
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
...................................
3500–Cu B–2020.
D4190–15 .................
993.14,3 I–4020–
05,70 I–4472–97.81
See footnote.34
3500–Cu C–2020 ......
...................................
See footnote.19
...................................
...................................
Kelada-01.55
4500–CN¥ P–2021 ..
D7511–12(17).
4500–CN¥ B–2021
and C–2021.
D2036–09(15)(A),
D7284–20.
...................................
D2036–09(15)(A)
D7284–20.
ICP/MS ......................
lotter on DSK11XQN23PROD with PROPOSALS2
VerDate Sep<11>2014
...................................
200.9, Rev. 2.2
(1994).
200.7, Rev. 4.4
(1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
Platinum cobalt visual
comparison.
Spectrophotometric ...
Digestion,4 followed
by any of the following:
AA direct aspiration 36
ICP/AES 36 ................
23. Cyanide—Total,
mg/L.
...................................
DCP 36 .......................
Colorimetric
(Neocuproine).
Colorimetric
...................................
(Bathocuproine).
Automated UV diges...................................
tion/distillation and
Colorimetry.
Segmented Flow In...................................
jection, In-Line Ultraviolet Digestion,
followed by gas diffusion amperometry.
Manual distillation
335.4, Rev. 1.0
with MgCl2, fol(1993) 57.
lowed by any of the
following:
Flow Injection, gas
...................................
diffusion amperometry.
19:11 Feb 17, 2023
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21FEP2
10–204–00–1–X.56
10748
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
24. Cyanide-Available,
mg/L.
24. A Cyanide-Free,
mg/L.
25. Fluoride—Total,
mg/L.
26. Gold—Total,4 mg/L
lotter on DSK11XQN23PROD with PROPOSALS2
27. Hardness—Total,
as CaCO3, mg/L.
28. Hydrogen ion (pH),
pH units.
VerDate Sep<11>2014
Methodology 58
EPA 52
Standard methods 84
ASTM
Titrimetric ..................
Spectrophotometric,
manual.
Semi-Automated 20 ....
...................................
...................................
4500–CN¥ D–2021 ..
4500–CN¥ E–2021 ..
D2036–09(15)(A) ......
D2036–09(15)(A) ......
p. 22.9
I–3300–85.2
335.4, Rev. 1.0
(1993) 57.
...................................
...................................
4500–CN¥ N–2021 ..
...................................
10–204–00–1–X,56 I–
4302–85.2
...................................
4500–CN¥ F–2021 ...
D2036–09(15)(A).
D2036–09(15)(A).
...................................
4500–CN¥ G–2021 ..
D2036–09(15)(B).
...................................
4500–CN¥ Q–2021 ..
D6888–16 .................
OIA–1677–09.44
...................................
...................................
...................................
Kelada-01.55
...................................
4500–CN¥ R–2021 ..
D7237–18 (A) ...........
OIA–1677–09.44
...................................
...................................
D4282–15.
...................................
4500–F¥ B–2021 .....
D1179–16 (A).
...................................
...................................
...................................
4500–F¥ C–2021 .....
4500–F¥ G–2021 .....
4500–F¥ D–2021.
D1179–16 (B).
...................................
I–4327–85.2
...................................
4500–F¥ E–2021.
300.0, Rev 2.1 (1993)
and 300.1, Rev 1.0
(1997).
...................................
4110 B–2020 or C–
2020.
D4327–17 .................
993.30.3
4140 B–2020 ............
D6508–15 .................
D6508, Rev. 2.54
...................................
231.2 (Issued 1978) 1
200.8, Rev. 5.4
(1994).
...................................
130.1 (Issued 1971) 1.
3111 B–2019.
3113 B–2020.
3125 B–2020 ............
D5673–16 .................
993.14.3
...................................
...................................
See footnote.34
...................................
2340 C–2021 ............
D1126–17 .................
973.52B,3 I–1338–
85.2
...................................
2340 B–2021.
...................................
4500–H+ B–2021 ......
D1293–18 (A or B) ...
973.41,3 I–1586–85.2
150.2 (Dec. 1982) 1 ...
...................................
...................................
See footnote,21 I–
2587–85.2
Ion Chromatography
Ion Selective Electrode.
Cyanide Amenable to
Chlorination
(CATC); Manual
distillation with
MgCl2, followed by
Titrimetric or
Spectrophotometric.
Flow injection and
ligand exchange,
followed by gas diffusion amperometry 59.
Automated Distillation
and Colorimetry (no
UV digestion).
Flow Injection, followed by gas diffusion amperometry.
Manual micro-diffusion and colorimetry.
Manual distillation,6
followed by any of
the following:
Electrode, manual .....
Electrode, automated
Colorimetric,
(SPADNS).
Automated
complexone.
Ion Chromatography
CIE/UV ......................
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
ICP/MS ......................
DCP ..........................
Automated colorimetric.
Titrimetric (EDTA) .....
Ca plus Mg as their
carbonates, by any
approved method
for Ca and Mg (See
Parameters 13 and
33), provided that
the sum of the lowest point of quantitation for Ca and
Mg is below the
NPDES permit requirement for Hardness.
Electrometric measurement.
Automated electrode
19:11 Feb 17, 2023
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21FEP2
USGS/AOAC/other
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10749
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
29. Iridium—Total,4
mg/L.
30. Iron—Total,4 mg/L
Methodology 58
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
ICP/MS ......................
Digestion,4 followed
by any of the following:
AA direct aspiration 36
AA furnace ................
STGFAA ....................
ICP/AES 36 ................
ICP/MS ......................
lotter on DSK11XQN23PROD with PROPOSALS2
31. Kjeldahl Nitrogen 5—Total, (as N),
mg/L.
DCP 36 .......................
Colorimetric (Phenanthroline).
Manual digestion 20
and distillation or
gas diffusion, followed by any of the
following:
Titration .....................
Nesslerization ...........
Electrode ...................
EPA 52
Standard methods 84
ASTM
USGS/AOAC/other
3111 B–2019 or 3111
C–2019.
3113 B–2020 ............
D1068–15 (A) ...........
974.27,3 I–3381–85.2
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
993.14.3
...................................
3500–Fe B–2011 ......
D4190–15 .................
D1068–15 (C) ...........
See footnote.34
See footnote.22
...................................
4500–Norg B–2021 or
C–2021 and 4500–
NH3 B–2021.
D3590–17 (A) ...........
I–4515–91.45
...................................
...................................
...................................
4500–NH3 C–2021 ...
...................................
4500–NH3 D–2021 or
E–2021.
4500–NH3 G–2021 or
4500–NH3 H–2021.
4500–NH3 F–2021 ....
...................................
D1426–15 (A).
D1426–15 (B).
973.48.3
...................................
235.2 (Issued 1978) 1.
...................................
...................................
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
3111 B–2019.
3125 B–2020.
D1068–15 (B).
Semi-automated
350.1, Rev. 2.0
phenate.
(1993).
Manual phenate, sa...................................
...................................
licylate, or other
substituted phenols
in Berthelot reaction based methods.
Automated gas diffu................................... ................................... ...................................
sion, followed by
conductivity cell
analysis.
Automated gas diffu................................... ................................... ...................................
sion followed by
fluorescence detector analysis.
Automated Methods for TKN that do not require manual distillation
Automated phenate,
351.1 (Rev. 1978) 1 ... ................................... ...................................
salicylate, or other
substituted phenols
in Berthelot reaction-based methods
colorimetric (auto
digestion and distillation).
Semi-automated
351.2, Rev. 2.0
4500–Norg D–2021 .... D3590–17 (B) ...........
block digestor col(1993).
orimetric (distillation
not required).
Block digester, fol................................... ................................... ...................................
lowed by Auto distillation and Titration.
Block digester, fol................................... ................................... ...................................
lowed by Auto distillation and
Nesslerization.
Block Digester, fol................................... ................................... ...................................
lowed by Flow injection gas diffusion
(distillation not required).
VerDate Sep<11>2014
19:11 Feb 17, 2023
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21FEP2
See footnote.60
Timberline Ammonia001.74
FIAlab 100.82
I–4551–78.8
I–4515–91.45
See footnote.39
See footnote.40
See footnote.41
10750
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
32. Lead—Total,4 mg/
L.
Methodology 58
EPA 52
Standard methods 84
ASTM
Digestion with
peroxdisulfate, followed by
Spectrophotometric
(2,6-dimethyl phenol).
Digestion with
persulfate, followed
by Colorimetric.
Digestion,4 followed
by any of the following:
AA direct aspiration 36
...................................
...................................
...................................
Hach 10242.76
...................................
...................................
...................................
NCASI TNTP
W10900.77
...................................
D3559–15 (A or B) ...
974.27,3 I–3399–85.2
AA furnace ................
STGFAA ....................
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
...................................
3111 B–2019 or 3111
C–2019.
3113 B–2020 ............
D3559–15 (D) ...........
I–4403–89.51
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
...................................
...................................
3500-Pb B–2020.
D4190–15 .................
D3559–15 (C).
993.14,3 I–4472–
97.81
See footnote.34
...................................
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
3111 B–2019 ............
3120 B–2020 ............
D511–14 (B) .............
D1976–20 .................
974.27,3 I–3447–85.2
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
993.14.3
...................................
...................................
...................................
D6919–17.
See footnote.34
...................................
3111 B–2019 or 3111
C–2019.
3113 B–2020 ............
D858–17 (A or B) .....
974.27,3 I–3454–85.2
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
ICP/AES 36 ................
ICP/MS ......................
33. Magnesium—
Total,4 mg/L.
DCP 36 .......................
Voltammetry 11 ..........
Colorimetric (Dithizone).
Digestion,4 followed
by any of the following:
AA direct aspiration ..
ICP/AES ....................
ICP/MS ......................
34. Manganese—
Total,4 mg/L.
DCP ..........................
Ion Chromatography
Digestion,4 followed
by any of the following:
AA direct aspiration 36
AA furnace ................
STGFAA ....................
ICP/AES 36 ................
ICP/MS ......................
lotter on DSK11XQN23PROD with PROPOSALS2
35. Mercury—Total,
mg/L.
36. Molybdenum—
Total,4 mg/L.
VerDate Sep<11>2014
DCP 36 .......................
Colorimetric
(Persulfate).
Colorimetric
(Periodate).
Cold vapor, Manual ..
Cold vapor, Automated.
Cold vapor atomic fluorescence spectrometry (CVAFS).
Purge and Trap
CVAFS.
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
ICP/AES ....................
19:11 Feb 17, 2023
Jkt 259001
USGS/AOAC/other
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
D858–17 (C).
3125 B–2020 ............
D5673–16 .................
...................................
3500–Mn B–2020 .....
D4190–15 .................
...................................
993.14,3 I–4472–
97.81
See footnote.34
920.203.3
...................................
...................................
...................................
See footnote.23
245.1, Rev. 3.0
(1994).
245.2 (Issued 1974) 1.
3112 B–2020 ............
D3223–17 .................
977.22,3 I–3462–85.2
245.7 Rev. 2.0
(2005) 17.
...................................
...................................
I–4464–01.71
3111 D–2019 ............
3113 B–2020 ............
3120 B–2020 ............
...................................
...................................
D1976–20 .................
I–3490–85.2
I–3492–96.47
I–4471–97.50
1631E 43.
...................................
...................................
200.7, Rev. 4.4
(1994).
PO 00000
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E:\FR\FM\21FEP2.SGM
21FEP2
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10751
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
37. Nickel—Total,4
mg/L.
Methodology 58
EPA 52
Standard methods 84
ASTM
ICP/MS ......................
200.8, Rev. 5.4
(1994).
...................................
3125 B–2020 ............
D5673–16 .................
...................................
...................................
993.14,3 I–4472–
97.81
See footnote.34
...................................
3111 B–2019 or 3111
C–2019.
3113 B–2020 ............
D1886–14 (A or B) ...
I–3499–85.2
D1886–14 (C) ...........
I–4503–89.51
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
DCP ..........................
Digestion,4 followed
by any of the following:
AA direct aspiration 36
AA furnace ................
STGFAA ....................
ICP/AES 36 ................
ICP/MS ......................
38. Nitrate (as N), mg/
L.
39. Nitrate-nitrite (as
N), mg/L.
DCP 36 .......................
Ion Chromatography
CIE/UV ......................
Ion Selective Electrode.
Colorimetric (Brucine
sulfate).
Spectrophotometric
(2,6dimethylphenol).
Nitrate-nitrite N minus
Nitrite N (See parameters 39 and
40).
Cadmium reduction,
Manual.
Cadmium reduction,
Automated.
Automated hydrazine
Reduction/Colorimetric.
Ion Chromatography
lotter on DSK11XQN23PROD with PROPOSALS2
40. Nitrite (as N), mg/L
CIE/UV ......................
Enzymatic reduction,
followed by automated colorimetric
determination.
Enzymatic reduction,
followed by manual
colorimetric determination.
Spectrophotometric
(2,6dimethylphenol).
Spectrophotometric:
Manual.
Automated
(Diazotization).
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
300.0, Rev. 2.1
(1993) and 300.1,
Rev. 1.0 (1997).
...................................
...................................
...................................
4110 B–2020 or C–
2020.
D4190–15 .................
D4327–17 .................
993.14,3 I–4020–
05,70 I–4472–97.81
See footnote.34
993.30.3
4140 B–2020 ............
4500–NO3¥ D–2019.
D6508–15 .................
D6508, Rev. 2.54
352.1 (Issued 1971) 1
...................................
...................................
...................................
...................................
...................................
973.50,3 419D,86 p.
28.9
Hach 10206.75
...................................
4500–NO3¥ E–2019
D3867–16 (B).
353.2, Rev. 2.0
(1993).
4500–NO3¥ F–2019
or 4500–NO3¥ I–
2019.
4500–NO3¥ H–2019.
...................................
D3867–16 (A) ...........
I–2545–90.51
...................................
See footnote.62
300.0, Rev. 2.1
(1993) and 300.1,
Rev. 1.0 (1997).
...................................
...................................
4110 B–2020 or C–
2020.
D4327–17 .................
993.30.3
4140 B–2020 ............
...................................
D6508–15 .................
D7781–14 .................
D6508, Rev. 2.54
I–2547–11,72 I–2548–
11,72 N07–0003.73
...................................
4500–NO3¥ J–2018.
...................................
...................................
...................................
Hach 10206.75
...................................
4500–NO2¥ B–2021
...................................
See footnote.25
...................................
...................................
...................................
I–4540–85,2 See footnote.62 I–2540–
90.80
I–4545–85.2
...................................
...................................
Automated (*bypass
353.2, Rev. 2.0
cadmium reduction).
(1993).
Manual (*bypass cad- ...................................
mium or enzymatic
reduction).
Ion Chromatography
300.0, Rev. 2.1
(1993) and 300.1,
Rev. 1.0 (1997).
CIE/UV ...................... ...................................
Automated (*bypass
...................................
Enzymatic reduction).
VerDate Sep<11>2014
19:11 Feb 17, 2023
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USGS/AOAC/other
PO 00000
Frm 00029
Fmt 4701
4500–NO3¥ F–2019
D3867–16 (A) ...........
4500–NO3¥ I–2019.
4500–NO3¥ E–2019, D3867–16 (B).
4500–NO3¥ J–
2018.
4110 B–2020 or C–
D4327–17 .................
2020.
4140 B–2020 ............
...................................
Sfmt 4702
D6508–15 .................
D7781–14 .................
E:\FR\FM\21FEP2.SGM
21FEP2
993.30.3
D6508, Rev. 2.54
I–2547–11,72 I–2548–
11,72 N07–0003.73
10752
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
41. Oil and grease—
Total recoverable,
mg/L.
42. Organic carbon—
Total (TOC), mg/L.
43. Organic nitrogen
(as N), mg/L.
44. Ortho-phosphate
(as P), mg/L.
Methodology 58
46. Oxygen, dissolved,
mg/L.
47. Palladium—Total,4
mg/L.
48. Phenols, mg/L ......
lotter on DSK11XQN23PROD with PROPOSALS2
49. Phosphorus (elemental), mg/L.
50. Phosphorus—
Total, mg/L.
51. Platinum—Total,4
mg/L.
VerDate Sep<11>2014
Standard methods 84
ASTM
USGS/AOAC/other
Hexane extractable
material (HEM): nHexane extraction
and gravimetry.
Silica gel treated
HEM (SGT–HEM):
Silica gel treatment
and gravimetry.
Combustion ...............
1664 Rev. A; 1664
Rev. B 42.
5520 B or G–2021 38.
1664 Rev. A; 1664
Rev. B 42.
5520 B or G–2021 38
and 5520 F–
2021 38.
...................................
5310 B–2014 ............
D7573–18a e1 ............
973.47,3 p. 14 24
Heated persulfate or
UV persulfate oxidation.
Total Kjeldahl N (Parameter 31) minus
ammonia N (Parameter 4).
Ascorbic acid method:
Automated .................
...................................
5310 C–2014 5310
D–2011.
D4839–03(17) ...........
973.47,3 p. 14.24
365.1, Rev. 2.0
(1993).
...................................
4500–P F–2021 or
G–2021.
4500–P E–2021 ........
...................................
D515–88 (A) .............
973.56,3 I–4601–85,2
I–2601–90.80
973.55.3
4110 B–2020 or C–
2020.
D4327–17 .................
993.30.3
4140 B–2020 ............
D6508–15 .................
D6508, Rev. 2.54
973.45B,3 I–1575–
78.8
I–1576–78.8
See footnote.63 See
footnote.64
Manual, single-reagent.
Manual, two-reagent
Ion Chromatography
45. Osmium—Total,4
mg/L.
EPA 52
CIE/UV ......................
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
Winkler (Azide modification).
Electrode ...................
Luminescence-Based
Sensor.
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
ICP/MS ......................
DCP ..........................
Manual distillation,26
followed by any of
the following:.
Colorimetric (4AAP)
manual.
Automated colorimetric (4AAP).
Gas-liquid chromatography.
Digestion,20 followed
by any of the following:
Manual ......................
Automated ascorbic
acid reduction.
ICP/AES 4 36 ..............
Semi-automated
block digestor (TKP
digestion).
Digestion with
persulfate, followed
by Colorimetric.
Digestion,4 followed
by any of the following:
AA direct aspiration ..
19:11 Feb 17, 2023
Jkt 259001
365.3 (Issued 1978) 1.
300.0, Rev. 2.1
(1993) and 300.1,
Rev. 1.0 (1997).
...................................
...................................
252.2 (Issued 1978) 1.
...................................
3111 D–2019.
4500–O (B–F)-2021 ..
D888–18 (A) .............
...................................
...................................
4500–O G–2021 .......
4500–O H–2021 .......
D888–18 (B) .............
D888–18 (C) .............
...................................
253.2 (Issued 1978) 1.
...................................
...................................
420.1 (Rev. 1978) 1 ...
3111 B–2019.
3125 B–2020.
...................................
5530 B–2021 ............
420.1 (Rev. 1978) 1 ...
5530 D–2021 27 .........
D1783–01(12) (A or
B).
...................................
...................................
...................................
See footnote.28
...................................
4500–P B (5)–2021 ..
...................................
973.55.3
365.3 (Issued 1978) 1
365.1 Rev. 2.0 (1993)
4500–P E–2021 ........
4500–P (F–H)–2021
D515–88 (A).
...................................
973.56,3 I–4600–85.2
200.7, Rev. 4.4
(1994).
365.4 (Issued 1974) 1
3120 B–2020 ............
...................................
I–4471–97.50
...................................
D515–88 (B) .............
I–4610–91.48
...................................
...................................
...................................
NCASI TNTP
W10900.77
...................................
3111 B–2019.
...................................
D1783–01(12).
See footnote.34
420.4 Rev. 1.0 (1993).
PO 00000
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Fmt 4701
Sfmt 4702
E:\FR\FM\21FEP2.SGM
21FEP2
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10753
TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
Methodology 58
EPA 52
Standard methods 84
ASTM
255.2 (Issued 1978) 1.
...................................
...................................
3125 B–2020.
...................................
...................................
See footnote.34
52. Potassium—Total,4
mg/L.
AA furnace ................
ICP/MS ......................
DCP ..........................
Digestion,4 followed
by any of the following:
AA direct aspiration ..
ICP/AES ....................
3111 B–2019 ............
3120 B–2020.
...................................
973.53,3 I–3630–85.2
ICP/MS ......................
53. Residue—Total,
mg/L.
54. Residue—filterable, mg/L.
55. Residue—non-filterable (TSS), mg/L.
56. Residue—settleable, mg/L.
57. Residue—Volatile,
mg/L.
58. Rhodium—Total,4
mg/L.
59. Ruthenium—
Total,4 mg/L.
60. Selenium—Total,4
mg/L.
Flame photometric ....
Electrode ...................
Ion Chromatography
Gravimetric, 103–
105°.
Gravimetric, 180° ......
Gravimetric, 103–
105° post-washing
of residue.
Volumetric (Imhoff
cone), or
gravimetric.
Gravimetric, 550° ......
Digestion,4 followed
by any of the following:
AA direct aspiration,
or.
AA furnace ................
ICP/MS ......................
Digestion,4 followed
by any of the following:
AA direct aspiration,
or.
AA furnace ................
ICP/MS ......................
Digestion,4 followed
by any of the following:
AA furnace ................
STGFAA ....................
ICP/AES 36 ................
ICP/MS ......................
AA gaseous hydride
61. Silica—Dissolved,37 mg/L.
0.45-micron filtration
followed by any of
the following:
Colorimetric, Manual
Automated
(Molybdosilicate).
ICP/AES ....................
lotter on DSK11XQN23PROD with PROPOSALS2
ICP/MS ......................
62. Silver—Total,4 31
mg/L.
Digestion,4 29 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
STGFAA ....................
VerDate Sep<11>2014
19:11 Feb 17, 2023
Jkt 259001
USGS/AOAC/other
...................................
200.7, Rev. 4.4
(1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
...................................
...................................
3125 B–2020 ............
D5673–16 .................
993.14.3
3500–K B–2020.
3500–K C–2020.
...................................
2540 B–2020 ............
D6919–17.
...................................
I–3750–85.2
...................................
2540 C–2020 ............
D5907–18 (B) ...........
I–1750–85.2
...................................
2540 D–2020 ............
D5907–18 (A) ...........
I–3765–85.2
...................................
2540 F–2020.
160.4 (Issued 1971) 1
2540 E–2020 ............
...................................
I–3753–85.2
...................................
3111 B–2019.
265.2 (Issued 1978) 1.
...................................
3125 B–2020.
...................................
3111 B–2019.
267.2 1.
...................................
3125 B–2020.
3113 B–2020 ............
D3859–15 (B) ...........
I–4668–98.49
3120 B–2020 ............
D1976–20.
3125 B–2020 ............
D5673–16 .................
3114 B–2020, or
3114 C–2020.
D3859–15 (A) ...........
993.14,3 I–4020–
05,70 I–4472–97.81
I–3667–85.2
4500–SiO2 C–2021 ...
4500–SiO2 E–2021 or
F–2021.
3120 B–2020 ............
D859–16 ...................
...................................
I–1700–85.2
I–2700–85.2
...................................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
993.14.3
3111 B–2019 or 3111
C–2019.
3113 B–2020 ............
...................................
974.27,3 p. 37,9 I–
3720–85.2
I–4724–89.51
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
...................................
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
200.9, Rev. 2.2
(1994).
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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
Methodology 58
EPA 52
Standard methods 84
ASTM
ICP/AES ....................
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
...................................
...................................
993.14,3 I–4472–
97.81
See footnote.34
3111 B–2019 ............
3120 B–2020 ............
...................................
...................................
973.54,3 I–3735–85.2
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
993.14.3
DCP ..........................
Flame photometric ....
Ion Chromatography
Wheatstone bridge ....
...................................
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
...................................
120.1 (Rev. 1982) 1 ...
...................................
3500-Na B–2020.
...................................
2510 B–2021 ............
...................................
See footnote.34
D6919–17.
D1125–95(99) (A) .....
973.40,3 I–2781–85.2
Automated colorimetric.
Gravimetric ................
375.2, Rev. 2.0
(1993).
...................................
...................................
925.54. 3
Turbidimetric .............
Ion Chromatography
...................................
300.0, Rev. 2.1
(1993) and 300.1,
Rev. 1.0 (1997).
...................................
...................................
4500–SO42¥ F–2021
or G–2021.
4500–SO42¥ C–2021
or D–2021.
4500–SO42¥ E–2021
4110 B–2020 or C–
2020.
ICP/MS ......................
63. Sodium—Total,4
mg/L.
DCP ..........................
Digestion,4 followed
by any of the following:
AA direct aspiration ..
ICP/AES ....................
ICP/MS ......................
64. Specific conductance, micromhos/cm
at 25 °C.
65. Sulfate (as SO4),
mg/L.
66. Sulfide (as S), mg/
L.
67. Sulfite (as SO3),
mg/L.
68. Surfactants, mg/L
69. Temperature, °C ..
70. Thallium—Total,4
mg/L.
CIE/UV ......................
Sample Pretreatment
Titrimetric (iodine) .....
Colorimetric (methylene blue).
Ion Selective Electrode.
Titrimetric (iodineiodate).
Colorimetric (methylene blue).
Thermometric ............
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
STGFAA ....................
ICP/AES ....................
ICP/MS ......................
71. Tin—Total,4 mg/L
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
STGFAA ....................
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ICP/AES ....................
ICP/MS ......................
72. Titanium—Total,4
mg/L.
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AA direct aspiration ..
AA furnace ................
ICP/AES ....................
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D4327–17 .................
USGS/AOAC/other
993.30,3 I–4020–
05.70
4140 B–2020 ............ D6508–15 .................
4500–S2¥ B, C–2021.
D6508, Rev. 2.54
...................................
...................................
4500–S2¥ F–2021 ....
4500–S2¥ D–2021.
...................................
I–3840–85.2
...................................
4500–S2¥ G–2021 ...
D4658–15.
...................................
4500–SO32¥ B–2021.
...................................
5540 C–2021 ............
D2330–20.
...................................
2550 B–2010 ............
...................................
...................................
279.2 (Issued 1978) 1
200.9, Rev. 2.2
(1994).
200.7, Rev. 4.4
(1994).
200.8, Rev. 5.4
(1994).
3111 B–2019.
3113 B–2020.
...................................
...................................
200.9, Rev. 2.2
(1994).
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
283.2 (Issued 1978) 1.
200.7, Rev. 4.4
(1994).
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3120 B–2020 ............
D1976–20.
3125 B–2020 ............
D5673–16 .................
993.14,3 I–4471–
97,50 I–4472–97.81
3111 B–2019 ............
3113 B–2020.
...................................
I–3850–78.8
3125 B–2020 ............
D5673–16 .................
993.14.3
3111 D–2019.
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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued
Parameter
73. Turbidity, NTU 53 ..
74. Vanadium—Total,4
mg/L.
Methodology 58
EPA 52
Standard methods 84
ASTM
ICP/MS ......................
200.8, Rev. 5.4
(1994).
...................................
180.1, Rev. 2.0
(1993).
3125 B–2020 ............
D5673–16 .................
993.14.3
...................................
2130 B–2020 ............
...................................
D1889–00 .................
See footnote.34
I–3860–85.2 See footnote.65 See footnote.66 See footnote.67
...................................
...................................
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
3111 D–2019.
3113 B–2020 ............
3120 B–2020 ............
D3373–17.
D1976–20 .................
3125 B–2020 ............
D5673–16 .................
...................................
3500–V B–2011.
D4190–15 .................
3111 B–2019 or 3111
C–2019.
D1691–17 (A or B) ...
974.27,3 p. 37,9 I–
3900–85.2
3120 B–2020 ............
D1976–20 .................
I–4471–97.50
3125 B–2020 ............
D5673–16 .................
...................................
3500 Zn B–2020 .......
D4190–15 .................
...................................
993.14,3 I–4020–
05,70 I–4472–97.81
See footnote.34
See footnote.33
DCP ..........................
Nephelometric ...........
Digestion,4 followed
by any of the following:
AA direct aspiration ..
AA furnace ................
ICP/AES ....................
ICP/MS ......................
75. Zinc—Total,4 mg/L
DCP ..........................
Colorimetric (Gallic
Acid).
Digestion,4 followed
by any of the following:
AA direct aspiration 36
AA furnace ................
ICP/AES 36 ................
ICP/MS ......................
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76. Acid Mine Drainage.
DCP 36 .......................
Colorimetric (Zincon)
...................................
...................................
289.2 (Issued 1978) 1.
200.5, Rev. 4.2
(2003); 68 200.7,
Rev. 4.4 (1994).
200.8, Rev. 5.4
(1994).
...................................
...................................
1627 69.
USGS/AOAC/other
I–4471–97.50
993.14,3 I–4020–
05.70
See footnote.34
Table IB Notes:
1 Methods for Chemical Analysis of Water and Wastes, EPA–600/4–79–020. Revised March 1983 and 1979, where applicable. U.S. EPA.
2 Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resource Investigations of the U.S. Geological Survey, Book 5, Chapter A1., unless otherwise stated. 1989. USGS.
3 Official Methods of Analysis of the Association of Official Analytical Chemists, Methods Manual, Sixteenth Edition, 4th Revision, 1998. AOAC
International.
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 (as
specified in Section 4.1.3 of Methods for Chemical Analysis of Water and Wastes) 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
(FLAA) determinations, a combination acid (nitric and hydrochloric acids) digestion is preferred, prior to analysis. The approved 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 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 of this section); 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 or other catalysts that have been found suitable may 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. In general, the analytical method should be consulted regarding the need for distillation. If the method is not clear, the laboratory may compare a minimum of 9 different sample matrices to
evaluate the need for distillation. For each matrix, a matrix spike and matrix spike duplicate are analyzed both with and without the distillation
step (for a total of 36 samples, assuming 9 matrices). If results are comparable, the laboratory may dispense with the distillation step for future
analysis. Comparable is defined as <20% RPD for all tested matrices). Alternatively, the two populations of spike recovery percentages may be
compared using a recognized statistical test.
7 Industrial Method Number 379–75 WE Ammonia, Automated Electrode Method, Technicon Auto Analyzer II. February 19, 1976. Bran &
Luebbe Analyzing Technologies Inc.
8 The approved method is that cited in Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, Techniques of
Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1979. USGS.
9 American National Standard on Photographic Processing Effluents. April 2, 1975. American National Standards Institute.
10 In-Situ Method 1003–8–2009, Biochemical Oxygen Demand (BOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.
11 The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable.
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12 Carbonaceous biochemical oxygen demand (CBOD ) must not be confused with the traditional BOD test method which measures ‘‘total 55
5
day 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. 1978. Oceanography International Corporation.
14 Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company.
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. 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 Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry, EPA–821–R–05–001. Revision 2.0, February 2005. US
EPA.
18 National Council of the Paper Industry for Air and Stream Improvement (NCASI) Technical Bulletin 253 (1971) and Technical Bulletin 803,
May 2000.
19 Method 8506, Bicinchoninate Method for Copper, Hach Handbook of Water Analysis. 1979. Hach Company.
20 When using a method with block digestion, this treatment is not required.
21 Industrial Method Number 378–75WA, Hydrogen ion (pH) Automated Electrode Method, Bran & Luebbe (Technicon) Autoanalyzer II. October 1976. Bran & Luebbe Analyzing Technologies.
22 Method 8008, 1,10-Phenanthroline Method using FerroVer Iron Reagent for Water. 1980. Hach Company.
23 Method 8034, Periodate Oxidation Method for Manganese, Hach Handbook of Wastewater Analysis. 1979. Hach Company.
24 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, (1972 Revised 1987). 1987. USGS.
25 Method 8507, Nitrogen, Nitrite-Low Range, Diazotization Method for Water and Wastewater. 1979. Hach Company.
26 Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH.
27 The colorimetric reaction must be conducted at a pH of 10.0 ± 0.2.
28 Addison, R.F., and R.G. Ackman. 1970. Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography, Journal of Chromatography, 47(3):421–426.
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 use of EDTA decreases method sensitivity. Analysts may omit EDTA or replace with another suitable complexing reagent provided that
all method-specified quality control acceptance criteria are met.
31 For samples known or suspected to contain high levels of silver (e.g., in excess of 4 mg/L), cyanogen iodide should be used to keep the silver in solution for analysis. Prepare a cyanogen iodide solution by adding 4.0 mL of concentrated NH4OH, 6.5 g of KCN, and 5.0 mL of a 1.0 N
solution of I2 to 50 mL of reagent water in a volumetric flask and dilute to 100.0 mL. After digestion of the sample, adjust the pH of the digestate
to >7 to prevent the formation of HCN under acidic conditions. Add 1 mL of the cyanogen iodide solution to the sample digestate and adjust the
volume to 100 mL with reagent water (NOT acid). If cyanogen iodide is added to sample digestates, then silver standards must be prepared that
contain cyanogen iodide as well. Prepare working standards by diluting a small volume of a silver stock solution with water and adjusting the pH
>7 with NH4OH. Add 1 mL of the cyanogen iodide solution and let stand 1 hour. Transfer to a 100-mL volumetric flask and dilute to volume with
water.
32 ‘‘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. USGS.
33 Method 8009, Zincon Method for Zinc, Hach Handbook of Water Analysis, 1979. Hach Company.
34 Method AES0029, Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes.
1986-Revised 1991. Thermo Jarrell Ash Corporation.
35 In-Situ Method 1004–8–2009, Carbonaceous Biochemical Oxygen Demand (CBOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.
36 Microwave-assisted digestion may be employed for this metal, when analyzed by this methodology. Closed Vessel Microwave Digestion of
Wastewater Samples for Determination of Metals. April 16, 1992. 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 (n-Hexane—85% minimum purity, 99.0% min. saturated C6 isomers, residue less than 1 mg/L) extraction solvent when
determining Oil and Grease parameters—Hexane Extractable Material (HEM), or Silica Gel Treated HEM (analogous to EPA Methods 1664 Rev.
A and 1664 Rev. B). Use of other extraction solvents is prohibited.
39 Method PAI–DK01, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Titrimetric Detection. Revised December 22, 1994. OI Analytical.
40 Method PAI–DK02, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Colorimetric Detection. Revised December 22, 1994. OI Analytical.
41 Method PAI–DK03, Nitrogen, Total Kjeldahl, Block Digestion, Automated FIA Gas Diffusion. Revised December 22, 1994. OI Analytical.
42 Method 1664 Rev. B is the revised version of EPA Method 1664 Rev. A. U.S. EPA. February 1999, Revision A. Method 1664, 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. U.S. EPA. February 2010, Revision B. Method 1664, 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–10–
001.
43 Method 1631, Revision E, Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry, EPA–821–
R–02–019. Revision E. August 2002, U.S. EPA. The application of clean techniques described in EPA’s 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 Method OIA–1677–09, Available Cyanide by Ligand Exchange and Flow Injection Analysis (FIA). 2010. OI Analytical.
45 Open File Report 00–170, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Ammonium Plus Organic Nitrogen by a Kjeldahl Digestion Method and an Automated Photometric Finish that Includes Digest Cleanup by Gas Diffusion. 2000. USGS.
46 Open File Report 93–449, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Chromium in Water by Graphite Furnace Atomic Absorption Spectrophotometry. 1993. USGS.
47 Open File Report 97–198, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Molybdenum by Graphite Furnace Atomic Absorption Spectrophotometry. 1997. USGS.
48 Open File Report 92–146, 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. 1992. USGS.
49 Open File Report 98–639, 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. 1999. USGS.
50 Open File Report 98–165, 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. 1998. USGS.
51 Open File Report 93–125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. USGS.
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52 Unless otherwise indicated, all EPA methods, excluding EPA Method 300.1, are published in U.S. EPA. May 1994. Methods for the Determination of Metals in Environmental Samples, Supplement I, EPA/600/R–94/111; or U.S. EPA. August 1993. Methods for the Determination of
Inorganic Substances in Environmental Samples, EPA/600/R–93/100. EPA Method 300.1 is U.S. EPA. Revision 1.0, 1997, including errata cover
sheet April 27, 1999. Determination of Inorganic Ions in Drinking Water by Ion Chromatography.
53 Styrene divinyl benzene beads (e.g., AMCO–AEPA–1 or equivalent) and stabilized formazin (e.g., Hach StablCal TM or equivalent) are acceptable substitutes for formazin.
54 Method D6508–15, Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis
and Chromate Electrolyte. 2015. ASTM.
55 Kelada–01, Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, and Thiocyanate, EPA 821–B–01–009, Revision
1.2, August 2001. US EPA. Note: A 450-W UV lamp may be used in this method instead of the 550-W lamp specified if it provides performance
within the quality control (QC) acceptance criteria of the method in a given instrument. Similarly, modified flow cell configurations and flow conditions may be used in the method, provided that the QC acceptance criteria are met.
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. Revision 2.2, March 2005. Lachat Instruments.
57 When using sulfide removal test procedures described in EPA 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 Samples analyzed for available cyanide using OI Analytical method OIA–1677–09 or ASTM method D6888–16 that contain particulate matter may be filtered only after the ligand exchange reagents have been added to the samples, because the ligand exchange process converts
complexes containing available cyanide to free cyanide, which is not removed by filtration. Analysts are further cautioned to limit the time between the addition of the ligand exchange reagents and sample filtration to no more than 30 minutes to preclude settling of materials in samples.
60 Analysts should be aware that pH optima and chromophore absorption maxima might differ when phenol is replaced by a substituted phenol
as the color reagent in Berthelot Reaction (‘‘phenol-hypochlorite reaction’’) colorimetric ammonium determination methods. For example, when
phenol is used as the color reagent, pH optimum and wavelength of maximum absorbance are about 11.5 and 635 nm, respectively—see, Patton, C.J. and S.R. Crouch. March 1977. Anal. Chem. 49:464–469. These reaction parameters increase to pH > 12.6 and 665 nm when salicylate
is used as the color reagent—see, Krom, M.D. April 1980. The Analyst 105:305–316.
61 If atomic absorption or ICP instrumentation is not available, the aluminon colorimetric method detailed in the 19th Edition of Standard Methods for the Examination of Water and Wastewater may be used. This method has poorer precision and bias than the methods of choice.
62 Easy (1–Reagent) Nitrate Method, Revision November 12, 2011. Craig Chinchilla.
63 Hach Method 10360, Luminescence Measurement of Dissolved Oxygen in Water and Wastewater and for Use in the Determination of BOD
5
and CBOD5. Revision 1.2, October 2011. Hach Company. This method may be used to measure dissolved oxygen when performing the methods approved in Table IB of this section for measurement of biochemical oxygen demand (BOD) and carbonaceous biochemical oxygen demand
(CBOD).
64 In-Situ Method 1002–8–2009, Dissolved Oxygen (DO) Measurement by Optical Probe. 2009. In-Situ Incorporated.
65 Mitchell Method M5331, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.
66 Mitchell Method M5271, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.
67 Orion Method AQ4500, Determination of Turbidity by Nephelometry. Revision 5, March 12, 2009. Thermo Scientific.
68 EPA Method 200.5, Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma-Atomic Emission
Spectrometry, EPA/600/R–06/115. Revision 4.2, October 2003. US EPA.
69 Method 1627, Kinetic Test Method for the Prediction of Mine Drainage Quality, EPA–821–R–09–002. December 2011. US EPA.
70 Techniques and Methods Book 5–B1, Determination of Elements in Natural-Water, Biota, Sediment and Soil Samples Using Collision/Reaction Cell Inductively Coupled Plasma-Mass Spectrometry, Chapter 1, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis, 2006. USGS.
71 Water-Resources Investigations Report 01–4132, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—
Determination of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural Water with Cold Vapor-Atomic Fluorescence Spectrometry,
2001. USGS.
72 USGS Techniques and Methods 5–B8, Chapter 8, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis, 2011 USGS.
73 NECi Method N07–0003, ‘‘Nitrate Reductase Nitrate-Nitrogen Analysis,’’ Revision 9.0, March 2014, The Nitrate Elimination Co., Inc.
74 Timberline Instruments, LLC Method Ammonia–001, ‘‘Determination of Inorganic Ammonia by Continuous Flow Gas Diffusion and Conductivity Cell Analysis,’’ June 2011, Timberline Instruments, LLC.
75 Hach Company Method 10206, ‘‘Spectrophotometric Measurement of Nitrate in Water and Wastewater,’’ Revision 2.1, January 2013, Hach
Company.
76 Hach Company Method 10242, ‘‘Simplified Spectrophotometric Measurement of Total Kjeldahl Nitrogen in Water and Wastewater,’’ Revision
1.1, January 2013, Hach Company.
77 National Council for Air and Stream Improvement (NCASI) Method TNTP–W10900, ‘‘Total (Kjeldahl) Nitrogen and Total Phosphorus in Pulp
and Paper Biologically Treated Effluent by Alkaline Persulfate Digestion,’’ June 2011, National Council for Air and Stream Improvement, Inc.
78 The pH adjusted sample is to be adjusted to 7.6 for NPDES reporting purposes.
79 I–2057–85 U.S. Geological Survey Techniques of Water-Resources Investigations, Book 5, Chap. A11989, Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, 1989.
80 Methods I–2522–90, I–2540–90, and I–2601–90 U.S. Geological Survey Open-File Report 93–125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments, 1993.
81 Method I–1472–97, U.S. Geological Survey Open-File Report 98–165, Methods of Analysis by the U.S. Geological Survey National Water
Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments, 1998.
82 FIAlab Instruments, Inc. Method FIAlab 100, ‘‘Determination of Inorganic Ammonia by Continuous Flow Gas Diffusion and Fluorescence Detector Analysis’’, April 4, 2018, FIAlab Instruments, Inc.
83 MACHEREY-NAGEL GmbH and Co. Method 036/038 NANOCOLOR® COD LR/HR, ‘‘Spectrophotometric Measurement of Chemical Oxygen
Demand in Water and Wastewater’’, Revision 1.5, May 2018, MACHEREY-NAGEL GmbH and Co. KG.
84 Please refer to the following applicable Quality Control Sections: Part 2000 Methods, Physical and Aggregate Properties 2020 (2021); Part
3000 Methods, Metals, 3020 (2021); Part 4000 Methods, Inorganic Nonmetallic Constituents, 4020 (2022); Part 5000 Methods, and Aggregate
Organic Constituents, 5020 (2022). These Quality Control Standards are available for download at www.standardmethods.org at no charge.
85 Each laboratory may establish its own control limits by performing at least 25 glucose-glutamic acid (GGA) checks over several weeks or
months and calculating the mean and standard deviation. The laboratory may then use the mean ± 3 standard deviations as the control limit for
future GGA checks. However, GGA acceptance criteria can be no wider than 198 ± 30.5 mg/L for BOD5. GGA acceptance criteria for CBOD
must be either 198 ± 30.5 mg/L, or the lab may develop control charts under the following conditions: dissolved oxygen uptake from the seed
contribution is between 0.6–1.0 mg/L; control charts are performed on at least 25 GGA checks with three standard deviations from the derived
mean; the RSD must not exceed 7.5%; and any single GGA value cannot be less than 150 mg/L or higher than 250 mg/L.
86 The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition, 1976.
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TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS
ASTM
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
...................................
...................................
O–4127–96.13
6410 B–2020 ............
6440B–2021 ..............
6200 C–2020.
6200 B–2020 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
...................................
...................................
625.1,5 1625B ...........
605.
610.
625.1, 1625B ............
610 ............................
610.
625.1, 1625B ............
610 ............................
610.
...................................
6410 B–2020.
...................................
O–4127–96,13 O–
4436–16.14
See footnote,3 p. 1.
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
GC/MS ......................
HPLC ........................
GC .............................
625.1, 1625B ............
610 ............................
610.
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
GC/MS ......................
HPLC ........................
GC .............................
625.1, 1625B ............
610 ............................
610.
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
625.1, 1625B ............
610 ............................
...................................
...................................
6410 B–2020 ............
6440 B–2021 ............
...................................
...................................
...................................
D4657–92 (98).
...................................
...................................
See footnote,9 p. 27.
GC .............................
606.
GC/MS ......................
GC .............................
625.1, 1625B ............
611.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
625.1, 1625B ............
611.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
625.1, 1625B ............
606.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
625.1, 1625B ............
601 ............................
6410 B–2020 ............
6200 C–2020.
...................................
See footnote,9 p. 27.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
601 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
601 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
611.
GC/MS ......................
GC .............................
625.1, 1625B ............
601 ............................
6410 B–2020 ............
6200 C–2020 ............
...................................
...................................
See footnote,9 p. 27.
See footnote,3 p. 130.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
Method
EPA 2 7
1. Acenaphthene ........
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
610.
625.1, 1625B ............
610 ............................
610.
625.1, 1625B ............
610 ............................
603.
624.1,4 1624B.
603.
624.1,4 1624B ...........
610.
625.1, 1625B ............
610 ............................
602 ............................
624.1, 1624B ............
Spectro-photometric ..
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
2. Acenaphthylene .....
3. Acrolein ..................
4. Acrylonitrile .............
5. Anthracene .............
6. Benzene .................
7. Benzidine ...............
8. Benzo(a)anthracene
9. Benzo(a)pyrene ......
10. Benzo(b)fluoranthene.
11.
Benzo(g,h,i)perylene.
12. Benzo(k)fluoranthene.
13. Benzyl chloride .....
14. Butyl benzyl
phthalate.
15. bis(2Chloroethoxy) methane.
16. bis(2-Chloroethyl)
ether.
17. bis(2-Ethylhexyl)
phthalate.
18.
Bromodichloromethane.
19. Bromoform ...........
20. Bromomethane .....
lotter on DSK11XQN23PROD with PROPOSALS2
Standard
methods 15
Parameter 1
21. 4-Bromophenyl
phenyl ether.
22. Carbon tetrachloride.
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See footnote,3 p. 130.
See footnote,6 p.
S102.
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10759
TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued
Method
EPA 2 7
23. 4-Chloro-3-methyl
phenol.
GC .............................
604 ............................
6420 B–2020.
GC/MS ......................
GC .............................
GC/MS ......................
625.1, 1625B ............
601, 602 ....................
624.1, 1624B ............
GC .............................
GC/MS ......................
GC .............................
601 ............................
624.1, 1624B ............
601.
GC/MS ......................
GC .............................
GC/MS ......................
24. Chlorobenzene .....
25. Chloroethane ........
26. 2-Chloroethylvinyl
ether.
27. Chloroform ...........
28. Chloromethane .....
29. 2Chloronaphthalene.
30. 2-Chlorophenol .....
31. 4-Chlorophenyl
phenyl ether.
32. Chrysene ..............
33.
Dibenzo(a,h)anthracene.
34.
Dibromochloromethane.
35. 1,2Dichlorobenzene.
36. 1,3Dichlorobenzene.
37. 1,4Dichlorobenzene.
38. 3,3′Dichlorobenzidine.
39. Dichlorodifluoromethane.
40. 1,1-Dichloroethane
lotter on DSK11XQN23PROD with PROPOSALS2
Standard
methods 15
Parameter 1
41. 1,2-Dichloroethane
42. 1,1-Dichloroethene
43. trans-1,2Dichloroethene.
VerDate Sep<11>2014
ASTM
Other
6410 B–2020 ............
6200 C–2020 ............
6200 B–2020 ............
...................................
...................................
...................................
See footnote,9 p. 27.
See footnote,3 p. 130.
O–4127–96,13 O–
4436–16.14
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96.13
624.1, 1624B.
601 ............................
624.1, 1624B ............
6200 C–2020 ............
6200 B–2020 ............
...................................
...................................
See footnote,3 p. 130.
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
601 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
612.
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
625.1, 1625B ............
604 ............................
625.1, 1625B ............
611.
6410 B–2020 ............
6420 B–2020.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
625.1, 1625B ............
610.
625.1, 1625B ............
610 ............................
610.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
GC/MS ......................
HPLC ........................
GC .............................
625.1, 1625B ............
610 ............................
601 ............................
6410 B–2020 ............
6440 B–2021 ............
6200 C–2020.
...................................
D4657–92 (98).
See footnote,9 p. 27.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
601, 602 ....................
6200 C–2020.
GC/MS ......................
624.1, 1625B ............
6200 B–2020 ............
...................................
See footnote,9 p. 27
O–4127–96,13 O–
4436–16.14
GC .............................
601, 602 ....................
6200 C–2020.
GC/MS ......................
624.1, 1625B ............
6200 B–2020 ............
...................................
See footnote,9 p. 27
O–4127–96.13
GC .............................
601, 602 ....................
6200 C–2020.
GC/MS ......................
624.1, 1625B ............
6200 B–2020 ............
...................................
See footnote,9 p. 27
O–4127–96,13 O–
4436–16.14
GC/MS ......................
625.1, 1625B ............
6410 B–2020.
HPLC ........................
GC .............................
605.
601.
GC/MS ......................
...................................
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
601 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
601 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
601 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
601 ............................
6200 C–2020.
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued
Method
EPA 2 7
Standard
methods 15
ASTM
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
GC .............................
604 ............................
625.1, 1625B ............
601 ............................
6420 B–2020..
6410 B–2020 ............
6200 C–2020.
...................................
See footnote,9 p. 27.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
601 ............................
6200 C–2020.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
601 ............................
6200 C–2020.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
606.
625.1, 1625B ............
604 ............................
625.1, 1625B ............
606.
625.1, 1625B ............
606.
6410 B–2020 ............
6420 B–2020.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
...................................
See footnote,9 p. 27.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
625.1, 1625B ............
606.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
625.1, 1625B ............
604 ............................
625.1, 1625B ............
609.
625.1, 1625B ............
609.
625.1, 1625B ............
...................................
...................................
6410 B–2020 ............
6420 B–2020 ............
6410 B–2020.
...................................
...................................
See footnote,9 p. 27.
See footnote,9 p. 27.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
6410 B–2020 ............
...................................
...................................
...................................
...................................
...................................
See footnote,9 p. 27.
See footnote,3 p. 130.
See footnote,6 p.
S102.
GC .............................
GC/MS ......................
602 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
HPLC ........................
GC/MS ......................
610.
625.1, 1625B ............
610 ............................
610.
625.1, 1625B ............
610 ............................
1613B 10 ....................
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
6410 B–2020 ............
6440 B–2021 ............
...................................
...................................
D4657–92 (98).
...................................
See footnote,9 p. 27.
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC .............................
612.
GC/MS ......................
GC .............................
625.1, 1625B ............
612.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
625.1, 1625B ............
6410 B–2020 ............
...................................
See footnote,9 p. 27
O–4127–96.13
GC .............................
612.
GC/MS ......................
625.1,5 1625B ...........
6410 B–2020 ............
...................................
GC/MS ......................
1613B 10 ....................
...................................
...................................
See footnote,9 p. 27
O–4127–96.13
ATM 16130,15 PAM
16130–SSI.16
Parameter 1
44. 2,4-Dichlorophenol
45. 1,2Dichloropropane.
46. cis-1,3Dichloropropene.
47. trans-1,3Dichloropropene.
48. Diethyl phthalate ..
49. 2,4-Dimethylphenol
50. Dimethyl phthalate
51. Di-n-butyl phthalate.
52. Di-n-octyl phthalate.
53. 2, 4-Dinitrophenol
54. 2,4-Dinitrotoluene
55. 2,6-Dinitrotoluene
56. Epichlorohydrin ....
57. Ethylbenzene .......
58. Fluoranthene ........
59. Fluorene ...............
60. 1,2,3,4,6,7,8Heptachlorodibenzofuran.
61. 1,2,3,4,7,8,9Heptachlorodibenzofuran.
62. 1,2,3,4,6,7,8Heptachlorodibenzo-p-dioxin.
63.
Hexachlorobenzene.
lotter on DSK11XQN23PROD with PROPOSALS2
64.
Hexachlorobutadiene.
65.
Hexachlorocyclopentadiene.
66. 1,2,3,4,7,8Hexachlorodibenzofuran.
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ATM 16130,15 PAM
16130–SSI.16
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10761
TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued
Parameter 1
Method
EPA 2 7
Standard
methods 15
ASTM
67. 1,2,3,6,7,8Hexachlorodibenzofuran.
68. 1,2,3,7,8,9Hexachlorodibenzofuran.
69. 2,3,4,6,7,8Hexachlorodibenzofuran.
70. 1,2,3,4,7,8Hexachloro-dibenzop-dioxin.
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
71. 1,2,3,6,7,8Hexachloro-dibenzop-dioxin.
72. 1,2,3,7,8,9Hexachloro-dibenzop-dioxin.
73. Hexachloroethane
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI,16 G
BHTYHGTGB B VB
B5 BV.
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC .............................
GC/MS ......................
612.
625.1, 1625B ............
6410 B–2020 ............
...................................
See footnote,9 p. 27
O–4127–96.13
GC .............................
610.
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
625.1, 1625B ............
610 ............................
609.
625.1, 1625B ............
601 ............................
624.1, 1624B ............
6410 B–2020 ............
6440 B–2021 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
6410 B–2020 ............
6200 C–2020 ............
6200 B–2020 ............
...................................
...................................
...................................
See footnote,9 p. 27.
See footnote,3 p. 130.
O–4127–96,13 O–
4436–16.14
GC .............................
604 ............................
6420 B–2020.
GC/MS ......................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
GC .............................
625.1, 1625B ............
610.
625.1, 1625B ............
610 ............................
609.
625.1, 1625B ............
...................................
604 ............................
625.1, 1625B ............
604 ............................
625.1, 1625B ............
607.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
6410 B–2020 ............
6440 B–2021.
...................................
See footnote,9 p. 27.
6410 B–2020 ............
...................................
6420 B–2020.
6410 B–2020 ............
6420 B–2020.
6410 B–2020 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
...................................
See footnote,9 p. 27.
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
625.1,5 1625B ...........
607.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
GC .............................
625.1,5 1625B ...........
607.
6410 B–2020 ............
...................................
See footnote,9 p. 27.
GC/MS ......................
GC/MS ......................
625.1,5 1625B ...........
1613B 10 ....................
6410 B–2020 ............
...................................
...................................
...................................
See footnote,9 p. 27.
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC .............................
611.
GC/MS ......................
GC .............................
625.1, 1625B ............
608.3 .........................
6410 B–2020 ............
...................................
...................................
...................................
See footnote,9 p. 27.
See footnote,3 p. 43;
See footnote.8
GC/MS ......................
625.1 .........................
6410 B–2020.
74. Indeno(1,2,3-c,d)
pyrene.
75. Isophorone ...........
76. Methylene chloride
77. 2-Methyl-4,6dinitrophenol.
78. Naphthalene .........
79. Nitrobenzene ........
80. 2-Nitrophenol ........
81. 4-Nitrophenol ........
82. NNitrosodimethylamine.
83. N-Nitrosodi-n-propylamine.
lotter on DSK11XQN23PROD with PROPOSALS2
84. NNitrosodiphenylamine.
85.
Octachlorodibenzofuran.
86.
Octachlorodibenzop-dioxin.
87. 2,2′-oxybis(1chloropropane) 12
[also known as
bis(2-Chloro-1methylethyl) ether].
88. PCB–1016 ............
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued
Parameter 1
Method
EPA 2 7
Standard
methods 15
ASTM
89. PCB–1221 ............
GC .............................
608.3 .........................
...................................
...................................
See footnote,3 p. 43;
See footnote.8
90. PCB–1232 ............
GC/MS ......................
GC .............................
625.1 .........................
608.3 .........................
6410 B–2020.
...................................
...................................
See footnote,3 p. 43;
See footnote.8
91. PCB–1242 ............
GC/MS ......................
GC .............................
625.1 .........................
608.3 .........................
6410 B–2020.
...................................
...................................
See footnote,3 p. 43;
See footnote.8
92. PCB–1248 ............
GC/MS ......................
GC .............................
625.1 .........................
608.3 .........................
6410 B–2020.
...................................
...................................
See footnote,3 p. 43;
See footnote.8
93. PCB–1254 ............
GC/MS ......................
GC .............................
625.1 .........................
608.3 .........................
6410 B–2020.
...................................
...................................
See footnote,3 p. 43;
See footnote.8
94. PCB–1260 ............
GC/MS ......................
GC .............................
625.1 .........................
608.3 .........................
6410 B–2020.
...................................
...................................
See footnote,3 p. 43;
See footnote.8
GC/MS ......................
GC/MS ......................
625.1 .........................
1613B 10 ....................
6410 B–2020.
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC/MS ......................
1613B 10 ....................
...................................
...................................
ATM 16130,15 PAM
16130–SSI.16
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
HPLC ........................
GC .............................
GC/MS ......................
GC .............................
GC/MS ......................
HPLC ........................
GC/MS ......................
604 ............................
625.1, 1625B ............
610.
625.1, 1625B ............
610 ............................
604 ............................
625.1, 1625B ............
610.
625.1, 1625B ............
610 ............................
1613B 10 ....................
6420 B–2020 ............
6410 B–2020 ............
...................................
...................................
See footnote,3 p. 140.
See footnote,9 p. 27.
6410
6440
6420
6410
B–2020 ............
B–2021 ............
B–2020.
B–2020 ............
...................................
D4657–92 (98).
See footnote,9 p. 27.
...................................
See footnote,9 p. 27.
6410 B–2020 ............
6440 B–2021 ............
...................................
...................................
D4657–92 (98).
...................................
See footnote,9 p. 27.
GC/MS ......................
613, 625.1,5a 1613B
...................................
...................................
GC .............................
601 ............................
6200 C–2020 ............
...................................
See footnote,3 p. 130.
GC/MS ......................
GC .............................
624.1, 1624B ............
601 ............................
6200 B–2020 ............
6200 C–2020 ............
...................................
...................................
O–4127–96.13
See footnote,3 p. 130.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
602 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
GC .............................
612 ............................
...................................
...................................
O–4127–96,13 O–
4436–16.14
See footnote,3 p. 130.
GC/MS ......................
625.1, 1625B ............
6410 B–2020 ............
...................................
See footnote,9 p. 27
O–4127–96,13 O–
4436–16.14
GC .............................
601 ............................
6200 C–2020.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
GC .............................
601 ............................
6200 C–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
See footnote,3 p. 130.
GC/MS ......................
624.1, 1624B ............
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
GC/MS ......................
601 ............................
624.1, 1624B ............
6200 C–2020.
6200 B–2020 ............
...................................
O–4127–96,13 O–
4436–16.14
GC .............................
601 ............................
6200 C–2020.
95. 1,2,3,7,8Pentachlorodibenzofuran.
96. 2,3,4,7,8Pentachlorodibenzofuran.
97. 1,2,3,7,8Pentachlorodibenzo-p-dioxin.
98. Pentachlorophenol
99. Phenanthrene .......
100. Phenol ................
101. Pyrene ................
102. 2,3,7,8-Tetrachloro-dibenzofuran.
103. 2,3,7,8-Tetrachloro-dibenzo-pdioxin.
104. 1,1,2,2Tetrachloroethane.
105.
Tetrachloroethene.
106. Toluene ..............
107. 1,2,4Trichlorobenzene.
lotter on DSK11XQN23PROD with PROPOSALS2
108. 1,1,1-Trichloroethane.
109. 1,1,2-Trichloroethane.
110. Trichloroethene ..
111.
Trichlorofluoromethane.
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ATM 16130,15 PAM
16130–SSI.16
ATM 16130,15 PAM
16130–SSI.16
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10763
TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued
Method
EPA 2 7
Standard
methods 15
ASTM
GC/MS ......................
GC .............................
624.1 .........................
604 ............................
6200 B–2020 ............
6420 B–2020.
...................................
O–4127–96.13
GC/MS ......................
GC .............................
GC/MS ......................
625.1, 1625B ............
601 ............................
624.1, 1624B ............
6410 B–2020 ............
6200 C–2020.
6200 B–2020 ............
...................................
See footnote,9 p. 27.
...................................
O–4127–96,13 O–
4436–16.14
GC/MS ......................
GC/MS ......................
...................................
...................................
...................................
...................................
D7065–17.
D7065–17.
GC/MS ......................
...................................
...................................
D7065–17.
GC/MS ......................
...................................
...................................
D7065–17.
GC/MS ......................
...................................
...................................
D7065–17.
Adsorption and
Coulometric Titration.
In Situ Acetylation
and GC/MS.
1650 11.
Parameter 1
112. 2,4,6Trichlorophenol.
113. Vinyl chloride ......
114. Nonylphenol .......
115. Bisphenol A
(BPA).
116. p-tert-Octylphenol
(OP).
117. Nonylphenol
Monoethoxylate
(NP1EO).
118. Nonylphenol
Diethoxylate
(NP2EO).
119. Adsorbable Organic Halides (AOX).
lotter on DSK11XQN23PROD with PROPOSALS2
120. Chlorinated
Phenolics.
Other
1653 11.
Table IC notes:
1 All parameters are expressed in micrograms per liter (μg/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, 1613B, 1624B, and 1625B are provided at appendix A, Test Procedures for Analysis of Organic Pollutants.
The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at appendix B of
this part, Definition and Procedure for the Determination of the Method Detection Limit. These methods are available at: https://www.epa.gov/
cwa-methods as individual PDF files.
3 Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S.
EPA.
4 Method 624.1 may be used for quantitative determination of acrolein and acrylonitrile, provided that the laboratory has documentation to substantiate the ability to detect and quantify these analytes at levels necessary to comply with any associated regulations. In addition, the use of
sample introduction techniques other than simple purge-and-trap may be required. QC acceptance criteria from Method 603 should be used
when analyzing samples for acrolein and acrylonitrile in the absence of such criteria in Method 624.1.
5 Method 625.1 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, N-nitrosodi-n-propylamine, and Nnitrosodiphenylamine. However, when they are known to be present, Methods 605, 607, and 612, or Method 1625B, are preferred methods for
these compounds.
5a Method 625.1 screening only.
6 Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency, Supplement to the 15th Edition of
Standard Methods for the Examination of Water and Wastewater. 1981. American Public Health Association (APHA).
7 Each analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601–
603, 1624B, and 1625B in accordance with procedures 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 624.1 and 625.1 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
quality control (QC) acceptance criteria in the pertinent method, analytical results for that parameter in the unspiked sample are suspect. The results should be reported but cannot be used to demonstrate regulatory compliance. If the method does not contain QC acceptance criteria, control limits of ± three standard deviations around the mean of a minimum of five replicate measurements must be used. 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. Revised October 28, 1994. 3M Corporation.
9 Method O–3116–87 is in Open File Report 93–125, Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. USGS.
10 Analysts may use Fluid Management Systems, Inc. Power-Prep system in place of manual cleanup provided the analyst meets the requirements of Method 1613B (as specified in Section 9 of the method) and permitting authorities. Method 1613, Revision B, Tetra- through OctaChlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS. Revision B, 1994. U.S. EPA. The full text of this method is provided in appendix A to this part and at https://www.epa.gov/cwa-methods/approved-cwa-test-methods-organic-compounds.
11 Method 1650, Adsorbable Organic Halides by Adsorption and Coulometric Titration. Revision C, 1997 U.S. EPA. Method 1653, Chlorinated
Phenolics in Wastewater by In Situ Acetylation and GCMS. Revision A, 1997 U.S. EPA. The full text for both of these methods is provided at appendix A in part 430 of this chapter, The Pulp, Paper, and Paperboard Point Source Category.
12 The compound was formerly inaccurately labeled as 2,2′-oxybis(2-chloropropane) and bis(2-chloroisopropyl) ether. Some versions of Methods 611, and 1625 inaccurately list the analyte as ‘‘bis(2-chloroisopropyl) ether,’’ but use the correct CAS number of 108–60–1.
13 Method O–4127–96, U.S. Geological Survey Open-File Report 97–829, Methods of analysis by the U.S. Geological Survey National Water
Quality Laboratory—Determination of 86 volatile organic compounds in water by gas chromatography/mass spectrometry, including detections
less than reporting limits, 1998, USGS.
14 Method O–4436–16 U.S. Geological Survey Techniques and Methods, book 5, chap. B12, Determination of heat purgeable and ambient
purgeable volatile organic compounds in water by gas chromatography/mass spectrometry, 2016, USGS.
15 Please refer to the following Quality Control Section: Part 6000 Individual Organic Compounds, 6020 (2019) 16 SGS AXYS Method ATM
16130, ‘‘Determination of 2,3,7,8-Substituted Tetra- through Octa-Chlorinated Dibenzo-p-Dioxins and Dibenzofurans (CDDs/CDFs) Using Waters
and Agilent Gas Chromatography-Tandem-Mass Spectrometry (GC/MS/MS), Revision 1.0, ’’ is available at: https://www.sgsaxys.com/wp-content/
uploads/2022/09/SGS-AXYS-Method-16130-Rev-1.0.pdf.
16 Pace Analytical Method PAM–16130–SSI, ‘‘Determination of 2,3,7,8-Substituted Tetra- through Octa-Chlorinated Dibenzo-p-Dioxins and
Dibenzofurans (CDDs/CDFs) Using Shimadzu Gas Chromatography Mass Spectrometry (GC–MS/MS), Revision 1.1,’’ is available at:
www.pacelabs.com.
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1
Parameter
Method
EPA 2 7 10
1. Aldrin ......................
GC .............................
617, 608.3 .................
2. Ametryn ..................
GC/MS ......................
GC .............................
ASTM
Other
6630 B–2021 & C–
2021.
D3086–90, D5812–96
(02).
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
625.1 .........................
507, 619 ....................
6410 B–2020.
...................................
...................................
GC/MS ......................
525.2, 625.1 ..............
...................................
...................................
3. Aminocarb ..............
TLC ...........................
...................................
...................................
...................................
See footnote,3 p. 83;
See footnote,9 O–
3106–93; See footnote,6 p. S68.
See footnote,14 O–
1121–91.
See footnote,3 p. 94;
See footnote,6 p.
S60.
4. Atraton ....................
HPLC ........................
GC .............................
632.
619 ............................
...................................
...................................
See footnote,3 p. 83;
See footnote,6 p.
S68.
5. Atrazine ..................
GC/MS ......................
GC .............................
625.1.
507, 619, 608.3 .........
...................................
...................................
HPLC/MS ..................
...................................
...................................
...................................
GC/MS ......................
525.1, 525.2, 625.1 ...
...................................
...................................
GC .............................
614, 622, 1657 ..........
...................................
...................................
GC–MS .....................
625.1 .........................
...................................
...................................
7. Barban ....................
TLC ...........................
...................................
...................................
...................................
See footnote,3 p. 83;
See footnote,6 p.
S68; See footnote,9
O–3106–93.
See footnote,12 O–
2060–01.
See footnote,11 O–
1126–95.
See footnote,3 p. 25;
See footnote,6 p.
S51.
See footnote,11 O–
1126–95.
See footnote,3 p. 104;
See footnote,6 p.
S64.
8. a-BHC ....................
HPLC ........................
GC/MS ......................
GC .............................
632.
625.1.
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
GC/MS ......................
625.1 5 .......................
6410 B–2020 ............
...................................
9. b-BHC .....................
GC .............................
617, 608.3 .................
D3086–90, D5812–
96(02).
10. d-BHC ...................
GC/MS ......................
GC .............................
625.1 .........................
617, 608.3 .................
D3086–90, D5812–
96(02).
See footnote,8
3M0222.
11. g-BHC (Lindane) ...
GC/MS ......................
GC .............................
625.1 .........................
617, 608.3 .................
6630 B–2021 & C–
2021.
6410 B–2020.
6630 B–2021 & C–
2021.
6410 B–2020.
6630 B–2021 & C–
2021.
See footnote,3 p. 7;
See footnote,8
3M0222.
See footnote,11 O–
1126–95.
See footnote,8
3M0222.
D3086–90, D5812–
96(02).
GC/MS ......................
625.1 5 .......................
6410 B–2020 ............
...................................
12. Captan ..................
GC .............................
617, 608.3 .................
6630 B–2021 ............
13. Carbaryl ................
TLC ...........................
...................................
...................................
D3086–90, D5812–
96(02).
...................................
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
See footnote,11 O–
1126–95.
See footnote,3 p. 7.
HPLC ........................
HPLC/MS ..................
531.1, 632.
553 ............................
...................................
...................................
GC/MS ......................
625.1 .........................
...................................
...................................
GC .............................
617, 608.3 .................
6630 B–2021 ............
...................................
GC/MS ......................
625.1.
6. Azinphos methyl .....
lotter on DSK11XQN23PROD with PROPOSALS2
Standard
methods 15
14. Carbophenothion ..
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See footnote,3 p. 94,
See footnote,6 p.
S60.
See footnote,12 O–
2060–01.
See footnote,11 O–
1126–95.
See footnote,4 page
27; See footnote,6
p. S73.
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10765
lotter on DSK11XQN23PROD with PROPOSALS2
TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued
Standard
methods 15
Parameter
Method
EPA 2 7 10
15. Chlordane .............
GC .............................
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
16. Chloropropham ....
GC/MS ......................
TLC ...........................
625.1 .........................
...................................
6410 B–2020.
...................................
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
17. 2,4–D ....................
HPLC ........................
GC/MS ......................
GC .............................
632.
625.1.
615 ............................
6640 B–2021 ............
...................................
HPLC/MS ..................
...................................
...................................
...................................
18. 4,4′-DDD ..............
GC .............................
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
See footnote,3 p. 115;
See footnote,4 O–
3105–83.
See footnote,12 O–
2060–01.
See footnote,3 p. 7;
See footnote,4 O–
3105–83; See footnote,8 3M0222.
19. 4,4′-DDE ...............
GC/MS ......................
GC .............................
625.1 .........................
617, 608.3 .................
6410 B–2020.
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
GC/MS ......................
625.1 .........................
6410 B–2020 ............
...................................
20. 4,4′-DDT ...............
GC .............................
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
21. Demeton-O ...........
GC/MS ......................
GC .............................
625.1 .........................
614, 622 ....................
6410 B–2020.
...................................
...................................
See footnote,3 p. 25;
See footnote,6 p.
S51.
22. Demeton-S ...........
GC/MS ......................
GC .............................
625.1.
614, 622 ....................
...................................
...................................
See footnote,3 p. 25;
See footnote,6 p.
S51.
23. Diazinon ...............
GC/MS ......................
GC .............................
625.1.
507, 614, 622, 1657
...................................
...................................
GC/MS ......................
525.2, 625.1 ..............
...................................
...................................
24. Dicamba ...............
GC .............................
HPLC/MS ..................
615 ............................
...................................
...................................
...................................
...................................
...................................
25. Dichlofenthion ......
GC .............................
622.1 .........................
...................................
...................................
26. Dichloran ..............
27. Dicofol ..................
GC .............................
GC .............................
608.2, 617, 608.3 ......
617, 608.3 .................
6630 B–2021 ............
...................................
...................................
...................................
28. Dieldrin .................
GC .............................
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
GC/MS ......................
625.1 .........................
6410 B–2020 ............
...................................
29. Dioxathion ............
GC .............................
614.1, 1657 ...............
...................................
...................................
30. Disulfoton .............
GC .............................
507, 614, 622, 1657
...................................
...................................
GC/MS ......................
525.2, 625.1 ..............
...................................
...................................
TLC ...........................
...................................
...................................
...................................
See footnote,3 p. 25;
See footnote,4 O–
3104–83; See footnote,6 p. S51.
See footnote,11 O–
1126–95.
See footnote,3 p. 115.
See footnote,12 O–
2060–01.
See footnote,4 page
27; See footnote,6
p. S73.
See footnote,3 p. 7.
See footnote,4 O–
3104–83.
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
See footnote,11 O–
1126–95.
See footnote,4 page
27; See footnote,6
p. S73.
See footnote,3 p. 25;
See footnote,6 p.
S51.
See footnote,11 O–
1126–95.
See footnote,3 p. 104;
See footnote,6 p.
S64.
31. Diuron ...................
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See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
See footnote,11 O–
1126–95.
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
10766
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued
Method
EPA 2 7 10
Standard
methods 15
ASTM
Other
HPLC ........................
HPLC/MS ..................
632.
553 ............................
...................................
...................................
GC .............................
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
GC/MS ......................
625.1 5 .......................
6410 B–2020 ............
...................................
GC .............................
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
GC/MS ......................
625.1 5 .......................
6410 B–2020 ............
...................................
34. Endosulfan Sulfate
GC .............................
617, 608.3 .................
6630 C–2021 ............
...................................
See footnote,12 O–
2060–01.
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M022).
See footnote,13 O–
2002–01.
See footnote,3 p. 7;
See footnote,8
3M0222.
See footnote,13 O–
2002–01.
See footnote,8
3M0222.
35. Endrin ...................
GC/MS ......................
GC .............................
625.1 .........................
505, 508, 617, 1656,
608.3.
6410 B–2020.
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
36. Endrin aldehyde ...
GC/MS ......................
GC .............................
525.1, 525.2, 625.1 5
617, 608.3 .................
6410 B–2020.
6630 C–2021 ............
...................................
See footnote,8
3M0222.
37. Ethion ...................
GC/MS ......................
GC .............................
625.1 .........................
614, 614.1, 1657 .......
6410 B–2020.
...................................
...................................
GC/MS ......................
625.1 .........................
...................................
...................................
TLC ...........................
...................................
...................................
...................................
See footnote,4 page
27; See footnote,6
p. S73.
See footnote,13 O–
2002–01.
See footnote,3 p. 104;
See footnote,6 p.
S64.
HPLC ........................
HPLC/MS ..................
632.
...................................
...................................
...................................
39. Fenuron-TCA .......
TLC ...........................
...................................
...................................
...................................
40. Heptachlor ............
HPLC ........................
GC .............................
632.
505, 508, 617, 1656,
608.3.
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
GC/MS ......................
GC .............................
525.1, 525.2, 625.1 ...
617, 608.3 .................
6410 B–2020.
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,6 p. S73; See
footnote,8 3M0222.
42. Isodrin ..................
GC/MS ......................
GC .............................
625.1 .........................
617, 608.3 .................
6410 B–2020.
6630 B–2021 & C–
2021.
...................................
See footnote,4 O–
3104–83; See footnote,6 p. S73.
43. Linuron .................
GC/MS ......................
GC .............................
625.1.
...................................
...................................
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
HPLC ........................
HPLC/MS ..................
632.
553 ............................
...................................
...................................
GC/MS ......................
...................................
...................................
...................................
GC .............................
614, 1657 ..................
6630 B–2021 ............
...................................
GC/MS ......................
625.1 .........................
...................................
...................................
TLC ...........................
...................................
...................................
...................................
See footnote,12 O–
2060–01.
See footnote,11 O–
1126–95.
See footnote,3 p. 25;
See footnote,6 p.
S51.
See footnote,11 O–
1126–95.
See footnote,3 p. 94;
See footnote,6 p.
S60.
Parameter
32. Endosulfan I .........
33. Endosulfan II ........
38. Fenuron ................
lotter on DSK11XQN23PROD with PROPOSALS2
41. Heptachlor epoxide.
44. Malathion ..............
45. Methiocarb ...........
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See footnote,12 O–
2060–01.
See footnote,3 p. 104;
See footnote,6 p.
S64.
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
10767
TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued
Method
EPA 2 7 10
Standard
methods 15
ASTM
Other
HPLC ........................
HPLC/MS ..................
632.
...................................
...................................
...................................
GC .............................
505, 508, 608.2, 617,
1656, 608.3.
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
GC/MS ......................
525.1, 525.2, 625.1 ...
...................................
...................................
47. Mexacarbate ........
TLC ...........................
...................................
...................................
...................................
See footnote,12 O–
2060–01.
See footnote,3 p. 7;
See footnote,4 O–
3104–83; See footnote,8 3M0222.
See footnote,11 O–
1126–95.
See footnote,3 p. 94;
See footnote,6 p.
S60.
48. Mirex ....................
HPLC ........................
GC/MS ......................
GC .............................
632.
625.1.
617, 608.3 .................
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
See footnote,3 p. 7;
See footnote,4 O–
3104–83.
49. Monuron ...............
GC/MS ......................
TLC ...........................
625.1.
...................................
...................................
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
50. Monuron-TCA .......
HPLC ........................
TLC ...........................
632.
...................................
...................................
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
51. Neburon ...............
HPLC ........................
TLC ...........................
632.
...................................
...................................
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
HPLC ........................
HPLC/MS ..................
632.
...................................
...................................
...................................
GC .............................
614, 622, 1657 ..........
6630 B–2021 ............
...................................
GC/MS ......................
625.1 .........................
...................................
...................................
GC .............................
614 ............................
6630 B–2021 ............
...................................
GC/MS ......................
...................................
...................................
...................................
54. PCNB ...................
GC .............................
608.1, 617, 608.3 ......
55. Perthane ...............
GC .............................
617, 608.3 .................
6630 B–2021 & C–
2021.
...................................
56. Prometon ..............
GC .............................
507, 619 ....................
...................................
D3086–90, D5812–
96(02).
D3086–90, D5812–
96(02).
...................................
See footnote,12 O–
2060–01.
See footnote,4 page
27; See footnote,3
p. 25.
See footnote,11 O–
1126–95.
See footnote,4 page
27; See footnote,3
p. 25.
See footnote,11 O–
1126–95.
See footnote,3 p. 7.
GC/MS ......................
525.2, 625.1 ..............
...................................
...................................
GC .............................
507, 619 ....................
...................................
...................................
GC/MS ......................
525.1, 525.2, 625.1 ...
...................................
...................................
58. Propazine .............
GC .............................
507, 619, 1656, 608.3
...................................
...................................
59. Propham ...............
GC/MS ......................
TLC ...........................
525.1, 525.2, 625.1.
...................................
...................................
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
HPLC ........................
HPLC/MS ..................
632.
...................................
...................................
...................................
See footnote,12 O–
2060–01.
Parameter
46. Methoxychlor ........
52. Parathion methyl ..
53. Parathion ethyl .....
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57. Prometryn .............
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See footnote,4 O–
3104–83.
See footnote,3 p. 83;
See footnote,6 p.
S68; See footnote,9
O–3106–93.
See footnote,11 O–
1126–95.
See footnote,3 p. 83;
See footnote,6 p.
S68; See footnote,9
O–3106–93.
See footnote,13 O–
2002–01.
See footnote,3 p. 83;
See footnote,6 p.
S68; See footnote,9
O–3106–93.
10768
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued
Parameter
Method
EPA 2 7 10
Standard
methods 15
ASTM
60. Propoxur ...............
TLC ...........................
...................................
...................................
...................................
See footnote,3 p. 94;
See footnote,6 p.
S60.
61. Secbumeton .........
HPLC ........................
TLC ...........................
632.
...................................
...................................
...................................
See footnote,3 p. 83;
See footnote,6 p.
S68.
62. Siduron .................
GC .............................
TLC ...........................
619.
...................................
...................................
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
HPLC ........................
HPLC/MS ..................
632.
...................................
...................................
...................................
GC .............................
505, 507, 619, 1656,
608.3.
...................................
...................................
GC/MS ......................
525.1, 525.2, 625.1 ...
...................................
...................................
64. Strobane ...............
GC .............................
617, 608.3 .................
...................................
65. Swep ....................
TLC ...........................
...................................
6630 B–2021 & C–
2021.
...................................
See footnote,12 O–
2060–01.
See footnote,3 p. 83;
See footnote,6 p.
S68; See footnote,9
O–3106–93.
See footnote,11 O–
1126–95.
See footnote,3 p. 7.
...................................
See footnote,3 p. 104;
See footnote,6 p.
S64.
66. 2,4,5–T .................
HPLC ........................
GC .............................
632.
615 ............................
6640 B–2021 ............
...................................
67. 2,4,5–TP (Silvex) ..
GC .............................
615 ............................
6640 B–2021 ............
...................................
68. Terbuthylazine ......
GC .............................
619, 1656, 608.3 .......
...................................
...................................
GC/MS ......................
...................................
...................................
...................................
69. Toxaphene ...........
GC .............................
505, 508, 617, 1656,
608.3.
6630 B–2021 & C–
2021.
D3086–90, D5812–
96(02).
See footnote,3 p. 115;
See footnote,4 O–
3105–83.
See footnote,3 p. 115;
See footnote,4 O–
3105–83.
See footnote,3 p. 83;
See footnote,6 p.
S68.
See footnote,13 O–
2002–01.
See footnote,3 p. 7;
See footnote; 8 See
footnote,4 O–3105–
83.
70. Trifluralin ..............
GC/MS ......................
GC .............................
525.1, 525.2, 625.1 ...
508, 617, 627, 1656,
608.3.
6410 B–2020.
6630 B–2021 ............
...................................
GC/MS ......................
525.2, 625.1 ..............
...................................
...................................
lotter on DSK11XQN23PROD with PROPOSALS2
63. Simazine ..............
Other
See footnote,3 p. 7;
See footnote,9 O–
3106–93.
See footnote,11 O–
1126–95.
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 IC of
this section, where entries are listed by chemical name.
2 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.
3 Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S.
EPA. This EPA publication includes thin-layer chromatography (TLC) methods.
4 Methods for the Determination of Organic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the
U.S. Geological Survey, Book 5, Chapter A3. 1987. USGS.
5 The method may be extended to include a-BHC, g-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 United States Environmental Protection Agency, Supplement to the 15th Edition of
Standard Methods for the Examination of Water and Wastewater.1981. American Public Health Association (APHA).
7 Each analyst must make an initial, one-time, demonstration of their ability to generate acceptable precision and accuracy with Methods 608.3
and 625.1 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 608.3 or 5% of all samples analyzed with Method 625.1 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. Revised October 28, 1994. 3M Corporation.
9 Method O–3106–93 is in Open File Report 94–37, 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. 1994.
USGS.
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10 EPA Methods 608.1, 608.2, 614, 614.1, 615, 617, 619, 622, 622.1, 627, and 632 are found in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, EPA 821–R–92–002, April 1992, U.S. EPA. EPA Methods 505, 507, 508, 525.1, 531.1
and 553 are in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume II, EPA 821–R–93–
010B, 1993, U.S. EPA. EPA Method 525.2 is in Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary
Column Gas Chromatography/Mass Spectrometry, Revision 2.0, 1995, U.S. EPA. EPA methods 1656 and 1657 are in Methods for The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume I, EPA 821–R–93–010A, 1993, U.S. EPA. Methods
608.3 and 625.1 are available at: cwa-methods/approved-cwa-test-methods-organic-compounds.
11 Method O–1126–95 is in Open-File Report 95–181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—
Determination of pesticides in water by C–18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selectedion monitoring. 1995. USGS.
12 Method O–2060–01 is in Water-Resources Investigations Report 01–4134, Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory—Determination of Pesticides in Water by Graphitized Carbon-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass Spectrometry. 2001. USGS.
13 Method O–2002–01 is in Water-Resources Investigations Report 01–4098, Methods of Analysis by the U.S. Geological Survey National
Water Quality Laboratory—Determination of moderate-use pesticides in water by C–18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry. 2001. USGS.
14 Method O–1121–91 is in Open-File Report 91–519, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—
Determination of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with
selected-ion monitoring. 1992. USGS.
15 Please refer to the following applicable Quality Control Section: Part 6000 Methods, Individual Organic Compounds 6020 (2019). These
Quality Control Standards are available for download at www.standardmethods.org at no charge.
*
*
*
*
*
*
*
*
*
*
TABLE IH—LIST OF APPROVED MICROBIOLOGICAL METHODS FOR AMBIENT WATER
Method 1
Parameter and units
EPA
Standard methods
AOAC, ASTM,
USGS
Other
Bacteria
1. Coliform (fecal),
number per 100 mL.
2. Coliform (total), number per 100 mL.
Most Probable Number (MPN),
5 tube, 3 dilution, or
Membrane filter (MF),2 single
step.
MPN, 5 tube, 3 dilution, or ........
p.
132 3
........................
p.
124 3
........................
p. 114 3 ........................
B–0050–85. 4
9221 B–2014.
MF,2
single step or two step ......
MF 2 with enrichment .................
MPN,5 7 13 multiple tube, or
p.
........................
p. 111 3 ........................
.....................................
Multiple tube/multiple well, or ....
MF,2 5 6 7 two step, or .................
.....................................
1103.2 18 .....................
Single step .................................
1603.1,19 1604 20 ........
9222 B–2015 27
9222 B.–2015. 27
9221 B.3–2014/9221
F–2014. 10 12 32
9223 B–2016 11 ...........
9222 B–2015/9222 I–
2015,17 9213 D–
2007.
.....................................
MPN, 5 tube, 3 dilution, or .........
p. 139 3 ........................
9230 B–2013.
MF,2 or .......................................
Plate count .................................
MPN,5 7 multiple tube/multiple
well, or
MF 2 5 6 7 two step, or .................
Single step, or ............................
Plate count .................................
p. 136 3
p. 143. 3
.....................................
9230 C–2013 30 ...........
B–0055–85. 4
9230 D–2013 ..............
D6503–99 8 .....
9230 C–2013 30 ...........
9230 C–2013. 30
D5259–92. 8
6. Cryptosporidium ......
Filtration/IMS/FA ........................
1622, 24
7. Giardia .....................
Filtration/IMS/FA ........................
1623.1. 25 31
1623, 25 1623.1. 25 31
3. E. coli, number per
100 mL.
4. Fecal streptococci,
number per 100 mL.
5. Enterococci, number
per 100 mL.
108 3
9221 E–2014, 9221 F–
2014 32.
9222 D–2015 26 ...........
1106.2 22 .....................
1600.1 23 .....................
p. 143. 3
B–0025–85. 4
991.15 9 ...........
D5392–93. 8
Colilert®,11 15 Colilert–18®.11 14 15
.........................
m-ColiBlue24®,16 KwikCountTM
EC 28 29
Enterolert® 11 21
lotter on DSK11XQN23PROD with PROPOSALS2
Protozoa
1623, 25
Table 1H notes:
1 The method must be specified when results are reported.
2 A 0.45-μm 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 Microbiological Methods for Monitoring the Environment, Water and Wastes. EPA/600/8–78/017. 1978. US EPA.
4 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. 1989. USGS.
5 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.
6 When the MF method has not been used previously to test waters with high turbidity, large numbers 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.
7 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.
8 Annual Book of ASTM Standards—Water and Environmental Technology. Section 11.02. 2000, 1999, 1996. ASTM International.
9 Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. 1995. AOAC International.
10 The multiple-tube fermentation test is used in 9221B.3–2014. 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.
11 These tests are collectively known as defined enzyme substrate tests.
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12 After prior enrichment in a presumptive medium for total coliform using 9221B.3–2014, 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–2014. Commercially available EC–MUG media or EC media supplemented in the laboratory with
50 μg/mL of MUG may be used.
13 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® may be enumerated with the multiple-well procedures,
Quanti-Tray® or Quanti-Tray®/2000, and the MPN calculated from the table provided by the manufacturer.
14 Colilert–18® is an optimized formulation of the Colilert® for the determination of total coliforms and E. coli that provides results within 18 h of incubation at 35 °C,
rather than the 24 h required for the Colilert® test and is recommended for marine water samples.
15 Descriptions of the Colilert®, Colilert–18®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories Inc.
16 A description of the mColiBlue24® test may be obtained from Hach Company.
17 Subject coliform positive samples determined by 9222B–2015 or other membrane filter procedure to 9222I–2015 using NA–MUG media.
18 Method 1103.2: Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC), [in draft as of 2023].
US EPA.
19 Method 1603.1: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar (Modified mTEC), [in
draft as of 2023]. US EPA.
20 Method 1604: Total Coliforms and Escherichia coli (E. coli) in Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI Medium), EPA
821–R–02–024. September 2002. US EPA.
21 A description of the Enterolert® test may be obtained from IDEXX Laboratories Inc.
22 Method 1106.2: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE–EIA), [in draft as of 2023]. US EPA.
23 Method 1600.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-b-D-Glucoside Agar (mEI), [in draft as of 2023]. US EPA.
24 Method 1622 uses a 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. Method 1622: Cryptosporidium
in Water by Filtration/IMS/FA, EPA–821–R–05–001. December 2005. US EPA.
25 Methods 1623 and 1623.1 use a 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. Method 1623: Cryptosporidium and Giardia in Water by Filtration/IMS/FA. EPA–821–R–05–002. December 2005. US
EPA. Method 1623.1: Cryptosporidium and Giardia in Water by Filtration/IMS/FA. EPA 816–R–12–001. January 2012. US EPA.
26 On a monthly basis, at least ten blue colonies from positive samples must be verified using Lauryl Tryptose Broth and EC broth, followed by count adjustment
based on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications should be done from randomized sample sources.
27 On a monthly basis, at least ten sheen colonies from positive samples must be verified using Lauryl Tryptose Broth and brilliant green lactose bile broth, followed
by count adjustment based on these results; and representative non-sheen colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications
should be done from randomized sample sources.
28 A description of KwikCountTM EC may be obtained from Micrology Laboratories LLC.
29 Approved for the analyses of E. coli in freshwater only.
30 Verification of colonies by incubation of BHI agar at 10 ± 0.5 °C for 48 ± 3 h is optional. As per the Errata to the 23rd Edition of Standard Methods for the Examination of Water and Wastewater ‘‘Growth on a BHI agar plate incubated at 10 ± 0.5 °C for 48 ± 3 h is further verification that the colony belongs to the genus
Enterococcus.’’
31 Method 1623.1 includes updated acceptance criteria for IPR, OPR, and MS/MSD and clarifications and revisions based on the use of Method 1623 for years and
technical support questions.
32 9221 F.2–2014 allows for simultaneous detection of E. coli and thermotolerant fecal coliforms by adding inverted vials to EC–MUG; the inverted vials collect gas
produced by thermotolerant fecal coliforms.
(b) The material listed in this
paragraph (b) is incorporated by
reference into this section with the
approval of the Director of the Federal
Register under 5 U.S.C. 552(a) and 1
CFR part 51. All approved material is
available for inspection at the EPA and
at the National Archives and Records
Administration (NARA). Contact the
EPA at: EPA’s Water Docket, EPA West,
1301 Constitution Avenue NW, Room
3334, Washington, DC 20004; telephone:
202–566–2426; email: docketcustomerservice@epa.gov. For
information on the availability of this
material at NARA, visit
www.archives.gov/federal-register/cfr/
ibr-locations.html or email
fr.inspection@nara.gov. The material
may be obtained from the following
sources in this paragraph (b).
*
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*
*
(8) * * *
(ii) Method 1103.2: Escherichia coli
(E. coli) in Water by Membrane
Filtration Using Modified membraneThermotolerant Escherichia coli Agar
(Modified mTEC). [in draft as of 2023].
EPA Table IH, Note 18.
(iii) Method 1106.2: Enterococci in
Water by Membrane Filtration Using
membrane-Enterococcus-Esculin Iron
Agar (mE–EIA). [in draft as of 2023].
Table IH, Note 22.
(iv) Method 1600.1: Enterococci in
Water by Membrane Filtration Using
membrane-Enterococcus Indoxyl-b-D-
VerDate Sep<11>2014
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Glucoside Agar (mEI). [in draft as of
2023]. EPA. Table 1A, Note 24; Table
IH, Note 23.
(v) Method 1603.1: Escherichia coli
(E. coli) in Water by Membrane
Filtration Using Modified membraneThermotolerant Escherichia coli Agar
(Modified mTEC). [in draft as of 2023].
EPA. Table IA, Note 21; Table IH, Note
19.
*
*
*
*
*
(10) * * *
(i) Standard Methods for the
Examination of Water and Wastewater.
14th Edition, 1975. Table IB, Notes 27
and 86.
*
*
*
*
*
(viii) 2120, Color. 2021. Table IB.
(ix) 2130, Turbidity. 2020. Table IB.
(x) 2310, Acidity. 2020. Table IB.
(xi) 2320, Alkalinity. 2021. Table IB.
(xii) 2340, Hardness. 2021. Table IB.
(xiii) 2510, Conductivity. 2021. Table
IB.
(xiv) 2540, Solids. 2020. Table IB.
*
*
*
*
*
(xvi) 3111, Metals by Flame Atomic
Absorption Spectrometry. 2019. Table
IB.
(xvii) 3112, Metals by Cold-Vapor
Atomic Absorption Spectrometry. 2020.
Table IB.
(xviii) 3113, Metals by Electrothermal
Atomic Absorption Spectrometry. 2020.
Table IB.
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(xix) 3114, Arsenic and Selenium by
Hydride Generation/Atomic Absorption
Spectrometry. 2020, Table IB.
(xx) 3120, Metals by Plasma Emission
Spectroscopy. 2020. Table IB.
(xxi) 3125, Metals by Inductively
Coupled Plasma-Mass Spectrometry.
2020. Table IB.
(xxii) 3500–Al, Aluminum. 2020.
Table IB.
(xxiii) 3500–As, Arsenic. 2020. Table
IB.
(xxiv) 3500–Ca, Calcium. 2020. Table
IB.
(xxv) 3500–Cr, Chromium. 2020.
Table IB.
(xxvi) 3500–Cu, Copper. 2020. Table
IB.
*
*
*
*
*
(xxviii) 3500–Pb, Lead. 2020. Table
IB.
(xxix) 3500–Mn, Manganese. 2020.
Table IB.
(xxx) 3500–K, Potassium. 2020. Table
IB.
(xxxi) 3500–Na, Sodium. 2020. Table
IB.
*
*
*
*
*
(xxxiii) 3500–Zn, Zinc. 2020. Table
IB.
(xxxiv) 4110, Determination of Anions
by Ion Chromatography. 2020. Table IB.
(xxxv) 4140, Inorganic Anions by
Capillary Ion Electrophoresis. 2020.
Table IB.
*
*
*
*
*
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Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 / Proposed Rules
(xxxvii) 4500 Cl¥, Chloride. 2021.
Table IB.
*
*
*
*
*
(xxxix) 4500–CN¥, Cyanide. 2021.
Table IB.
(xl) 4500–F¥, Fluoride. 2021. Table
IB.
(xli) 4500–H+, pH Value. 2021. Table
IB.
(xlii) 4500–NH3, Nitrogen (Ammonia).
2021. Table IB.
(xliii) 4500–NO2¥, Nitrogen (Nitrite).
2021. Table IB.
(xliv) 4500–NO3¥, Nitrogen (Nitrate).
2019. Table IB.
(xlv) 4500–N(org), Nitrogen (Organic).
2021. Table IB.
(xlvi) 4500–O, Oxygen (Dissolved).
2021. Table IB.
(xlvii) 4500–P, Phosphorus. 2021.
Table IB.
(xlviii) 4500–SiO2, Silica. 2021. Table
IB.
(xlix) 4500–S2¥, Sulfide. 2021. Table
IB.
(l) 4500–SO32¥, Sulfite. 2021. Table
IB.
(li) 4500–SO42¥, Sulfate. 2021. Table
IB.
*
*
*
*
*
(lv) 5520, Oil and Grease. 2021. Table
IB.
(lvi) 5530, Phenols. 2021. Table IB.
(lvii) 5540, Surfactants. 2021. Table
IB.
(lviii) 6200, Volatile Organic
Compounds. 2020. Table IC.
(lix) 6410, Extractable Base/Neutrals
and Acids. 2020. Tables IC and ID.
(lx) 6420, Phenols. 2020. Table IC.
(lxi) 6440, Polynuclear Aromatic
Hydrocarbons. 2021. Table IC.
(lxii) 6630, Organochlorine Pesticides.
2021. Table IC.
(lxiii) 6640, Acidic Herbicide
Compounds. 2021. Table IC.
*
*
*
*
*
(lxvii) 9221, Multiple-Tube
Fermentation Techniques for Members
of the Coliform Group. 2014. Table IA,
Notes 12, 14 and 33; Table IH, Notes 10,
12 and 32.
*
*
*
*
*
(15) * * *
(xi) ASTM D888–18, Standard Test
Methods for Dissolved Oxygen in Water.
May 2018. Table IB.
*
*
*
*
*
(xx) ASTM D1293–18, Standard Test
Methods for pH of Water. January 2018.
Table IB.
*
*
*
*
*
(xxx) ASTM D1976–20, Standard Test
Method for Elements in Water by
Inductively-Coupled Argon Plasma
Atomic Emission Spectroscopy. June
2020. Table IB.
*
*
*
*
*
(xxxii) ASTM D2330–20, Standard
Test Method for Methylene Blue Active
Substances. February 2020. Table 1B.
*
*
*
*
*
(lix) ASTM D5907–18, Standard Test
Methods for Filterable Matter (Total
Dissolved Solids) and Nonfilterable
Matter (Total Suspended Solids) in
Water. May 2018. Table IB.
*
*
*
*
*
(lxv) ASTM D7237–18, Standard Test
Method for Free Cyanide with Flow
Injection Analysis (FIA) Utilizing Gas
Diffusion Separation and Amperometric
Detection. January 2019. Table IB.
(lxvi) ASTM D7284–20, Standard Test
Method for Total Cyanide in Water by
Micro Distillation followed by Flow
Injection Analysis with Gas Diffusion
Separation and Amperometric
Detection. August 2020. Table IB.
(lxvii) ASTM D7365–09a (Reapproved
2015), Standard Practice for Sampling,
Preservation and Mitigating
Interferences in Water Samples for
Analysis of Cyanide. August 2015. Table
II, Notes 5 and 6.
*
*
*
*
*
(lxix) ASTM D7573–18ae1, Standard
Test Method for Total Carbon and
Organic Carbon in Water by High
Temperature Catalytic Combustion and
Infrared Detection, January 2019. Table
IB.
*
*
*
*
*
(33) Pace Analytical Services, LLC,
1800 Elm Street SE, Minneapolis, MN
55414. Telephone: 612–656–2240.
(i) PAM–16130–SSI, Determination of
2,3,7,8-Substituted Tetra- through OctaChlorinated Dibenzo-p-Dioxins and
Dibenzofurans (CDDs/CDFs) Using
Shimadzu Gas Chromatography Mass
Spectrometry (GC–MS/MS), Revision
1.1, May 20, 2022. Table IC, Note 17.
(ii) [Reserved]
(34) SGS AXYS Analytical Services,
Ltd., 2045 Mills Road, Sidney, British
Columbia, Canada, V8L 5X2. Telephone:
1–888–373–0881.
(i) ATM 16130, Determination of
2,3,7,8-Substituted Tetra- through OctaChlorinated Dibenzo-p-Dioxins and
Dibenzofurans (CDDs/CDFs) Using
Waters and Agilent Gas
Chromatography-Tandem-Mass
Spectrometry (GC/MS/MS)., Revision
1.0, August 2020. Table IC, Note 16
(ii) [Reserved]
*
*
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(e) * * *
TABLE II—REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES
*
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*
*
*
*
*
*
D7365–09a (15) specifies treatment options for samples containing oxidants (e.g., chlorine) for cyanide analyses. Also, Section 9060A
of Standard Methods for the Examination of Water and Wastewater (23rd edition) addresses dechlorination procedures for microbiological
analyses.
5 ASTM
*
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]]>Agencies
[Federal Register Volume 88, Number 34 (Tuesday, February 21, 2023)]
[Proposed Rules]
[Pages 10724-10771]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 2023-02391]
[[Page 10723]]
Vol. 88
Tuesday,
No. 34
February 21, 2023
Part III
Environmental Protection Agency
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40 CFR Part 136
Clean Water Act Methods Update Rule for the Analysis of Effluent;
Proposed Rule
Federal Register / Vol. 88, No. 34 / Tuesday, February 21, 2023 /
Proposed Rules
[[Page 10724]]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 136
[EPA-HQ-OW-2022-0901; FRL-9346-01-OW]
RIN 2040-AG25
Clean Water Act Methods Update Rule for the Analysis of Effluent
AGENCY: Environmental Protection Agency (EPA).
ACTION: Proposed rule.
-----------------------------------------------------------------------
SUMMARY: The Environmental Protection Agency (EPA) is proposing changes
to its test procedures required to be used by industries and
municipalities when analyzing the chemical, physical, and biological
properties of wastewater and other samples for reporting under EPA's
National Pollutant Discharge Elimination System (NPDES) permit program.
The Clean Water Act (CWA) requires EPA to promulgate these test
procedures (analytical methods) for analysis of pollutants. EPA
anticipates that these proposed changes would provide increased
flexibility for the regulated community in meeting monitoring
requirements while improving data quality. In addition, this proposed
update to the CWA methods would incorporate technological advances in
analytical technology and make a series of minor changes and
corrections to existing approved methods. As such, EPA expects that
there would be no negative economic impacts resulting from these
proposed changes.
DATES: Comments on this proposed rule must be received on or before
April 24, 2023.
ADDRESSES: You may send comments, identified by Docket ID No. EPA-HQ-
OW-2022-0901 by any of the following methods:
Federal eRulemaking Portal: https://www.regulations.gov
(our preferred method). Follow the online instructions for submitting
comments.
Email: [email protected]. Include Docket ID No. EPA-HQ-OW-
2022-0901 in the subject line of the message.
Mail: U.S. Environmental Protection Agency, EPA Docket
Center, Office of Water Docket, Mail Code 28221T, 1200 Pennsylvania
Avenue NW, Washington, DC 20460.
Hand Delivery or Courier: EPA Docket Center, WJC West
Building, Room 3334, 1301 Constitution Avenue NW, Washington, DC 20004.
The Docket Center's hours of operations are 8:30 a.m.-4:30 p.m.,
Monday-Friday (except Federal Holidays).
Instructions: All submissions received must include the Docket ID
No. for this rulemaking. Comments received may be posted without change
to https://www.regulations.gov/, including any personal information
provided. For detailed instructions on sending comments and additional
information on the rulemaking process, see the ``Public Participation''
heading of the SUPPLEMENTARY INFORMATION section of this document.
FOR FURTHER INFORMATION CONTACT: Tracy Bone, Engineering and Analysis
Division (4303T), Office of Water, Environmental Protection Agency,
1200 Pennsylvania Avenue NW, Washington, DC 20460-0001; telephone
number: 202-564-5257; email address: [email protected].
SUPPLEMENTARY INFORMATION:
Table of Contents
I. Public Participation
II. General Information
III. Background
IV. Incorporation by Reference
V. Statutory and Executive order Reviews
I. Public Participation
A. Written Comments
Submit your comments, identified by Docket ID No. EPA-HQ-OW-2022-
0901, at https://www.regulations.gov (our preferred method), or the
other methods identified in the ADDRESSES section. Once submitted,
comments cannot be edited or removed from the docket. EPA may publish
any comment received to its public docket. Do not submit to EPA's
docket at https://www.regulations.gov any information you consider to
be Confidential Business Information (CBI), Proprietary Business
Information (PBI), or other information whose disclosure is restricted
by statute. Multimedia submissions (audio, video, etc.) must be
accompanied by a written comment. The written comment is considered the
official comment and should include discussion of all points you wish
to make. EPA will generally not consider comments or comment contents
located outside of the primary submission (i.e., on the web, cloud, or
other file sharing system). Please visit https://www.epa.gov/dockets/commenting-epa-dockets for additional submission methods; the full EPA
public comment policy; information about CBI, PBI, or multimedia
submissions; and general guidance on making effective comments.
Publicly available docket materials are available electronically in
www.regulations.gov at the Water Docket in EPA Docket Center, EPA/DC,
EPA West William J. Clinton Building, Room 3334, 1301 Constitution
Avenue NW, Washington, DC. The Public Reading Room is open from 8:30
a.m. to 4:30 p.m., Monday through Friday, excluding legal holidays. Any
copyright material can be viewed at the Reading Room, please contact
the EPA Docket Center, public Reading Room. The telephone number for
the Public Reading Room is 202-566-1744, and the telephone number for
the Water Docket is 202-566-2426. Fax: 202-566-9744. Email: [email protected].
II. General Information
A. Does this action apply to me?
Entities potentially affected by the requirements of this proposed
action include:
----------------------------------------------------------------------------------------------------------------
Category Examples of potentially affected entities
----------------------------------------------------------------------------------------------------------------
State, Territorial, and Indian Tribal States authorized to administer the National Pollutant Discharge
Governments. Elimination System (NPDES) permitting program; states,
territories, and tribes providing certification under CWA section
401; state, territorial, and tribal-owned facilities that must
conduct monitoring to comply with NPDES permits.
Industry.................................... Facilities that must conduct monitoring to comply with NPDES
permits; the environmental monitoring industry.
Municipalities.............................. Publicly Owned Treatment Works (POTWs) or other municipality-owned
facilities 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 affected by this
action. This table lists types of entities that EPA is now aware of
that could potentially be affected by this action. Other types of
entities not listed in the table could also be affected. To determine
whether your facility is affected 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) and 40 CFR 403.1
(pretreatment standards purpose
[[Page 10725]]
and 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.
B. What action is the Agency taking?
Periodically, EPA proposes to update the approved methods in 40 CFR
part 136. In general, the changes proposed in this action fall into the
following categories. The first category is updated versions of EPA
methods currently approved in 40 CFR part 136. The second category is
new or revised methods published by a voluntary consensus standard body
(VCSB) or the United States Geologic Survey (USGS) that are similar to
methods previously adopted as EPA-approved methods in 40 CFR part 136.
The third category is methods EPA has reviewed under the agency's
national Alternate Test Procedure (ATP) program and preliminarily
concluded are appropriate for nationwide use. Finally, EPA is proposing
certain corrections or amendments to the text and tables of 40 CFR part
136. EPA is proposing adoption of these revisions to improve data
quality, update methods to keep current with technology advances, and
provide the regulated community with greater flexibility. The following
paragraphs provide details on the proposed revisions.
C. What is the agency's authority for taking this action?
EPA is proposing this regulation under the authorities of sections
301(a), 304(h), and 501(a) of the CWA; 33 U.S.C. 1251, 1311(a), 1314(h)
and 1361(a). Section 301(a) of the CWA prohibits the discharge of any
pollutant into navigable waters unless the discharge complies with,
among other provisions, an NPDES permit issued under section 402 of the
CWA. Section 304(h) of the CWA requires EPA Administrator 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 the CWA] or permit
application pursuant to [section 402 of the CWA].'' Section 501(a) of
the CWA authorizes the Administrator to ``. . . prescribe such
regulations as are necessary to carry out this function under [the
CWA].'' EPA generally has codified its test procedure regulations
(including analysis and sampling requirements) for CWA programs at 40
CFR part 136, though some requirements are codified in other parts
(e.g., 40 CFR Chapter I, Subchapters N and O).
III. Background
This preamble describes the abbreviations and acronyms; reasons for
the proposed rule; and a summary of the proposed changes and
clarifications; the legal authority for the proposed rule; methods
incorporated by reference; a summary of the proposed changes and
clarifications and solicits comment from the public.
Abbreviations and Acronyms Used in the Preamble and Proposed Rule Text
ADMI: American Dye Manufacturers Institute
ASTM: ASTM International \1\
---------------------------------------------------------------------------
\1\ Formerly known as the American Society for Testing and
Materials (ASTM).
---------------------------------------------------------------------------
ATP: Alternate Test Procedure
BHI: Brain heart infusion
BOD5: 5-day Biochemical Oxygen Demand
CATC: Cyanide Amenable to Chlorination
CBI: Confidential Business Information
CFR: Code of Federal Regulations
CIE: Capillary Ion Electrophoresis
CNCl: Cyanogen Chloride
CWA: Clean Water Act
EC-MUG: EC broth with 4-methylumbelliferyl-[beta]-D-glucuronide
EDTA: Ethylenediaminetetraacetic acid
EPA: Environmental Protection Agency
DO: Dissolved Oxygen
GC: Gas Chromatography
GC/MS/MS: Gas Chromatography-Tandem Mass Spectrometry
GC/HRMS: Gas Chromatography-High Resolution Mass Spectrometry
ICP/AES: Inductively Coupled Plasma-Atomic Emission Spectroscopy
MIBK: Methyl Isobutyl Ketone
NED: N-(1-naphthyl)-ethylenediamine dihydrochloride
MF: Membrane Filtration
MgCl2: Magnesium Chloride
MPN: Most Probable Number
nm: Nanometer
NPDES: National Pollutant Discharge Elimination System
NTTAA: National Technology Transfer and Advancement Act
QC: Quality Control
STGFAA: Stabilized Temperature Graphite Furnace Atomic Absorption
Spectroscopy
TKN: Total Kjeldahl Nitrogen
TOC: Total Organic Carbon
USGS: United States Geological Survey
VCSB: Voluntary Consensus Standards Body
NPDES permits must include conditions designed to ensure compliance
with the technology-based and water quality-based requirements of the
CWA, including in many cases, restrictions on the quantity of specific
pollutants that can be discharged as well as pollutant measurement and
reporting requirements. Often, entities have a choice in deciding which
approved test procedure they will use for a specific pollutant because
EPA has approved the use of more than one method.\2\
---------------------------------------------------------------------------
\2\ NPDES permit regulations also specify that the approved
method needs to be sufficiently sensitive. See 40 CFR 122.21(e)(3).
---------------------------------------------------------------------------
The procedures for the analysis of pollutants required by CWA
section 304(h) are a central element of the NPDES permit program.
Examples of where these EPA-approved analytical methods must be used
include the following: (1) applications for NPDES permits, (2) sampling
or other reports required under NPDES permits, (3) other requests for
quantitative or qualitative effluent data under the NPDES regulations,
(4) State CWA 401 certifications, and (5) sampling and analysis
required under EPA's General Pretreatment Regulations for Existing and
New Sources of Pollution, 40 CFR 136.1 and 40 CFR 403.12(b)(5)(v).
Periodically, EPA proposes to update the approved methods in 40 CFR
part 136. In general, the changes proposed in this action fall into the
following categories. The first category is updated versions of EPA
methods currently approved in 40 CFR part 136. The second is new or
revised methods published by the VCSBs or the USGS that are similar to
methods previously adopted as EPA-approved methods in 40 CFR part 136.
The third category is methods EPA has reviewed under the Agency's
national ATP program and preliminarily concluded are appropriate for
nationwide use. Finally, EPA is proposing certain corrections or
amendments to the text and tables of 40 CFR part 136. EPA is proposing
adoption of these revisions to improve data quality, update methods to
keep current with technology advances, and provide the regulated
community with greater flexibility. The following paragraphs provide
details on the proposed revisions.
A. Changes to 40 CFR 136.3 To Include New Versions of Previously
Approved EPA Methods
EPA proposes to approve revised versions of the EPA membrane
filtration methods 1103.2, 1106.2, 1600.1, and 1603.1 found in Tables
IA and IH. These methods were approved from 2002 to 2014. The revisions
include standardizing language between the related methods, updating to
reflect current lab practices and clarifying edits. Copies of these
proposed method updated versions are available in the docket to this
rule.
These methods each describe a membrane filter (MF) procedure for
the detection and enumeration of either enterococci or Escherichia coli
bacteria
[[Page 10726]]
by their growth after incubation on selective media. These methods
provide a direct count of bacteria in water samples based on the
development of colonies on the surface of the membrane filter.
1. E. coli. Method 1103.2 describes a MF procedure for the
detection and enumeration of Escherichia coli bacteria in ambient
(fresh) water and is currently approved in Table IH. This is a two-step
method which requires transferring the membrane filter after incubation
on membrane-Thermotolerant Escherichia coli Agar (mTEC) to a pad
saturated with urea substrate.
2. Enterococci. Method 1106.2 describes a MF procedure for the
detection and enumeration of enterococci bacteria in ambient water and
is currently approved in Table IH. This is a two-step method which
requires transferring the membrane filter after incubation on
membraneEnterococcus (mE) agar to Esculin Iron Agar (EIA) medium.
3. Enterococci. Method 1600.1 describes a MF procedure for the
detection and enumeration of enterococci bacteria in ambient (fresh and
marine) water and wastewater and is currently approved in Tables IA and
IH. This is a single-step method that is a modification of EPA Method
1106.1 (mE-EIA). The membrane filter containing the bacterial cells is
placed on membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI).
4. E. coli. Method 1603.1 describes a MF procedure for the
detection and enumeration of thermotolerant Escherichia coli bacteria
in ambient (fresh) waters and wastewaters using Modified membrane-
Thermotolerant Escherichia coli Agar (modified mTEC) and is currently
approved in Table IA and IH.
B. Changes to 40 CFR 136.3 To Include New Versions of Approved ASTM
Methods
EPA is proposing to approve new versions of ASTM methods previously
approved in 40 CFR part 136. These changes to currently approved ASTM
methods in 40 CFR part 136 include minor clarifications and editorial
changes. As an example, ASTM added text to the appropriate method scope
sections to indicate that the method was developed in accordance with
the ``Decision on Principles for the Development of International
Standards, Guides and Recommendations'' issued by the World Trade
Organization Technical Barriers to Trade (TBT) Committee. None of these
proposed changes will affect the performance of the method. The
following describes the changes to current ASTM methods that EPA
proposes to include in 40 CFR part 136. Each entry contains (in the
following order): the parameter, proposed ASTM method number (the last
two digits in the method number represent the year ASTM published), a
brief description of the analytical technique, and a brief description
of any minor procedural changes (if there are any) in this revision
from the last approved version of the method. Method revisions that are
only formatting in nature will have no description of the changes. The
methods listed below are organized according to the table at 40 CFR
part 136 in the order in which they appear.
EPA proposes the following changes to ASTM methods found in Table
IB, and Table II at 40 CFR part 136:
1. Dissolved Oxygen. D888-18 (A, B, C), Dissolved Oxygen, Winkler,
Electrode, Luminescent-based Sensor. Standard D888-18A measures
dissolved oxygen using the Winkler iodometric titration procedure. The
volume of titrant used is proportional to the concentration of
dissolved oxygen in the sample. Standard D888-18B measures dissolved
oxygen in the sample with an electrochemical probe that produces an
electrical potential which is logarithmically proportional to the
concentration of dissolved oxygen in the sample. Standard D888-18C
measures dissolved oxygen with a luminescence-based sensor probe that
employs frequency domain lifetime-based luminescence quenching and
signal processing. The 2012 versions, D888-12 (A), (B) and (C),
currently are approved in Table IB for determination of dissolved
oxygen.
2. Hydrogen Ion (pH). In D1293-18 (A, B), pH, Electrometric. The
activity of hydrogen ion (H+) in the sample is determined
electrometrically with an ion-selective electrode in comparison to at
least two standard reference buffers and pH is reported as the negative
log of that activity. The 1999 version currently is approved in Table
IB.
3. Metals Series. In D1976-20, Elements in Water by Inductively-
Coupled Plasma Atomic Emission Spectroscopy for determination of
aluminum, antimony, arsenic, beryllium, boron, cadmium, chromium,
cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel,
selenium, silver, thallium, vanadium, and zinc. The sample is acid
digested and analyzed by inductively-coupled plasma atomic emission
spectroscopy (ICP/AES) for the simultaneous or sequential determination
of 29 elements. The changes include changing the initial instrument
calibration from using four standards as the first option to using only
one standard and a calibration blank. The 2012 version of this method,
D1976-12, currently is approved in Table IB for 20 of the 29 elements.
4. Surfactants. In D2330-20, Methylene Blue Active Substances, the
sample is mixed with an acidic aqueous solution of methylene blue
reagent, which forms a blue-colored ion pair with any anionic
surfactants which is subsequently extracted with chloroform and washed
with an acidic solution to remove interferences. The intensity of the
blue color is measured using a photometer at 650 nanometers (nm). The
concentration of methylene blue active substances is determined in
comparison to a standard curve. The 2002 version, D2330-02, currently
is approved in Table IB for determination of surfactants.
5. Residue, filterable and nonfilterable. In D5907-18 (A and B),
Filterable Matter (Total Dissolved Solids) and Nonfilterable Matter
(Total Suspended Solids) under Test Method A, an aliquot of the sample
is filtered through a glass fiber filter and the solids trapped on the
filter are dried at 105 [deg]C and weighed to determine the
nonfilterable material (total suspended solids) by difference. Under
Test Method B, the filtrate from Test Method A, or a separate filtrate,
is evaporated to dryness at 180 [deg]C and the residue weighed to
determine the total dissolved solids. The 2013 version is currently
approved in Table IB.
6. Cyanide--Free. In D7237-18, Free Cyanide, Flow Injection,
followed by Gas Diffusion Amperometry an aliquot of the sample is
introduced into a flow injection analysis instrument, where it mixes
with a phosphate buffer to release hydrogen cyanide which diffuses
through a hydrophobic gas diffusion membrane into an alkaline solution
and is detected amperometrically with a silver electrode. This version
also added new information about sulfide interferences and potential
mitigation strategies that EPA anticipates will improve data quality.
There are no other procedural changes. The 2015 version, D7237-15,
currently is approved in Table IB for determination of free cyanide.
7. Cyanide--Total. In D7284-20, Total Cyanide, Manual Distillation
with MgCl2 followed by Flow Injection, Gas Diffusion
Amperometry, the sample is distilled with acid and a magnesium chloride
catalyst to release cyanide to a sodium hydroxide solution. An aliquot
of the sodium hydroxide solution is introduced into a flow injection
analysis instrument, where it is acidified, and
[[Page 10727]]
the hydrogen cyanide diffuses through a hydrophobic gas diffusion
membrane into an alkaline solution and is detected amperometrically
with a silver electrode. The 2017 reapproval of D7284-13 currently is
approved in Table IB for determination of total cyanide.
8. Organic Carbon. In D7573-18a\e1\, Total Organic Carbon,
Combustion, the sample is sparged with an inert gas to remove dissolved
inorganic carbon, acidified, and then combusted at high temperature to
convert organic carbon to carbon dioxide. The carbon dioxide is
measured with an infra-red detector. This version also adds data from
an interlaboratory method validation study and new method detection
limit values, but there are no procedural changes. The 2017 reapproval
of D7573-09 currently is approved in Table IB for determination of
total organic carbon (TOC).
C. Changes to 40 CFR 136.3 To Include New Versions of Approved
``Standard Methods'' Methods
EPA is proposing to approve new versions of methods developed by
the Standard Methods Committee that were previously approved in 40 CFR
part 136. Standard Methods has reviewed many of their methods in
preparation for releasing the next edition of ``Standard Methods for
the Examination of Water & Wastewater.'' The newer versions provide
clarifications and make editorial corrections. These edits include
removal of referents to specific brand names and trademarks,
incorporation of footnotes into the text, a reformatting of figures,
tables and reference lists, removal of bibliographical references that
are no longer available, small editorial changes based on current style
guides and changes to scientific publishing standards, and minor
clarifications to procedures based on input from users. For example,
the revisions replace distilled water with reagent water in all
methods. As was the case with the previous methods update rule (86 FR
27226, May 19, 2021), EPA generally proposes to approve and include in
40 CFR part 136 only the most recent version of a method published by
the Standard Methods Committee. EPA is proposing to list only one
version of the method with the year of publication designated by the
last four digits in the method number (e.g., 3111 C-2019). The date
indicates the date of the specific revision to the method. This allows
use of a specific method in any edition of the hard copy publication of
``Standard Methods for the Examination of Water & Wastewater'' that
includes a method with the same method number and year of publication.
The proposed revisions to methods previously approved in 40 CFR
part 136 will not affect the performance of the method. Below is a list
of the methods EPA is proposing to include in 40 CFR part 136. Each
entry contains the proposed Standard Methods number and date, the
parameter, and a brief description of the analytical method. The
methods listed below are organized according to the table at 40 CFR
part 136.
EPA proposes to make the following changes to Tables IA, IB, IC, ID
and IH at 40 CFR part 136 for the following parameters:
1. Color. 2120 B-2021, Visual Comparison Method, is a platinum-
cobalt method of measuring color, the unit of color being that produced
by one mg platinum per liter in the form of the chloroplatinate ion.
The 1:2 ratio of cobalt to platinum resulting from the preparation of
the standard platinum-cobalt solution matches the color of natural
waters. The 2011 editorial revision currently is approved in Table IB
for determination of color. 2120 F-2021, American Dye Manufacturers
Institute (ADMI) Weighted-Ordinate Spectrophotometric Method. In
accordance with the Adams-Nickerson chromatic value formula, this
method calculates single-number color difference values (i.e., uniform
color differences). Values are independent of chroma and hue.
Transmittance of light is measured spectrophotometrically at multiple
wavelengths and converted to a set of abstract numbers, which then are
converted to a single number that indicates color value. This number is
expressed on a scale used by the ADMI. The 2011 editorial revision
currently is approved in Table IB for determination of color.
2. Turbidity. 2130 B-2020, Nephelometric Method is based on a
comparison of the intensity of light scattered by the sample under
defined conditions with the intensity of light scattered by a standard
reference suspension under the same conditions. The higher the
intensity of scattered light, the higher the turbidity. Formazin
polymer is used as the primary standard reference suspension. The 2011
editorial revision currently is approved in Table IB for determination
of turbidity.
3. Acidity. 2310 B-2020, Titration Method measures the hydrogen
ions present in a sample as a result of dissociation or hydrolysis of
solutes that react with additions of standard alkali. Acidity thus
depends on the endpoint pH or indicator used. The construction of a
titration curve by recording a sample's pH after successive small,
measured additions of titrant permits identification of inflection
points and buffering capacity, if any, and allows the acidity to be
determined with respect to any pH of interest. Samples of industrial
wastes, acid mine drainage, or other solutions that contain appreciable
amounts of hydrolyzable metal ions such as iron, aluminum, or manganese
are treated with hydrogen peroxide to ensure the oxidation of any
reduced forms of polyvalent cations and are boiled to hasten
hydrolysis. Acidity results may be highly variable if this procedure is
not followed exactly. The 2011 editorial revision currently is approved
in Table IB for determination of acidity.
4. Alkalinity. 2320 B-2021 Titration Method, measures the hydroxyl
ions present in a sample resulting from dissociation or hydrolysis of
solutes that react with additions of standard acid. Alkalinity thus
depends on the endpoint pH used. For samples of low alkalinity (less
than 20 mg/L CaCO3) an extrapolation technique based on the
near proportionality of concentration of hydrogen ions to excess of
titrant beyond the equivalence point is used. The amount of standard
acid required to reduce the pH exactly 0.30 pH unit is measured
carefully. Because this change in pH corresponds to an exact doubling
of the hydrogen ion concentration, a simple extrapolation can be made
to the equivalence point. The 2011 editorial revision currently is
approved in Table IB for determination of alkalinity.
5. Hardness. 2340 B-2021, Hardness by Calculation is the preferred
method for determining hardness by calculating it from the results of
separate determinations of calcium and magnesium by any approved method
provided that the sum of the lowest point of quantitation for Ca and Mg
is below the NPDES permit requirement for hardness. The 2011 editorial
revision currently is approved in Table IB for determination of
hardness. In 2340 C-2021, Ethylenediaminetetraacetic acid (EDTA)
Titrimetric Method, EDTA forms a chelated soluble complex when added to
a solution of certain metal cations. If a small amount of a dye such as
eriochrome black T or calmagite is added to an aqueous solution
containing calcium and magnesium ions at a pH of 10.0 0.1,
the color of the solution becomes wine red. If EDTA is added as a
titrant, the calcium and magnesium will be complexed, and when all of
the magnesium and calcium has been complexed, the solution turns from
wine red to blue, marking the endpoint of the titration. The volume of
titrant used is proportional to hardness in the
[[Page 10728]]
sample. Magnesium ion must be present to yield a satisfactory endpoint.
To ensure this, a small amount of complexometrically neutral magnesium
salt of EDTA is added to the buffer; this automatically introduces
sufficient magnesium and obviates the need for a blank correction. The
2011 editorial revision currently is approved in Table IB for
determination of hardness.
6. Specific Conductance. 2510 B-2021 measures conductance (or
resistance) in the laboratory using a standard potassium chloride
solution and from the corresponding conductivity, a cell constant is
calculated. Most conductivity meters do not display the actual solution
conductance, or resistance, rather, they generally have a dial that
permits the user to adjust the internal cell constant to match the
conductivity of a standard. Once the cell constant has been determined,
or set, the conductivity of an unknown solution is displayed by the
meter. The 2011 editorial revision currently is approved in Table IB
for determination of specific conductance.
7. Residue--Total. In 2540 B-2020 an aliquot of a well-mixed sample
is evaporated in a pre-weighed evaporating dish at 103-105 [deg]C to
constant weight in a 103 to 105 [deg]C oven. The increase compared to
the empty pre-weighed dish weight represents total solids. The 2015
version of the method currently is approved in Table IB for
determination of total residue. In 2540 C-2020, Total Dissolved Solids
Dried at 180 [deg]C (Residue--filterable in Table IB) a measured volume
of a well-mixed sample is filtered through a glass fiber filter with
applied vacuum. The entire exposed surface of the filter is washed with
at least 3 successive volumes of reagent-grade water with continued
suction until all traces of water are removed. The total filtrate (with
washings) is then transferred to a pre-weighed dish and evaporated to
dryness. Successive volumes of sample are added to the same dish after
evaporation if necessary to yield between 2.5 and 200 mg of dried
residue. The evaporated residue is then dried for one hour or more in
an oven at 180 [deg]C, cooled in a desiccator to ambient temperature,
and weighed until the weight change is less than 0.5 mg. The 2015
version of the method currently is approved in Table IB for
determination of filterable residue. In 2540 D-2020, Total Suspended
Solids Dried from 103 to 105 [deg]C (Residue--non-filterable total
suspended solids (TSS) in Table IB) a well-mixed sample is filtered
through a pre-weighed standard glass-fiber filter. The filter and the
retained residue are then dried to a constant weight in a 103 to 105
[deg]C oven. The increase in filter weight represents TSS. The 2015
version of the method currently is approved in Table IB for
determination of non-filterable residue. In 2540 E-2020, Fixed and
Volatile Solids Ignited at 550 [deg]C (Residue--volatile in Table IB)
the residue obtained from the determination of total (Method 2540 B),
filterable (Method 2540 C), or non-filterable residue (Method 2540 D)
is ignited at 550 50 [deg]C in a muffle furnace, cooled in
a desiccator to ambient temperature and weighed. Repeated successive
cycles of drying, cooling, desiccating, and weighing are performed
until the weight change is less than 0.5 mg. The remaining solids are
fixed total, dissolved, or suspended solids, while those lost to
ignition are volatile total, dissolved, or suspended solids. The 2015
version of the method currently is approved in Table IB for
determination of volatile residue. In 2540 F-2020, Settleable Solids
(aka, Residue--settleable in Table IB), a well-mixed sample is used to
fill an Imhoff cone or graduated cylinder to the 1-L mark. The sample
is allowed to settle for 45 minutes, then gently agitated near the
sides of the cone (or graduated cylinder) with a rod or by spinning.
The sample is then allowed to settle for another 15 minutes and the
volume of settleable solids in the cone (or graduated cylinder) is
recorded as mL/L. When applicable, the recorded volume is corrected for
interference from pockets of liquid volume. The 2015 version of the
method currently is approved in Table IB for determination of
settleable residue.
8. Multiple metals by flame atomic absorption spectrometry.
a. 3111 B-2019, Direct Air-Acetylene Flame Method. The 2011
editorial revision currently is approved in Table IB for determination
of antimony, cadmium, calcium, chromium, cobalt, copper, gold, iridium,
iron, lead, magnesium, manganese, nickel, palladium, platinum,
potassium, rhodium, ruthenium, silver, sodium, thallium, tin, and zinc.
A sample is aspirated into a flame and the metals are atomized. A light
beam is directed through the flame, into a monochromator, and onto a
detector that measures the amount of light absorbed by the atomized
metal in the flame. Because each metal has its own characteristic
absorption wavelength, a source lamp composed of that element is used.
The amount of energy at the characteristic wavelength absorbed in the
flame is proportional to the concentration of the element in the sample
over a limited concentration range.
b. 3111 C-2019, Extraction and Air-Acetylene Flame Method consists
of chelation with ammonium pyrrolidine dithiocarbamate (APDC) and
extraction into methyl isobutyl ketone (MIBK), followed by aspiration
into an air-acetylene flame and is suitable for the determination of
low concentrations of cadmium, chromium, cobalt, copper, iron, lead,
manganese, nickel, silver, and zinc. The 2011 editorial revision
currently is approved in Table IB for determination of cadmium,
chromium, cobalt, copper, iron, lead, nickel, silver, and zinc.
EPA proposes to approve method 3111 C for manganese. This parameter
was inadvertently left off in an earlier rulemaking approving method
3111 C.
c. 3111 D-2019, Direct Nitrous Oxide-Acetylene Flame Method. A
sample is aspirated into a flame produced using a mixture of nitrous
oxide and acetylene and the metals are atomized. A light beam is
directed through the flame, into a monochromator, and onto a detector
that measures the amount of light absorbed by the atomized metal in the
flame. The 2011 editorial revision currently is approved in Table IB
for determination of aluminum, barium, beryllium, molybdenum, osmium,
titanium, and vanadium. In addition, EPA proposes to approve method
3111 D for calcium. This parameter was inadvertently left off in an
earlier rulemaking approving method 3111 D.
d. 3111 E-2019, Extraction and Nitrous Oxide-Acetylene Flame
Method. The method consists of chelation with 8-hydroxyquinoline,
extraction with MIBK, and aspiration into a nitrous oxide-acetylene
flame and is suitable for the determination of aluminum at
concentrations less than 900 [mu]g/L and beryllium at concentrations
less than 30 [mu]g/L. The 2011 editorial revision currently is approved
in Table IB for determination of aluminum, and beryllium.
9. Mercury--Total. 3112 B-2020, Metals by Cold-Vapor Atomic
Absorption Spectrometric Method is a flameless AA procedure based on
the absorption of radiation at 253.7 nm by mercury vapor. The mercury
in a sample is reduced to the elemental state and aerated from solution
in a closed system. The mercury vapor passes through a cell positioned
in the light path of an atomic absorption spectrophotometer. Absorbance
is measured as a function of mercury concentration. The 2011 editorial
revision currently is approved in Table IB for determination of
mercury.
[[Page 10729]]
10. Metals by AA Furnace. In 3113 B-2020, Electrothermal Atomic
Absorption Spectrometric Method, a discrete sample volume is dispensed
into the graphite sample tube (or cup). Typically, determinations are
made by heating the sample in three or more stages. First, a low
current heats the tube to dry the sample. The second, or charring,
stage destroys organic matter and volatilizes other matrix components
at an intermediate temperature. Finally, a high current heats the tube
to incandescence and, in an inert atmosphere, atomizes the element
being determined. Additional stages frequently are added to aid in
drying and charring, and to clean and cool the tube between samples.
The resultant ground-state atomic vapor absorbs monochromatic radiation
from the source. A photoelectric detector measures the intensity of
transmitted radiation. The inverse of the transmittance is related
logarithmically to the absorbance, which is directly proportional to
the number density of vaporized ground-state atoms (the Beer-Lambert
law) over a limited concentration range. The 2010 version of the method
currently is approved in Table IB for determination of aluminum,
antimony, arsenic, barium, beryllium, cadmium, chromium, cobalt,
copper, iron, lead, manganese, molybdenum, nickel, selenium, silver,
and tin. Although not specifically listed as target analytes in 3113 B,
the 2010 version of the method is also approved in Table IB for
determination of gold, thallium, and vanadium, as these elements may
also be determined using the method.
11. Arsenic and Selenium by AA Gaseous Hydride. 3114 B-2020, Manual
Hydride Generation/Atomic Absorption Spectrometric Method is a manual
hydride generation method that is applicable to the determination of
arsenic and selenium by conversion to their hydrides by sodium
borohydride reagent and transport into an atomic absorption atomizer.
The 2011 editorial revision currently is approved in Table IB for
determination of arsenic and selenium. 3114 C-2020, Continuous Hydride
Generation/Atomic Absorption Spectrometric Method is a continuous-flow
hydride generation method that is applicable to the determination of
arsenic and selenium by conversion to their hydrides by sodium
borohydride reagent and transport into an atomic absorption atomizer.
The continuous hydride generator offers the advantages of simplicity in
operation, excellent reproducibility, low detection limits, and high
sample volume throughput for selenium analysis following preparations
as described in 3500-Se B or 3114 B.4c and d. The 2011 editorial
revision currently is approved in Table IB for determination of arsenic
and selenium.
12. Multiple Metals by ICP/AES (Plasma Emission Spectroscopy). In
3120 B-2020, an Inductively Coupled Plasma (ICP) source consists of a
flowing stream of argon gas ionized by an applied radio frequency field
typically oscillating at 27.1 MHz. This field is inductively coupled to
the ionized gas by a water-cooled coil surrounding a quartz torch that
supports and confines the plasma. A sample aerosol is generated in an
appropriate nebulizer and spray chamber and is carried into the plasma
through an injector tube located within the torch. The sample aerosol
is injected directly into the ICP, subjecting the constituent atoms to
temperatures of about 6000 to 8000 [deg]K. Because this results in
almost complete dissociation of molecules, significant reduction in
chemical interferences is achieved. The high temperature of the plasma
excites atomic emission efficiently. Ionization of a high percentage of
atoms produces ionic emission spectra. The ICP provides an optically
thin source that is not subject to self-absorption except at very high
concentrations. Total metals are determined after appropriate
digestion. The 2011 editorial revision currently is approved in Table
IB for determination of aluminum, antimony, arsenic, barium, beryllium,
boron, cadmium, calcium, chromium, cobalt, copper, iron, lead,
magnesium, manganese, molybdenum, nickel, potassium, selenium, silica,
silver, sodium, thallium, vanadium, and zinc. Although not specifically
listed as a target analyte in method 3120 B, the 2011 version of the
method is also approved in Table IB for determination of phosphorus
because this element may also be determined using the method.
13. Multiple Metals by Inductively Coupled Plasma-Mass
Spectrometry. In this method, 3125 B-2020, Inductively Coupled Plasma-
Mass Spectrometry (ICP-MS) Method, a sample is introduced into an
argon-based, high-temperature radio-frequency plasma, usually via
pneumatic nebulization. As energy transfers from the plasma to the
sample stream, the target element desolvation, atomization, and
ionization. The resulting ions are extracted from the plasma through a
differential vacuum interface and separated based on their mass-to-
charge (m/z) ratio by a mass spectrometer. Typically, either a
quadrupole (with or without collision cell technology or dynamic
reaction cell) or magnetic sector (high-resolution) mass spectrometer
is used. An electron multiplier detector counts the separated ions, and
a computer-based data-management system processes the resulting
information. The 2011 editorial revision currently is approved in Table
IB for determination of aluminum, antimony, arsenic, barium, beryllium,
cadmium, chromium, cobalt, copper, lead, manganese, molybdenum, nickel,
potassium, selenium, silver, thallium, vanadium, and zinc. Although not
specifically listed as a target analyte in method 3125 B, the 2011
version of the method is also approved in Table IB for determination of
boron, calcium, gold, iridium, iron, magnesium, palladium, platinum,
potassium, rhodium, ruthenium, silica, sodium, tin, and titanium as
these elements may also be determined using the method.
14. 3500 Colorimetric Series for Multiple Metals.
a. Aluminum. In 3500-Al B-2020, Eriochrome Cyanine R Method with
Eriochrome cyanine R dye, dilute aluminum solutions buffered to a pH of
6.0 produce a red to pink complex that exhibits maximum absorption at
535 nm. The intensity of the developed color is influenced by the
aluminum concentration, reaction time, temperature, pH, alkalinity, and
concentration of other ions in the sample. To compensate for color and
turbidity, the aluminum in one portion of a sample is complexed with
EDTA to provide a blank. The interference of iron and manganese, two
elements commonly found in water when aluminum is present, is
eliminated by adding ascorbic acid. The 2011 editorial revision
currently is approved in Table IB for determination of aluminum.
b. Arsenic. In 3500-As B-2020, Silver Diethyldithiocarbamate
Method, arsenite, containing trivalent arsenic, is reduced selectively
by aqueous sodium borohydride solution to arsine, AsH3, in
an aqueous medium of pH 6. Arsenate, methylarsonic acid, and
dimethylarsinic acid are not reduced under these conditions. The
generated arsine is swept by a stream of oxygen-free nitrogen from the
reduction vessel through a scrubber containing glass wool or cotton
impregnated with lead acetate solution into an absorber tube containing
silver diethyldithiocarbamate and morpholine dissolved in chloroform.
The intensity of the red color that develops is measured at 520 nm. The
2011 editorial revision currently is approved in Table IB for
determination of arsenic.
c. Calcium. In 3500-Ca B-2020, EDTA Titrimetric Method, EDTA is
added to water containing both calcium and
[[Page 10730]]
magnesium, where it combines first with the calcium. Calcium can be
determined directly, with EDTA, when the pH is made sufficiently high
that the magnesium is largely precipitated as the hydroxide and an
indicator is used that combines with calcium only. Several indicators
give a color change when all the calcium has been complexed by the EDTA
at a pH of 12 to 13. The 2011 editorial revision currently is approved
in Table IB for determination calcium.
d. Chromium. 3500-Cr B-2020, Colorimetric Method. This procedure
measures only hexavalent chromium, (chromium VI). The hexavalent
chromium is determined colorimetrically by reaction with
diphenylcarbazide in acid solution. A red-violet colored complex of
unknown composition is produced. The 2011 editorial revision currently
is approved in Table IB for determination of dissolved hexavalent
chromium (chromium VI). 3500-Cr C-2020, Ion Chromatographic Method.
This method is applicable to determination of dissolved hexavalent
chromium in drinking water, groundwater, and industrial wastewater
effluents. An aqueous sample is filtered, and its pH adjusted to
between 9 and 9.5 with a concentrated buffer. This pH adjustment
reduces the solubility of trivalent chromium and preserves the
hexavalent chromium oxidation state. The sample is introduced into the
instrument's eluent stream of ammonium sulfate and ammonium hydroxide.
Trivalent chromium in solution is separated from the hexavalent
chromium by the column. After separation, hexavalent chromium reacts
with an azide dye to produce a chromogen that is measured at 530 or 540
nm. Hexavalent chromium is identified based on retention time. The 2011
editorial revision currently is approved in Table IB for determination
of dissolved hexavalent chromium (chromium VI).
e. Copper Colorimetric. In 3500-Cu B-2020, Neocuproine Method, the
sample is treated with hydroxylamine hydrochloride to reduce any cupric
ions (Cu\2+\) to cuprous ions (Cu\+\). Sodium citrate is used to
complex metallic ions that might precipitate when the pH is raised. The
pH is adjusted to between 4 and 6 with ammonium hydroxide
(NH4OH), a solution of neocuproine (2,9-dimethyl-1,10-
phenanthroline) in methanol is added, and the resultant complex is
extracted into chloroform (CHCl3). After dilution of the
CHCl3 to an exact volume with methanol (CH3OH),
the absorbance of the solution is measured at 457 nm. The 2011
editorial revision currently is approved in Table IB for determination
of copper. In 3500-Cu C-2020, Bathocuproine Method, cuprous ion forms a
water-soluble orange-colored chelate with disodium bathocuproine
disulfonate (sodium 4,4'-(2,9-dimethyl-1,10-phenanthroline-4,7-
diyl)dibenzenesulfonate). While the color forms over the pH range 3.5
to 11.0, the recommended pH range is between 4 and 5. The sample is
buffered at a pH of about 4.3 and reduced with hydroxylamine
hydrochloride. The absorbance is measured at 484 nm. The 2011 editorial
revision currently is approved in Table IB for determination of copper.
f. Potassium. In 3500-K B-2020, Flame Photometric Method, trace
amounts of potassium can be determined in either a direct-reading or
internal-standard type of flame photometer at a wavelength of 766.5 nm.
The 2011 editorial revision currently is approved in Table IB for
determination of potassium. In 3500-K C-2020, Potassium-Selective
Electrode Method, potassium ions are measured potentiometrically by
using a potassium ion-selective electrode and a double-junction,
sleeve-type reference electrode. The analysis is performed with either
a pH meter having an expanded millivolt scale capable of being read to
the nearest 0.1 mV or a specific-ion meter having a direct
concentration scale for potassium. Before measurement, an ionic
strength adjustor reagent is added to both standards and samples to
maintain a constant ionic strength. The electrode response is measured
in standard solutions with potassium concentrations spanning the range
of interest using a calibration line derived either by the instrument
meter or manually. The electrode response in sample solutions is
measured following the same procedure and potassium concentration
determined from the calibration line or instrument direct readout. The
2011 editorial revision currently is approved in Table IB for
determination of potassium.
g. Manganese. In 3500-Mn B-2020, Persulfate Method, persulfate
oxidation of soluble manganous compounds to form permanganate is
carried out in the presence of silver nitrate. The resulting color is
stable for at least 24 hours if excess persulfate is present and
organic matter is absent. The 2011 editorial revision currently is
approved in Table IB for determination of manganese.
h. Sodium. In 3500-Na B-2020, Flame Emission Photometric Method a
sample is nebulized into a gas flame under carefully controlled,
reproducible excitation conditions. The sodium resonant spectral line
at 589 nm is isolated by interference filters or by light-dispersing
devices such as prisms or gratings. Emission light intensity is
measured by a phototube, photomultiplier, or photodiode. The light
intensity at 589 nm is approximately proportional to the sodium
concentration. The 2011 editorial revision currently is approved in
Table IB for determination of sodium.
i. Lead. In 3500-Pb B-2020, Dithizone Method, an acidified sample
containing microgram quantities of lead is mixed with ammoniacal
citrate-cyanide reducing solution and extracted with dithizone in
chloroform (CHCl3) to form a cherry-red lead dithizonate.
The color of the mixed color solution is measured photometrically. The
2011 editorial revision currently is approved in Table IB for
determination of lead.
j. Zinc. 3500-Zn B-2020, Zincon Method. Zinc forms a blue complex
with zincon (2-carboxy-2'-hydroxy-5'-sulfoformazyl benzene) in a
solution buffered to pH 9.0. Other heavy metals likewise form colored
complexes with zincon. Cyanide is added to complex zinc and heavy
metals. Cyclohexanone is added to selectively free zinc from its
cyanide complex so that it can be complexed with zincon to form a blue
color which is measured spectrophotometrically at 620 nm. Sodium
ascorbate reduces manganese interference. The developed color is stable
except in the presence of copper. The 2011 editorial revision currently
is approved in Table IB for determination of zinc.
15. 4110 Series, Ion Chromatography.
a. In 4110 B-2020, Ion Chromatography with Chemical Suppression of
Eluent Conductivity, is approved in Table IB for determination of
bromide, chloride, fluoride, nitrate, nitrite, orthophosphate, and
sulfate. A water sample is injected into a stream of eluent and passed
through a series of ion exchangers. The anions of interest are
separated based on their relative affinities for a low-capacity,
strongly basic anion exchanger (guard and analytical columns). The
separated anions are directed through a suppressor device that provides
continuous suppression of eluent conductivity and enhances analyte
response. In the suppressor, the separated anions are converted to
their highly conductive acid forms while the conductivity of the eluent
is greatly decreased. The separated anions in their acid forms are
measured by conductivity. They are identified based on retention time
as compared to standards. Quantitation is by measurement of peak area
or peak height. The 2011 editorial revision
[[Page 10731]]
currently is approved in Table IB for determination of bromide,
chloride, fluoride, nitrate, combined nitrate-nitrite, nitrite,
orthophosphate, and sulfate.
b. 4110 C-2020, Single-Column Ion Chromatography with Direct
Conductivity Detection. An aqueous sample is injected into an ion
chromatograph consisting of an injector port, analytical column, and
conductivity detector. The sample merges with the eluent stream and is
pumped through the analytical column where the anions are separated
based on their affinity for the active sites of the column packing
material. Concentrations are determined by direct conductivity
detection without chemical suppression. The 2011 editorial revision
currently is approved in Table IB for determination of bromide,
chloride, fluoride, nitrate, combined nitrate-nitrite, nitrite,
orthophosphate, and sulfate.
c. 4110 D-2020, Ion Chromatographic Determination of Oxyhalides and
Bromide. The sample is analyzed in a manner similar to that in 4110 B-
2020. However, bromate has been shown to be subject to positive
interferences in some matrices. The interference is noticeable usually
as a flattened peak. It often can be eliminated by passing the sample
through an H\+\ off-line solid-phase extraction (SPE) cartridge, by
selection of a different column-eluent combination, or by diluting the
eluent, which will increase retention times and spread the
chromatogram. Additionally, chloride or a nontarget analyte present in
unusually high concentration may overlap with a target analyte
sufficiently to cause problems in quantitation or may cause retention-
time shifts. Dilution of the sample may resolve this problem. The 2011
editorial revision currently is approved in Table IB for determination
of bromide.
16. Inorganic Anions by CIE/UV (Capillary Ion Electrophoresis). In
4140 B-2020, Capillary Ion Electrophoresis with Indirect UV Detection,
the sample is introduced at the cathodic end of the capillary and
anions are separated based on their differences in mobility in the
electric field as they migrate through the capillary. Cations migrate
in the opposite direction and are not detected. Water and neutral
organics are not attracted toward the anode. They migrate after the
anions and thus do not interfere with anion analysis. Anions are
detected as they displace charge-for-charge the UV-absorbing
electrolyte anion (chromate), causing a net decrease in UV absorbance
in the analyte anion zone compared to the background electrolyte.
Detector polarity is reversed to provide positive millivolt response to
the data system. As in chromatography, the analytes are identified by
their migration time and quantitated by using time-corrected peak area
relative to standards. The 2011 editorial revision currently is
approved in Table IB for determination of bromide, chloride, fluoride,
nitrate, combined nitrate-nitrite, nitrite, orthophosphate, and
sulfate.
17. 4500 Series, Chloride.
a. 4500-Cl- B-2021, Titrimetric Method. In a neutral or
slightly alkaline solution, potassium chromate can indicate the
endpoint of the silver nitrate titration of chloride. Silver chloride
is precipitated quantitatively before red silver chromate is formed. In
this version of the method approved by the Standard Methods Committee
in 2021, additional information regarding removal of interferences
caused by sulfide, thiosulfate, and sulfite ions by digestion of the
sample with hydrogen peroxide prior to titration has been added to the
sample preparation procedures. A tighter pH range of 8-10, as opposed
to 7-10, is specified for adjustment of the pH of the sample prior to
titration. A reference has been added for the 2021 Standard Methods
Joint Task Group validation report titled: ``Interlaboratory validation
study for the use of H2O2 with boiling for
determining Cl-.'' The 2011 editorial revision currently is
approved in Table IB for determination of chloride.
b. 4500-Cl- C-2021, Mercuric Nitrate Method. Chloride
can be titrated with mercuric nitrate, Hg(NO3)2,
because of the formation of soluble, slightly dissociated mercuric
chloride. In the pH range 2.3 to 2.8, diphenylcarbazone indicates the
titration endpoint by formation of a purple complex with the excess
mercuric ions. Xylene cyanol FF serves as a pH indicator and endpoint
enhancer. Increasing the strength of the titrant and modifying the
indicator mixtures extend the range of measurable chloride
concentrations. The 2011 editorial revision currently is approved in
Table IB for determination of chloride.
c. 4500-Cl- D-2021, Potentiometric Method. Chloride is
determined by potentiometric titration with 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 endpoint of the titration is
that instrument reading at which the greatest change in voltage has
occurred for a small and constant increment of silver nitrate added.
The 2011 editorial revision currently is approved in Table IB for
determination of chloride.
d. 4500-Cl- E-2021, Automated Ferricyanide Method.
Thiocyanate ion is liberated from mercuric thiocyanate by the formation
of soluble mercuric chloride. In the presence of ferric ion, free
thiocyanate ion forms a highly colored ferric thiocyanate, of which the
intensity is proportional to the chloride concentration. The 2011
editorial revision currently is approved in Table IB for determination
of chloride.
18. 4500 Series Cyanide Total or Available.
a. 4500-CN- B-2021, Manual Distillation (as Preliminary
Treatment of Samples). Total cyanides are measured after preliminary
treatment of samples for preservation and to remove interferences. The
preliminary treatment required depends on which interfering substances
the samples contain. Distillation removes many interfering substances,
but other pretreatment procedures will be needed for sample containing
sulfides, fatty acids, oxidizing agents, nitrites, and nitrates. The
2016 version of the method currently is approved in Table IB for
preliminary treatment of samples to be used for determination of
cyanide.
b. 4500-CN- C-2021, Total Cyanide after Distillation.
Hydrogen cyanide (HCN) is liberated from an acidified sample by
distillation and purging with air, with the HCN gas collected in a NaOH
scrubbing solution. The cyanide concentration in the scrubbing solution
is determined via titrimetric, colorimetric, or potentiometric
procedures. The 2016 version of the method currently is approved in
Table IB for preliminary treatment of samples to be used for
determination of cyanide.
c. 4500-CN- D-2021, Titrimetric Method. CN-
in the alkaline distillate from the preliminary treatment procedures
(4500-CN- B and C) is titrated with standard silver nitrate
(AgNO3) to form the soluble cyanide complex
Ag(CN)2-. As soon as all CN- has been
complexed and a small excess of Ag\+\ has been added, the silver-
sensitive indicator, p-dimethylaminobenzalrhodanine, detects the excess
Ag\+\ and immediately changes color from yellow to salmon. The 2016
version of the method currently is approved in Table IB for
determination of cyanide.
d. 4500-CN- E-2021, Spectrophotometric Method. Total
CN- in the alkaline distillate from the preliminary
treatment procedures (4500-CN- B and C) is converted to
cyanogen chloride (CNCl) by reaction with chloramine-T at pH <8 without
hydrolyzing to cyanate (CNO-). After
[[Page 10732]]
the reaction is complete, adding a pyridine-barbituric acid reagent
turns CNCl a red-blue color. Maximum color absorbance in aqueous
solution is between 575 and 582 nm. The 2016 version of the method
currently is approved in Table IB for determination of cyanide.
e. 4500-CN- F-2021, Ion Selective Electrode Method.
Total CN- in the alkaline distillate from the preliminary
treatment procedures (4500-CN- B and C) is determined
potentiometrically by using a CN--ion selective electrode.
The 2016 version of the method currently is approved in Table IB for
determination of cyanide.
f. 4500-CN- G-2021, Cyanides Amenable to Chlorination
after Distillation. Available cyanide, or cyanide amenable to
chlorination (CATC), can be determined when a portion of the sample is
chlorinated at high pH and cyanide levels in the chlorinated sample are
determined after manual distillation followed by titrimetric or
spectrophotometric measurement. CATC is calculated by the difference
between the results for cyanide in the unchlorinated sample and the
results for the chlorinated sample. The 2016 version of the method
currently is approved in Table IB for preliminary treatment of samples
to be used for determination of available cyanide.
g. 4500-CN- N-2021, Total Cyanide after Distillation by
Flow Injection Analysis. Total cyanides are digested and steam-
distilled from the sample (4500-CN- C), The cyanide in this
distillate is converted to CNCl by reaction with chloramine-T at pH <8.
The CNCl then forms a red-blue dye by reacting with pyridine-barbituric
acid reagent. The absorbance of this red dye is measured at 570 nm and
is proportional to the total or weak acid dissociable cyanide in the
sample. The 2016 version of the method currently is approved in Table
IB for determination of cyanide.
19. 4500 Total Fluoride Series.
a. 4500-F- B-2021, Preliminary Distillation Step.
Fluoride is separated from other nonvolatile constituents in water by
conversion to hydrofluoric or fluosilicic acid and subsequent
distillation. The conversion is accomplished by using a strong, high-
boiling acid. To protect against glassware etching, hydrofluoric acid
is converted to fluosilicic acid by using soft glass beads.
Quantitative fluoride recovery is accomplished by using a relatively
large sample. Acid and sulfate carryover are minimized by distilling
over a controlled temperature range. The 2011 editorial revision
currently is approved in Table IB for preliminary treatment of samples
to be used for determination of fluoride.
b. 4500-F- C-2021, Ion-Selective Electrode Method. The
fluoride electrode is an ion-selective sensor that measures the ion
activity of fluoride in solution rather than concentration. The key
element in the fluoride electrode is the laser-type doped lanthanum
fluoride crystal across which a potential is established by fluoride
solutions of different concentrations. The crystal contacts the sample
solution at one face and an internal reference solution at the other.
Fluoride ion activity depends on the solution total ionic strength and
pH, and on fluoride complexing species. Adding an appropriate buffer
provides a nearly uniform ionic strength background, adjusts pH, and
breaks up complexes. In effect, the electrode measures concentration.
The 2011 editorial revision currently is approved in Table IB for
determination of fluoride.
c. 4500-F- D-2021, SPADNS Method. The SPADNS
colorimetric method is based on the reaction between fluoride and a
``lake'' of zirconium-dye. Fluoride reacts with the dye lake,
dissociating a portion of it into a colorless complex anion
(ZrF62-) and the dye. As the amount of fluoride
increases, the color produced becomes progressively lighter and
absorbance is measured colorimetrically at 570 nm. The 2011 editorial
revision currently is approved in Table IB for determination of
fluoride.
d. 4500-F- E-2021, Complexone Method. The sample is
distilled in the automated system, and the distillate is reacted with
alizarin fluorine blue-lanthanum reagent to form a blue complex that is
measured colorimetrically at 620 nm. The 2011 editorial revision
currently is approved in Table IB for determination of fluoride.
20. 4500 Hydrogen ion (pH). 4500-H\+\ B-2021, Electrometric Method.
The basic principle of electrometric pH measurement is determination of
the activity of the hydrogen ions by potentiometric measurement using a
standard hydrogen electrode and a reference electrode. The hydrogen
electrode consists of a platinum electrode across which hydrogen gas is
bubbled at a pressure of 101 kilopascal. Because of difficulty in its
use and the potential for poisoning the hydrogen electrode, the glass
electrode commonly is used. The electromotive force (emf) produced in
the glass electrode system varies linearly with pH. This linear
relationship is described by plotting the measured emf against the pH
of different buffers. A sample's pH is determined by extrapolation.
This version of the method adds information to Section 2--Apparatus,
regarding equipment that may be used for manual or automatic
temperature compensation. The 2011 editorial revision currently is
approved in Table IB for determination of pH.
21. 4500 Kjeldahl Nitrogen (TKN) Series.
a. 4500-Norg B-2021, Macro-Kjeldahl Method. In the presence of
sulfuric acid (H2SO4), potassium sulfate
(K2SO4), and a cupric sulfate (CuSO4)
catalyst, amino nitrogen of many organic materials is converted to
ammonium. Free ammonia also is converted to ammonium. After the
addition of base, the ammonia is distilled from an alkaline medium and
absorbed in boric or sulfuric acid. The ammonia may be determined
colorimetrically, by ammonia-selective electrode, or by titration with
a standard mineral acid. The 2011 editorial revision currently is
approved in Table IB for preliminary treatment of samples to be used
for determination of total Kjeldahl nitrogen (TKN).
b. 4500-Norg C-2021, Semi-Micro-Kjeldahl Method. This is a reduced-
volume version of 4500 Norg B that specifies use of Kjeldahl
flasks with a capacity of 100 mL in a semi-micro-Kjeldahl digestion
apparatus equipped with heating elements to accommodate Kjeldahl flasks
and a suction outlet to vent fumes. The 2011 editorial revision
currently is approved in Table IB for preliminary treatment of samples
to be used for determination of total Kjeldahl nitrogen (TKN).
c. 4500-Norg D-2021, Block Digestion and Flow Injection Analysis.
Samples are digested in a block digestor with sulfuric acid and copper
sulfate as a catalyst. The digested sample is injected onto the FIA
manifold, where its pH is controlled by raising it to a known, basic pH
by neutralization with a concentrated buffer. This in-line
neutralization converts the ammonium cation to ammonia, and also
prevents undue influence of the sulfuric acid matrix on the pH-
sensitive color reaction that follows. The ammonia thus produced is
heated with salicylate and hypochlorite to produce a blue color that is
proportional to the ammonia concentration. The color is intensified by
adding sodium nitroprusside. The presence of EDTA in the buffer
prevents the precipitation of calcium and magnesium. The resulting
peak's absorbance is measured at 660 nm. The peak area is proportional
to the concentration of total Kjeldahl nitrogen in the original sample.
The 2011 editorial revision currently is approved
[[Page 10733]]
in Table IB for determination of total Kjeldahl nitrogen.
22. 4500-NH3 Nitrogen (Ammonia as nitrogen) Series.
a. 4500-NH3 B-2021, Preliminary Manual Distillation Step. The
sample is buffered at pH 9.5 with a borate buffer to decrease
hydrolysis of cyanates and organic nitrogen compounds. It is distilled
into a solution of boric acid when titration is to be used, or into
H2SO4, when the phenate method is used as the
determinative step. The ammonia in the distillate can be determined
either colorimetrically by the phenate method or titrimetrically with
standard H2SO4 and a mixed indicator or a pH
meter. Ammonia in the distillate also can be determined by the ammonia-
selective electrode method, using 0.04 N H2SO4 to
trap the ammonia. This revision replaces instructions for storage of
ammonia-free water with instructions for preparation of ammonia-free
water using an ion exchange resin and simply says that if high blank
values are produced, the analyst should prepare fresh ammonia-free
water. The 2011 editorial revision currently is approved in Table IB
for preliminary treatment of samples to be used for determination of
ammonia.
b. 4500-NH3 C-2021, Titration Method. The titrimetric method is
used only on samples that have been carried through preliminary
distillation. Ammonia is titrated with a standardized sulfuric acid
titrant using a mixed indicator of methyl red and methylene blue. The
2011 editorial revision currently is approved in Table IB for
determination of ammonia as well as for determination of total Kjeldahl
nitrogen after appropriate digestion/distillation of the sample.
c. 4500-NH3 D-2021, Electrode Method. The ammonia-selective
electrode uses a hydrophobic gas-permeable membrane to separate the
sample solution from an electrode internal solution of ammonium
chloride. Dissolved ammonia (NH3(aq) and
NH4+) is converted to NH3(aq) by
raising the pH to above 11 with a strong base. NH3(aq)
diffuses through the membrane and changes the internal solution pH that
is sensed by a pH electrode. The fixed level of chloride in the
internal solution is sensed by a chloride ion-selective electrode that
serves as the reference electrode of the sample. Potentiometric
measurements are made with a pH meter having an expanded millivolt
scale or with a specific ion meter. The 2011 editorial revision
currently is approved in Table IB for determination of ammonia, as well
as for determination of total Kjeldahl nitrogen after appropriate
digestion/distillation of the sample.
d. 4500-NH3 E-2021, Electrode Method. Ammonia is determined using
an ammonia-selective electrode. When a linear relationship exists
between concentration and response, known addition is convenient for
measuring occasional samples because no calibration is needed. Because
an accurate measurement requires that the concentration at least double
as a result of the addition, sample concentration must be known within
a factor of three. The total concentration of ammonia can be measured
in the absence of complexing agents down to 0.8 mg/L NH3-N
or in the presence of a large excess (50 to 100 times) of complexing
agent. The 2011 editorial revision currently is approved in Table IB
for determination of ammonia, as well as for determination of total
Kjeldahl nitrogen after appropriate digestion/distillation of the
sample.
e. 4500-NH3 F-2021, Phenate Method. An intensely blue compound,
indophenol, is formed by the reaction of ammonia, hypochlorite, and
phenol catalyzed by sodium nitroprusside. The color is measured
spectrophotometrically at 640 nm. The 2011 editorial revision currently
is approved in Table IB for determination of ammonia, as well as for
determination of total Kjeldahl nitrogen after appropriate digestion/
distillation of the sample.
f. 4500-NH3 G-2021, Semi-Automated Phenate Method. Alkaline phenol
and hypochlorite react with ammonia to form indophenol blue that is
proportional to the ammonia concentration. The blue color formed is
intensified with sodium nitroprusside. The color is measured
spectrophotometrically at 630 to 660 nm. The 2011 editorial revision
currently is approved in Table IB for determination of ammonia, as well
as for determination of total Kjeldahl nitrogen after appropriate
digestion/distillation of the sample.
g. 4500-NH3 H-2021, Semi-Automated Phenate Method. A water sample
containing ammonia or ammonium cation is injected into an FIA carrier
stream to which a complexing buffer (alkaline phenol) and hypochlorite
are added. This reaction, the Berthelot reaction, produces the blue
indophenol dye. The blue color is intensified by the addition of
nitroferricyanide. The resulting peak's absorbance is measured at 630
nm. The peak area is proportional to the concentration of ammonia in
the original sample. The 2011 editorial revision currently is approved
in Table IB for determination of ammonia, as well as for determination
of total Kjeldahl nitrogen after appropriate digestion/distillation of
the sample.
23. 4500-NO2- Nitrite as Nitrogen. 4500-NO2-
B-2021, Spectrophotometric Method. Nitrite (NO2-)
in a sample is determined through formation of a reddish-purple azo dye
produced at pH 2.0 to 2.5 by coupling diazotized sulfanilamide with N-
(1-naphthyl)-ethylenediamine dihydrochloride (NED) and absorbance is
measured spectrophotometrically at 543 nm. The 2011 editorial revision
currently is approved in Table IB for determination of nitrite.
24. 4500-NO3- Nitrogen (Nitrite/Nitrate as Nitrogen Series).
a. 4500-NO3- D-2019, Nitrate Electrode Method. Nitrate is measured
using an ion-selective electrode that develops a potential across a
thin, inert membrane holding in place a water-immiscible liquid ion
exchanger. The 2016 version of the method currently is approved in
Table IB for determination of nitrate.
b. 4500-NO3- E-2019, Cadmium Reduction Method. Nitrate
(NO3-) is reduced almost quantitatively to
nitrite (NO2-) in the presence of cadmium (Cd).
This method uses commercially available Cd granules treated with copper
sulfate (CuSO4) and packed in a glass column. The
NO2- is then diazotized with sulfanilamide and
coupled with NED to form a highly colored azo dye that is measured
spectrophotometrically. To correct for any NO2-
present in the sample before NO3- reduction,
samples also must be analyzed without the reduction step. The 2016
version of the method currently is approved in Table IB for
determination of nitrate (by subtraction), as well as for determination
of combined nitrate + nitrite, and for determination of nitrite singly
when bypassing the reduction step.
c. 4500-NO3- F-2019, Automated Cadmium Reduction Method. This is an
automated version of the cadmium reduction method 4500
NO3- E. Nitrate in a sample is reduced to nitrite
using cadmium reduction and then diazotized with sulfanilamide and
coupled with NED to form a highly colored azo dye that is measured
spectrophotometrically. To correct for any NO2-
present in the sample before NO3- reduction,
samples also must be analyzed without the reduction step. The 2016
version of the method currently is approved in Table IB for
determination of nitrate (by subtraction), as well as for determination
of combined nitrate +
[[Page 10734]]
nitrite, and for determination of nitrite singly when bypassing the
reduction step.
d. 4500-NO3- H-2019, Automated Hydrazine Reduction Method. Nitrate
in a sample is reduced to nitrite using hydrazine sulfate then
diazotized with sulfanilamide and coupled with NED to form a highly
colored azo dye that is measured spectrophotometrically. The 2016
version of the method currently is approved in Table IB for
determination of combined nitrate and nitrite.
e. 4500-NO3- I-2019, Cadmium Reduction Flow Injection Method. A
sample is passed through a copperized cadmium column to quantitatively
reduce its nitrate content to nitrite. The nitrite is diazotized with
sulfanilamide and coupled with NED to yield a water-soluble dye with a
magenta color whose absorbance at 540 nm is proportional to the nitrate
+ nitrite in the sample. Nitrite concentrations may be determined by
bypassing the cadmium column and nitrate concentration may be
calculated by subtraction of the result for the nitrite concentration
from the result for the combined nitrate + nitrite concentration. The
2016 version of the method currently is approved in Table IB for
determination of nitrate, as well as for determination of combined
nitrate + nitrite, and for determination of nitrite singly by bypassing
the reduction step.
25. 4500-O Oxygen (Dissolved) Series.
a. 4500-O B-2021, Iodometric Methods. A divalent manganese solution
is added and then a strong alkali is added to a sample in a glass-
stoppered bottle and dissolved oxygen (DO) rapidly oxidizes an
equivalent amount of the dispersed divalent manganous hydroxide
precipitate into higher-valency hydroxides. Oxidized manganese reverts
to the divalent state in the presence of iodide ions in an acidic
solution, liberating an amount of iodine equivalent to the original DO
content. The iodine is then titrated with a standard thiosulfate
solution. The 2016 version of the method currently is approved in Table
IB for determination of dissolved oxygen.
b. 4500-O C-2021, Azide Modification. The sample is treated with
manganous sulfate, potassium hydroxide, and potassium iodide (the
latter two reagents combined in one solution) and finally sulfuric
acid. The initial precipitate of manganous hydroxide,
Mn(OH)2, combines with the dissolved oxygen in the sample to
form a brown precipitate, manganic hydroxide, MnO(OH)2. Upon
acidification, the manganic hydroxide forms manganic sulfate, which
acts as an oxidizing agent to release free iodine from the potassium
iodide. The iodine, which is stoichiometrically equivalent to the
dissolved oxygen in the sample, is then titrated with sodium
thiosulfate or phenylarsine oxide (PAO). The azide modification
effectively removes nitrite interference, which is the most common
interference in biologically treated effluents and incubated
biochemical oxygen demand (BOD) samples. The 2016 version of the method
currently is approved in Table IB for determination of dissolved
oxygen.
c. 4500-O D-2021, Permanganate Modification. The permanganate
modification is used only on samples containing Fe(II) (e.g., acid mine
water). Concentrated sulfuric acid, potassium permanganate in solution
and potassium fluoride in solution are added to the sample. Enough
KMnO4 solution is added to obtain a violet tinge that
persists for 5 minutes. 0.5 to 1.0 mL potassium oxalate solution is
then added only until permanganate color is removed completely. From
this point, the procedure closely parallels that in 4500-O C. The 2016
version of the method currently is approved in Table IB for
determination of dissolved oxygen.
d. 4500-O E-2021, Alum Flocculation Modification. Samples high in
suspended solids may consume appreciable quantities of iodine in acid
solution. The interference due to solids may be removed by alum
flocculation. Concentrated ammonium hydroxide and aluminum potassium
sulfate solution are added to a sample. The sample is allowed to settle
for about 10 min and the clear supernatant is siphoned into a 250- to
300-mL DO bottle until it overflows. From this point, the procedure
closely parallels that in 4500-O C. The 2016 version of the method
currently is approved in Table IB for determination of dissolved
oxygen.
e. 4500-O F-2021, Copper Sulfate-Sulfamic Acid Flocculation
Modification. This modification is used for biological flocs (e.g.,
activated sludge mixtures), which have high oxygen utilization rates. A
copper sulfate-sulfamic acid inhibitor solution is added to the sample.
The suspended solids are allowed to settle, and the relatively clear
supernatant liquor is siphoned into a 250- to 300-mL DO bottle. From
this point, the procedure closely parallels that in 4500-O C. The 2016
version of the method currently is approved in Table IB for
determination of dissolved oxygen.
f. 4500-O G-2021, Electrode Method. Oxygen-sensitive polarographic
or galvanic membrane electrodes are composed of two solid metal
electrodes in contact with supporting electrolyte separated from the
test solution by a selective membrane. Polyethylene and fluorocarbon
membranes are commonly used because they are permeable to molecular
oxygen and are relatively rugged. The diffusion current is linearly
proportional to the molecular-oxygen concentration. The measured
current can be converted easily to concentration units (e.g., mg/L) by
a number of calibration procedures. The 2016 version of the method
currently is approved in Table IB for determination of dissolved
oxygen.
g. 4500-O H-2021, Luminescence-based Method. The optical probe uses
luminescence-based oxygen sensors to measure the light-emission
characteristics of a luminescent reaction; oxygen quantitatively
quenches the luminescence. The change in the luminescence signal's
lifetime correlates to the DO concentration. The 2016 version of the
method currently is approved in Table IB for determination of dissolved
oxygen.
26. 4500-P Phosphorus Total and Ortho Phosphorus Series.
a. 4500-P B-2021, Digestion Sample Preparation. Because phosphorus
may occur in combination with organic matter, a digestion method to
determine total phosphorus must be able to oxidize organic matter
effectively to release phosphorus as orthophosphate. Three digestion
methods are given in 4500-P B.3, 4, and 5. The perchloric acid method
in B.5 is the most vigorous and time-consuming method, and is
recommended for particularly difficult samples, such as sediments. The
nitric acid-sulfuric acid method is recommended for most samples. The
simplest digestion method that may be used for determination of total
phosphorus is the persulfate oxidation technique in which 50 mL of an
unfiltered sample is boiled with sulfuric acid and either ammonium
persulfate or potassium persulfate for approximately 30-40 minutes or
until a final volume of about 10 mL is reached. The 2011 editorial
revision is currently approved in Table IB for preliminary treatment of
samples to be used for determination of total phosphorus as
orthophosphorus using manual or automated versions of the ascorbic acid
reduction, colorimetric methods.
b. 4500-P E-2021, Manual Method. Ammonium molybdate and antimony
potassium tartrate react in an acid medium with orthophosphate to form
phosphomolybdic acid, a heteropoly acid that is reduced to intensely
colored molybdenum blue by ascorbic acid and is measured
spectrophotometrically. This revision adds that possible interference
from silicate should be
[[Page 10735]]
evaluated when reporting concentrations less than 10 [micro]g/L. The
2011 editorial revision currently is approved in Table IB for
determination of total phosphorus after digestion of the sample, as
well as for determination of orthophosphorus in a filtered, undigested
sample.
c. 4500-P F-2021, Automated Ascorbic Acid Reduction Method.
Ammonium molybdate and antimony potassium tartrate react with
orthophosphate in an acid medium to form an antimony-phosphomolybdate
complex, which on reduction with ascorbic acid yields an intense blue
color suitable for photometric measurement using continuous flow
analytical equipment. The 2011 editorial revision currently is approved
in Table IB for determination of total phosphorus after digestion of
the sample, as well as for determination of orthophosphorus in a
filtered, undigested sample.
d. 4500-P G-2021, Automated. Ammonium molybdate and antimony
potassium tartrate react with orthophosphate in an acid medium to form
an antimony-phosphomolybdate complex, which on reduction with ascorbic
acid yields an intense blue color suitable for photometric measurement
using flow injection analysis. The 2011 editorial revision currently is
approved in Table IB for determination of total phosphorus after
digestion of the sample as well, as for determination of
orthophosphorus in a filtered, undigested sample.
e. 4500-P H-2021, Automated Total Phosphorus. Samples are manually
digested using the approved procedure for preliminary treatment of
samples to be used for determination of total phosphorus. When the
resulting solution is injected onto the manifold, the orthophosphate
ion reacts with ammonium molybdate and antimony potassium tartrate
under acidic conditions to form a complex. This complex is reduced with
ascorbic acid to form a blue complex suitable for photometric
measurement using flow injection analysis. The 2011 editorial revision
currently is approved in Table IB for determination of total
phosphorus.
27. 4500-S2- Sulfide Series.
a. 4500-S2- B-2021, Sample Pretreatment. Dissolved
sulfide is measured by first removing insoluble matter. This is done by
adding sodium hydroxide and aluminum chloride solutions producing an
aluminum hydroxide floc that is settled, leaving a clear supernatant
for analysis. The 2011 editorial revision currently is approved in
Table IB for preliminary treatment of samples to be used for
determination of sulfide.
b. 4500-S2- C-2021, Sample Pretreatment. Interferences
due to sulfite, thiosulfate, iodide, and many other soluble substances,
but not ferrocyanide, are eliminated by first precipitating zinc
sulfide (ZnS) by addition of sodium hydroxide and zinc acetate
solutions, removing the supernatant, and replacing it with reagent
water. The same procedure is used even when not needed for removal of
interferences, to concentrate sulfide prior to analysis. The 2011
editorial revision currently is approved in Table IB for preliminary
treatment of samples to be used for determination of sulfide.
c. 4500-S2- D-2021, Colorimetric Method. The methylene
blue method is based on the reaction of sulfide, ferric chloride, and
dimethyl-p-phenylenediamine to produce methylene blue. Ammonium
phosphate is added after color development to remove ferric chloride
color, which is measured photometrically. The procedure is applicable
at sulfide concentrations between 0.1 and 20.0 mg/L. There are no other
procedural changes. The 2011 editorial revision currently is approved
in Table IB for determination of sulfide.
d. 4500-S2- F-2021, Titrimetric. Iodine oxidizes sulfide
in acid solution. A titration based on this reaction is an accurate
method for determining sulfide at concentrations above 1 mg/L if
interferences are absent and if loss of H2S is avoided. The
2011 editorial revision currently is approved in Table IB for
determination of sulfide.
e. 4500-S2- G-2021, Ion-Selective Electrode Method. The
potential of a sulfide ion-selective electrode (ISE) is related to the
sulfide ion activity. An alkaline antioxidant reagent (AAR) is added to
samples and standards to inhibit oxidation of sulfide by oxygen and to
provide a constant ionic strength and pH. Use of the AAR allows
calibration in terms of total dissolved sulfide concentration. All
samples and standards must be at the same temperature. Sulfide
concentrations between 0.032 mg/L and 100 mg/L can be measured without
preconcentration. For lower concentrations, preconcentration is
necessary. The 2011 editorial revision currently is approved in Table
IB for determination of sulfide.
28. 4500-SiO2 Silica Series.
a. 4500-SiO2 C-2021, Colorimetric Method. Ammonium molybdate at pH
approximately 1.2 reacts with silica and any phosphate present to
produce heteropoly acids. Oxalic acid is added to destroy the
molybdophosphoric acid, but not the molybdosilicic acid. Even if
phosphate is known to be absent, the addition of oxalic acid is highly
desirable and is a mandatory step. The intensity of the yellow color
produced is proportional to the concentration of molybdate-reactive
silica and is measured photometrically. The 2011 editorial revision
currently is approved in Table IB for determination of silica.
b. 4500-SiO2 E-2021, Automated Method for Molybdate-Reactive
Silica. Ammonium molybdate at pH approximately 1.2 reacts with silica
and any phosphate present to produce heteropoly acids. Oxalic acid is
added to destroy the molybdophosphoric acid, but not the molybdosilicic
acid. The yellow molybdosilicic acid is reduced by means of amino
naphthol sulfonic acid to heteropoly blue. The blue color is more
intense than the yellow color of 4500-SiO2 C and provides
increased sensitivity. The 2011 editorial revision currently is
approved in Table IB for determination of silica.
c. 4500-SiO2 F-2021, Automated Method for Molybdate-Reactive
Silicate. Silicate reacts with molybdate under acidic conditions to
form yellow beta-molybdosilicic acid. This acid is subsequently reduced
with stannous chloride to form a heteropoly blue complex that is
measured photometrically. Oxalic acid is added to reduce the
interference from phosphate. The 2011 editorial revision currently is
approved in Table IB for determination of silica.
29. 4500-SO42-Sulfate Series.
a. 4500-SO42-C-2021, Gravimetric Method with Ignition of Residue.
Sulfate is precipitated in a hydrochloric acid (HCl) solution as barium
sulfate (BaSO4) by the addition of barium chloride
(BaCl2). The precipitation is carried out near the boiling
temperature, and after a period of digestion, the precipitate is
filtered, washed with water until free of Cl-, ignited at
800 [deg]C for an hour and weighed as BaSO4. The 2011
editorial revision currently is approved in Table IB for determination
of sulfate.
b. 4500-SO42-D-2021, Gravimetric Method with Drying of Residue.
Sulfate is precipitated in a hydrochloric acid (HCl) solution as barium
sulfate (BaSO4) by the addition of barium chloride
(BaCl2). The precipitation is carried out near the boiling
temperature, and after a period of digestion the precipitate is
filtered, washed with water until free of Cl-, dried to a
constant weight in an oven at 105 [deg]C or higher, and weighed as
BaSO4. The 2011 editorial revision currently is approved in
Table IB for determination of sulfate.
c. 4500-SO42-E-2021, Turbidimetric Method. Sulfate ion
(SO42-) is precipitated in an acetic acid medium
[[Page 10736]]
with barium chloride (BaCl2) to form barium sulfate
(BaSO4) crystals of uniform size. Light absorbance of the
BaSO4 suspension is measured by a photometer and the
SO42- concentration is determined by comparison
of the reading with a standard curve. The 2011 editorial revision
currently is approved in Table IB for determination of sulfate.
d. 4500-SO42-F-2021, Automated Colorimetric Method. Barium sulfate
is formed by the reaction of the SO42- with
barium chloride (BaCl2) at a low pH. At high pH, excess
barium reacts with methylthymol blue (MTB) to produce a blue chelate.
The uncomplexed methylthymol blue is gray. The intensity of gray
(uncomplexed methylthymol blue) is measured photometrically and is
proportional to concentration of sulfate. The 2011 editorial revision
currently is approved in Table IB for determination of sulfate.
e. 4500-SO42-G-2021, Automated Colorimetric Method. At pH 13.0,
barium forms a blue complex with MTB. The sample is injected into a
low, but known, concentration of sulfate. The sulfate from the sample
then reacts with the ethanolic barium-MTB solution and displaces the
MTB from the barium to give barium sulfate and uncomplexed MTB.
Uncomplexed MTB has a grayish color. The pH is raised with NaOH and the
gray color of the uncomplexed MTB is measured photometrically. The
intensity of the gray color is proportional to the sulfate
concentration. The 2011 editorial revision currently is approved in
Table IB for determination of sulfate.
30. Sulfite 4500-SO32-B-2021, Titrimetric Iodometric Method. An
acidified sample containing sulfite (SO32-) is
titrated with a standardized potassium iodide-iodate titrant. Free
iodine, liberated by the iodide-iodate reagent, reacts with
SO32-. The titration endpoint is signaled by the
blue color resulting from the first excess of iodine reacting with a
starch indicator. The 2011 editorial revision currently is approved in
Table IB for determination of sulfite.
31. 5520 Oil and Grease Series.
a. 5520 B-2021, Liquid-Liquid, Partition-Gravimetric Method.
Dissolved or emulsified oil and grease is extracted from water by
intimate contact with an extracting solvent (n-hexane). The extract is
dried over sodium sulfate. The solvent is then distilled from the
extract and the hexane extractable material is desiccated and weighed.
Some extractables, especially unsaturated fats and fatty acids, oxidize
readily; hence, special precautions regarding temperature and solvent
vapor displacement are included to minimize this effect. Organic
solvents shaken with some samples may form an emulsion that is very
difficult to break. This method includes a means for handling such
emulsions. Recovery of solvents is discussed. Solvent recovery can
reduce both vapor emissions to the atmosphere and costs. The 2011
editorial revision currently is approved in Table IB for determination
of oil and grease (hexane extractable material or HEM).
b. 5520 F-2021, Hydrocarbons. The oil and grease extracted by 5520
B is used for this test. When only hydrocarbons are of interest, this
procedure is introduced before final measurement. When hydrocarbons are
to be determined after total oil and grease has been measured,
redissolve the extracted oil and grease in n-hexane. Silica gel has the
ability to adsorb polar materials. The solution of extracted
hydrocarbons and fatty materials in n-hexane is mixed with silica gel,
and the fatty acids are removed selectively from solution. The solution
is filtered to remove the silica gel, the solvent is distilled, and the
silica gel treated hexane extractable material (SGT-HEM) is weighed.
The materials not eliminated by silica gel adsorption are designated
hydrocarbons by this test. The 2011 editorial revision currently is
approved in Table IB for determination of oil and grease (hexane
extractable material or HEM).
32. 5530 Phenols Series.
a. 5530 B-2021, Manual Distillation. Phenols, defined as hydroxy
derivatives of benzene and its condensed nuclei, may occur in domestic
and industrial wastewaters, natural waters, and potable water supplies.
Phenols are distilled from nonvolatile impurities. Because the
volatilization of phenols is gradual, the distillate volume must
ultimately equal that of the original sample. The 2010 version of the
method currently is approved in Table IB for preliminary treatment of
samples to be used for determination of phenols.
b. 5530 D-2021, Colorimetric Method. Steam-distillable phenolic
compounds react with 4-aminoantipyrine at pH 7.9 0.1 in
the presence of potassium ferricyanide to form a colored antipyrine
dye. This dye is kept in aqueous solution and the absorbance is
measured photometrically at 500 nm. The 2010 version of the method
currently is approved in Table IB for determination of phenol. Note
that for regulatory compliance monitoring required under the Clean
Water Act, the colorimetric reaction must be performed at a pH of 10.0
0.2 as stated in 40 CFR 136.3, Table IB, footnote 27.
33. 5540 Surfactants.
5540 C-2021. This colorimetric method comprises three successive
extractions from an acid aqueous medium containing excess methylene
blue into chloroform (CHCl3), followed by an aqueous
backwash and measurement of the blue color in the CHCl3 by
spectrophotometry at 652 nm. The method is applicable at methylene blue
active substances concentrations down to about 0.025 mg/L. The 2011
editorial revision currently is approved in Table IB for determination
of surfactants.
34. 6200 Volatile Organic Compounds Series.
a. In the 6200 B-2020, Purge and Trap Capillary-Column Gas
Chromatographic/Mass Spectrometric (GC/MS) Method, volatile organic
compounds are transferred efficiently from the aqueous to the gaseous
phase by bubbling an inert gas (e.g., helium) through a water sample
contained in a specially designed purging chamber at ambient
temperature. The vapor is swept through a sorbent trap that adsorbs the
analytes of interest. After purging is complete, the trap is heated and
back-flushed with the same inert gas to desorb the compounds onto a gas
chromatographic column. The gas chromatograph is temperature-programmed
to separate the compounds. The detector is a mass spectrometer. The
2011 editorial revision currently is approved in Table IC for
determination of benzene, bromodichloromethane, bromoform,
bromomethane, carbon tetrachloride, chlorobenzene, chloroethane,
chloroform, chloromethane, dibromochloromethane, 1,2-dichlorobenzene,
1,3-dichlorobenzene, 1,4-dichlorobenzene, dichlorodifluoromethane, 1,1-
dichloroethane, 1,2-dichloroethane, 1,1-dichloroethene, trans-1,2-
dichloroethene, 1,2-dichloropropane, cis-1,3-dichloropropene, trans-
1,3-dichloropropene, ethylbenzene, methylene chloride, 1,1,2,2-
tetrachloroethane, tetrachloroethene, toluene, 1,1,1-trichloroethane,
1,1,2-trichloroethane, trichloroethene, trichlorofluoromethane, and
vinyl chloride.
b. 6200 C-2020, Purge and Trap Capillary-Column Gas Chromatographic
(GC) Method. Volatile organic compounds are transferred efficiently
from the aqueous to the gaseous phase by bubbling an inert gas (e.g.,
helium) through a water sample contained in a specially designed
purging chamber at ambient temperature. The vapor is swept through a
sorbent trap that adsorbs the analytes of interest. After
[[Page 10737]]
purging is complete, the trap is heated and back-flushed with the same
inert gas to desorb the compounds onto a gas chromatographic column.
The gas chromatograph is temperature-programmed to separate the
compounds and detected using a photoionization detection and an
electrolytic conductivity detection in series. The 2011 editorial
revision currently is approved in Table IC for determination of
benzene, bromodichloromethane, bromoform, bromomethane, carbon
tetrachloride, chlorobenzene, chloroethane, chloroform, chloromethane,
dibromochloromethane, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-
dichlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, 1,1-
dichloroethene, trans-1,2-dichloroethene, 1,2-dichloropropane, cis-1,3-
dichloropropene, trans-1,3-dichloropropene, ethylbenzene, methylene
chloride, 1,1,2,2-tetrachloroethane, tetrachloroethene, toluene, 1,1,1-
trichloroethane, 1,1,2-trichloroethane, trichloroethene,
trichlorofluoromethane, and vinyl chloride.
35. 6410 Extractable Base/Neutrals and Acids.
6410 B-2020, Liquid-Liquid Extraction Gas Chromatographic/Mass
Spectrometric Method. This method is applicable to the determination of
organic compounds that are partitioned into an organic solvent and are
amenable to gas chromatography in municipal and industrial discharges.
A measured volume of sample is extracted serially with methylene
chloride at a pH of approximately 2 and again at pH 11. The extract is
dried, concentrated, and analyzed by GC/MS. Qualitative compound
identification is based on retention time and relative abundance of
three characteristic masses (m/z). Quantitative analysis uses internal-
standard techniques with a single characteristic m/z. This revision
adds a note that although the method was validated extracting base
neutrals first and then acids, performance may be improved by
extracting acids first and then base neutrals. In addition, EPA
proposes to approve method 6410-B for endrin aldehyde in Table ID. This
parameter was inadvertently left off the 2000 MUR rulemaking. The 2000
version of the method currently is approved in Table IC for
determination of acenaphthene, acenaphthylene, anthracene, benzidine,
benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene,
benzo(g,h,i)perylene, benzo(k)fluoranthene, butyl benzyl phthalate,
bis(2-chloroethoxy) methane, bis(2-chloroethyl) ether, bis(2-
ethylhexyl) phthalate, bromodichloromethane, 4-bromophenyl phenyl
ether, 4-chloro-3-methyl phenol, 2-chloronaphthalene, 2-chlorophenol,
4-chlorophenyl phenyl ether, chrysene, dibenzo(a,h)anthracene, 3,3'-
dichlorobenzidine, 2,4-dichlorophenol, diethyl phthalate, 2,4-
dimethylphenol, dimethyl phthalate, di-n-butyl phthalate, di-n-octyl
phthalate, 2,4-dinitrophenol, 2,4-dinitrotoluene, 2,6-dinitrotoluene,
fluoranthene, fluorene, hexachlorobenzene, hexachlorobutadiene,
hexachlorocyclopentadiene, indeno(1,2,3-c,d) pyrene, isophorone, 2-
methyl-4,6-dinitrophenol, naphthalene, nitrobenzene, 2-nitrophenol, 4-
nitrophenol, n-nitrosodi-n-propylamine, n-nitrosodiphenylamine, PCB-
1016, PCB-1221, PCB-1232, PCB-1242, PCB-1248, PCB-1254, PCB-1260,
pentachlorophenol, phenanthrene, phenol, pyrene, 1,2,4-
trichlorobenzene, and 2,4,6-trichlorophenol and in Table ID for
determination of aldrin, [alpha]-BHC, [beta]-BHC, [delta]-BHC, [gamma]-
BHC (lindane), chlordane, 4,4'-DDD, 4,4'-DDE, 4,4'-DDT, dieldrin,
endosulfan I, endosulfan II, endosulfan sulfate, endrin, heptachlor,
heptachlor epoxide, and toxaphene.
36. 6420 Phenols.
6420 B-2020, Liquid-Liquid Extraction Gas Chromatographic Method. A
measured volume of sample is acidified and extracted with methylene
chloride. The extract is dried and exchanged to 2-propanol during
concentration. Target analytes in the extract are separated by gas
chromatography and are identified by retention time and measured with a
flame ionization detector, or derivatized and measured with an electron
capture detector. This revision of the method replaces distilled,
deionized water with reagent water, adds that the packed columns used
for validation of the method are no longer available or recommended,
and includes information on alternative capillary columns that may be
used. The 2000 version of the method currently is approved in Table IC
for determination of 4-chloro-3-methylphenol, 2-chlorophenol, 2,4-
dichlorophenol, 2,4-dimethylphenol, 2,4-dinitrophenol, 2-methyl-4,6-
dinitrophenol, 2-nitrophenol, 4-nitrophenol, pentachlorophenol, phenol,
and 2,4,6-trichlorophenol.
37. 6440 Polynuclear Aromatic Hydrocarbons.
6440 B-2021, Liquid-Liquid Extraction Chromatographic Method. A
measured volume of sample is extracted with methylene chloride. The
extract is dried, concentrated, and separated by the high-performance
liquid chromatographic (HPLC) or gas chromatographic (GC) method.
Ultraviolet (UV) and fluorescence detectors are used with HPLC to
identify and measure the polynuclear aromatic hydrocarbons. A flame
ionization detector is used with GC. The 2005 version of the method
currently is approved in Table IC for determination of acenaphthene,
acenaphthylene, anthracene, benzo(a)anthracene, benzo(a)pyrene,
benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene,
chrysene, dibenzo(a,h)anthracene, fluoranthene, fluorene, indeno(1,2,3-
c,d)pyrene, naphthalene, phenanthrene, and pyrene.
38. 6630 Organochlorine Pesticides Series.
a. 6630 B-2021, Liquid-Liquid Extraction Gas Chromatographic Method
I, in this procedure, the pesticides are extracted with a mixed
solvent, diethyl ether-hexane or methylene chloride-hexane, by either
liquid-liquid extraction using a separatory funnel or by continuous
liquid-liquid extraction. The extract is concentrated by evaporation
and, if necessary, is cleaned up by column adsorption chromatography.
The individual pesticides then are separated by gas chromatography and
the compounds are measured with an electron capture detector (ECD).
This revision of the method adds information regarding alternative
capillary columns that may be used in place of the packed columns that
were used for validation of the method, removes information regarding
preparation of packed columns, replaces information regarding manual
injection technique with use of an autosampler and states that gas
chromatography/mass spectrometry (GC/MS) may be used for confirmatory
analyses in place of a second column and ECD detection. There are no
other procedural changes. The 2007 version of the method currently is
approved in Table ID for determination of aldrin, [alpha]-BHC, [beta]-
BHC, [delta]-BHC, [gamma]-BHC (lindane), captan, carbophenothion,
chlordane, 4,4'-DDD, 4,4'-DDE, 4,4'-DDT, dichloran, dieldrin,
endosulfan I, endosulfan II, endrin, heptachlor, heptachlor epoxide,
isodrin, malathion, methoxychlor, mirex, parathion methyl, parathion
ethyl, PCNB, strobane, toxaphene, and trifluralin.
b. In 6630 C-2021, Liquid-Liquid Extraction Gas Chromatographic
Method II, a measured volume of sample is extracted with methylene
chloride either by liquid-liquid extraction using separatory funnels or
by continuous liquid-liquid extraction. The extract is dried and
exchanged to
[[Page 10738]]
hexane during concentration. The target analytes are separated by gas
chromatography and the compounds are measured with an electron capture
detector (ECD). This revision of the method adds information regarding
alternative capillary columns that may be used in place of the packed
columns that were used for validation of the method, and states that
gas chromatography/mass spectrometry (GC/MS) may be used for
confirmatory analyses in place of a second column and ECD detection.
There are no other procedural changes. The 2007 version of the method
currently is approved in Table ID for determination of aldrin, [alpha]-
BHC, [beta]-BHC, [delta]-BHC, [gamma]-BHC (lindane), chlordane, 4,4'-
DDD, 4,4'-DDE, 4,4'-DDT, dieldrin, endosulfan I, endosulfan II,
endosulfan sulfate, endrin, endrin aldehyde, heptachlor, heptachlor
epoxide, isodrin, methoxychlor, mirex, PCNB, strobane, and toxaphene.
39. 6640 Acidic Herbicide Compounds.
6640 B-2021, Micro Liquid-Liquid Extraction Gas Chromatographic
Method. A 40-mL sample is adjusted to pH >=12 with 4 N sodium hydroxide
and is kept for 1 hour at room temperature to hydrolyze derivatives.
Because the chlorphenoxy acid herbicides are formulated as a variety of
esters and salts, the hydrolysis step is required and may not be
skipped. The aqueous sample then is acidified with sulfuric acid to pH
<=1 and extracted with 4 mL of methyl tert-butyl ether (MtBE) that
contains the internal standard. The chlorinated acids, which have been
partitioned into the MtBE, then are converted to methyl esters by
derivatization with diazomethane. The target esters are separated and
detected by capillary column gas chromatography using an electron
capture detector (GC/ECD). Analytes are quantified using an internal-
standard-based calibration curve. The 2006 editorial revision currently
is approved in Table IC for determination of 2,4-D, 2,4,5-T, and 2,4,5-
TP (Silvex).
D. Changes to 40 CFR 136.3 To Include Alternate Test Procedures in
Table IC
To promote method innovation, EPA maintains a program that allows
method developers to apply for EPA review and potential approval of an
alternative method to an existing approved method. This alternate test
procedure (ATP) program is described for CWA applications at 40 CFR
136.4 and 136.5. EPA is proposing two ATPs for nationwide use. Based on
EPA's review, the performance of these ATPs is equally effective as
other methods already approved for measurement of 2,3,7,8-substituted
tetra- through octa-chlorinated dibenzo-p-dioxins and dibenzofurans
(PCDDs/PCDFs) in wastewater. The ATP applicants supplied EPA with study
reports that contain the data from their validation studies. These
study reports, the final methods, and the letters documenting EPA's
review are included as supporting documents in the docket for this
proposed rule.
These proposed new methods are: SGS AXYS Method ATM 16130,
``Determination of 2,3,7,8-Substituted Tetra- through Octa-Chlorinated
Dibenzo-p-Dioxins and Dibenzofurans (CDDs/CDFs) Using Waters and
Agilent Gas Chromatography-Tandem-Mass Spectrometry (GC/MS/MS),
Revision 1.0 and Pace Analytical Method PAM-16130-SSI, ``Determination
of 2,3,7,8-Substituted Tetra- through Octa-Chlorinated Dibenzo-p-
Dioxins and Dibenzofurans (CDDs/CDFs) Using Shimadzu Gas Chromatography
Mass Spectrometry (GC-MS/MS), Revision 1.1.'' These ATPs are the
results of separate collaborative efforts between SGS AXYS Analytical
Services Ltd, and the instrument manufacturers Waters Corporation,
Agilent Technologies, and between Pace Analytical Services LLC and the
instrument manufacturer Shimadzu Scientific Instruments, Inc. These
final methods are heavily adapted from Method 1613B. Neither ATP makes
changes to the extraction or cleanup procedures specified in Method
1613B. All required quality control tests (or analogous tests) and
associated QC acceptance criteria have been included in both SGS AXYS
16130 and PAM-16130-SSI.
To minimize costs to both the applicants and the Agency where
possible, SGS AXYS, Pace Analytical, and the instrument manufacturers
who collaborated on these methods worked closely with EPA's CWA ATP
Coordinator to design single-laboratory validation studies for these
methods. The goal of these validation studies was to demonstrate that
all of the performance criteria specified in Method 1613B could be met
and that comparable performance could be achieved when using GC-MS/MS
instrumentation for determination of PCDDs/PCDFs in extracts from real-
world samples.
EPA Method 1613B was promulgated at 40 CFR 136 in 1995 and remains
the only approved method for dioxins and furans at NPDES permit levels
(Methods 613 and 625.1 may only be used for screening). Method 1613B is
also the only method approved at 40 CFR part 136 that relies on gas
chromatography-high resolution mass spectrometry (GC/HRMS) as the
determinative technique. As a result, the need for GC/HRMS instruments
is somewhat limited, and market forces have led some instrument vendors
to move away from supporting new GC/HRMS instrumentation. In addition,
in the last 30 years, there has been substantial consolidation of
manufacturers, with the disappearance of many of the vendors whose
instruments were used to develop and validate Method 1613B.
In these two methods, referred to in the rule as ATM 16130 and PAM
16130-SSI, each sample is spiked with the same suite of carbon-13
labeled standards prior to extraction and those standards are used for
isotope dilution quantitation in the same way as is done in EPA Method
1613B. All of the relevant QC acceptance criteria are the same in the
methods as well. The difference between these methods and the approved
EPA method is the use of an MS/MS detector system that uses Multiple
Reaction Monitoring (MRM) in place of a high resolution mass
spectrometer (HRMS) detector system. The GC portions of the methods did
not change.
E. Corrections or Amendments to the Text and Tables of 40 CFR Part 136
In addition to the method revisions discussed in Section II.C of
this preamble, Standard Methods has revised certain of their general
quality control sections (2020, 3020, 4020 and 5020). EPA is proposing
to update the year of the current references to these sections in 136.3
Table IB footnote 85, as well as add a reference to an additional
Standard Methods Quality Control Section: Part 6000 Individual Organic
Compounds, 6020, based on EPA's review of these sections. These Quality
Control Standards are available for download at www.standardmethods.org
at no charge. Further, during the preparation of this proposed
rulemaking, EPA identified several minor errors or inconsistencies in
the tables of approved methods. Therefore, EPA is proposing the
following changes to 40 CFR 136.3, Tables IA, IB, IC or ID:
1. Table IA. Removing the units of ``number per 100 mL'' under
parameter 1. Coliform (fecal), because parameter 1 is specifically for
biosolids that are reported as ``number per gram dry weight''.
2. Table IA. Moving USGS Method ``B-0050-85'' from parameter 1.
Coliform (fecal) number per gram dry weight to parameter 2. Coliform
(fecal) number per 100 mL, to address an error from the previous
rulemaking when Parameter 1 Coliform (fecal) was split
[[Page 10739]]
into two parameters to eliminate confusion as to which methods were
approved for biosolids.
3. Table IA. Moving the phrase ``two-step'' in parameter 3, in the
``Method'' column from the second to the third line which returns the
phrase to the proper line after having been inadvertently moved.
4. Table IB. Revising footnote 85 to remove bullet formatting.
5. Table IB. EPA proposes adding footnote 86 to Method 419D, listed
as an approved method for determination nitrate using Colorimetric
(Brucine sulfate) methodology. This addition corrects a long-standing
typographical error regarding the appropriate footnote for this method
in Table IB.
6. Table IB. Correcting an inadvertent error to footnote 57. The
reference number was incorrectly changed to 335.4-1. The correct number
is 335.4.
7. Tables IC and ID. Proposes adding footnote 15 to the Standard
Method Column header and adding footnote 15 to refer to Quality Control
Section: Part 6000 Individual Organic Compounds, 6020 (2019).
8. Table IC. The parameter 39, dichlorodifluoromethane, should
refer to Method 6200 B rather than 6200 C for the GC/MS method.
9. Table IC. Parameters 66-72, 95, 96 and 97. These parameters are
missing the footnote 10 that was inadvertently dropped in an earlier
rulemaking. Footnote 10 to table IC applies to all of the 17 dioxin and
furan congeners.
10. Table IH. Parameter 2 has method B-0025-85 is moved down one
row because it was inadvertently moved. This method is a one-step
membrane filtration (MF) method rather than a most probable number
(MPN) method.
11. Footnote 5 to Table II for the preservation and holding time
requirements for cyanide to add the year (2015) of the ASTM method
D7365-09a (15). This practice is applicable for the collection and
preservation of water samples for the analysis of cyanide. Samples are
collected in appropriate containers and mitigated for known
interferences either in the field during sample collection or in the
laboratory prior to analysis. The sampling, preservation and mitigation
of interference procedures described in this practice are recommended
for the analysis of total cyanide, available cyanide, weak acid
dissociable cyanide, and free cyanide by ASTM Methods D2036, D4282,
D4374, D6888, D6994, D7237, D7284, and D7511.
The recommended sampling and preservation procedures in the ASTM
method have not changed since 2009, but the change to footnote 5 will
simplify identification of the current method that is available from
ASTM International. The 2015 reapproval date was already updated in
footnote 6 to Table II in the 2021 methods update rule; however, adding
the reapproval date was overlooked in the IBR section and in footnote 5
to Table II.
F. Changes to 40 CFR 136.3 To Include New Standard Methods Committee
Methods Based on Previously Approved Technologies
EPA is proposing adding five new methods in furtherance of the
National Technology Transfer and Advancement Act of 1995 (NTTAA),
Public Law 104-113, that provides that Federal agencies and departments
shall use technical standards developed or adopted by the VCSBs if
compliance would not be inconsistent with applicable law or otherwise
impracticable. These methods were submitted by Standard Methods and are
consistent with other already approved methods. EPA is adding 4500-
CN- P-2021, 4500-CN- Q-2021, 4500 CN-
R-2021, 4500-F- G-2021 to Table IB for cyanide and fluoride
and is adding 5520 G-2021 to Table IB for oil and grease, based on the
following reasons:
1. Cyanide. Although method 4500-CN- P-2021, Total
Cyanide by Segmented Flow Injection, UV-Irradiation with Gas Diffusion,
and Amperometric Measurement is new to Standard Methods for the
Examination of Water and Wastewater, it is based on ASTM D7511-12(17),
which is approved in Table IB for determination of total cyanide and
relies on the same underlying chemistry and determinative technique to
determine total cyanide. Total cyanide consists of dissolved HCN,
sodium cyanide (NaCN), and various metal-cyanide complexes, which a
continuous flow analyzer converts to aqueous HCN by mixing it with
sulfuric acid, irradiating with UV light, and precipitating potentially
interfering sulfides with bismuth ion. The aqueous HCN is captured in a
donor stream that is passed across a hydrophobic gas-permeable
membrane, which selectively diffuses the gaseous HCN into a parallel
acceptor stream of dilute sodium hydroxide forming dissolved
CN-. The cyanide ion in this acceptor stream is measured
using an amperometric detector, where the cyanide ion dissolves the
silver electrode, resulting in a proportional current.
2. 4500-CN- Q-2021, Weak and Dissociable Cyanide by Flow Injection,
Gas Diffusion, and Amperometric Measurement. Weak and dissociable
cyanide consists of dissolved HCN, NaCN, and various metal-cyanide
complexes and includes the same forms of cyanide as those measured
using other methods approved in Table IB for determination of available
cyanide. Analysts pretreat for weak and dissociable cyanide by mixing a
sample with ligand reagents. They then inject the sample into a
sulfuric acid and bismuth nitrate solution to produce a donor stream
containing aqueous dissolved HCN and precipitated sulfide, if sulfide
is present. The donor stream is passed across a hydrophobic gas-
permeable membrane, which selectively diffuses gaseous HCN into a
parallel acceptor stream of dilute sodium hydroxide, forming dissolved
CN-. The cyanide ion in this acceptor stream is measured using an
amperometric detector, where the cyanide ion dissolves the silver
electrode, resulting in a proportional current. Although this method is
new to Standard Methods for the Examination of Water and Wastewater, it
is based on ASTM D6888-16, which is approved in Table IB for
determination of available cyanide and relies on the same underlying
chemistry and determinative technique to determine available cyanide.
3. 4500-CN- R-2021, Free Cyanide by Flow Injection, Gas Diffusion,
and Amperometric Measurement. Free cyanide (FCN) consists of dissolved
HCN, NaCN, and the soluble fraction of various metal-cyanide complexes.
To determine FCN, analysts pretreat a sample by mixing it with a
buffered solution in the pH range of 6 to 8 that simulates the
receiving water resulting in a donor stream containing aqueous
dissolved HCN in equilibrium with the cyanide anion. The donor stream
is passed across a hydrophobic gas-permeable membrane, which
selectively diffuses gaseous HCN into a parallel acceptor stream that
consists of dilute sodium hydroxide, forming dissolved CN-. The cyanide
ions in this acceptor stream are measured when it is passed through an
amperometric detector, where the cyanide ion dissolves the silver
electrode, resulting in a proportional current. Although this method is
new to Standard Methods for the Examination of Water and Wastewater, it
is based on ASTM D7237-15, which is approved in Table IB for
determination of free cyanide and relies on the same underlying
chemistry and determinative technique to determine free cyanide.
4. Fluoride. 4500-F- G-2021, Ion-Selective Electrode Flow Injection
Analysis is an automated version of method 4500-F- C and
relies on the same underlying chemistry and
[[Page 10740]]
determinative technique as USGS Method I-4237-85, which currently is
approved in Table IB for determination of fluoride. Fluoride is
determined potentiometrically by using a combination fluoride ion
selective electrode (ISE) in a flow cell. The fluoride electrode
consists of a lanthanum fluoride crystal across which a potential is
developed by fluoride ions.
5. Oil and Grease. In 5520 G-2021, Solid-Phase, Partition-
Gravimetric Method, dissolved or emulsified oil and grease is extracted
from water by passing a sample through a solid-phase extraction (SPE)
disk where the oil and grease are adsorbed by the disk and subsequently
eluted with n-hexane. SPE is a modification allowed under EPA Methods
1664 A and B and relies on the same underlying chemistry and
determinative technique as Methods 1664 A and B. Some extractables,
especially unsaturated fats and fatty acids, oxidize readily; hence,
special precautions regarding temperature and solvent vapor
displacement are provided. This method is not applicable to materials
that volatilize at temperatures below 85 [deg]C, or crude and heavy
fuel oils containing a significant percentage of material not soluble
in n-hexane. This method may be a satisfactory alternative to liquid-
liquid extraction techniques, especially for samples that tend to form
difficult emulsions during the extraction step.
IV. Incorporation by Reference
Currently, hundreds of methods and ATPs are incorporated by
reference within 40 CFR part 136. In most cases, 40 CFR part 136
contains multiple approved methods for a single parameter (or
pollutant) and regulated entities often have a choice in selecting a
method. The proposed rule contains revisions to VCSB methods that are
currently incorporated by reference (see Sections III.B, III.C, and
III.F of this preamble). Two VCSBs have made such revisions, Standard
Methods and ASTM. The proposed VCSB methods are consistent with the
requirements of the National Technology Transfer and Advancement Act
(NTTAA), under which Federal agencies use technical standards developed
or adopted by the VCSBs if compliance would not be inconsistent with
applicable law or otherwise impracticable (see Section V.I of this
preamble). The proposed copyrighted VCSB methods are available on their
respective websites (standardmethods.org and astm.org) to everyone at a
cost determined by the VCSB, generally from $60 to $80. Both
organizations also offer memberships or subscriptions that allow
unlimited access to their methods. The cost of obtaining these methods
is not a significant financial burden for a discharger or environmental
laboratory, making the methods reasonably available.
This proposal also includes two vendor ATPs (see Section III.D of
this preamble) and four revised EPA methods (see Section III.A of this
preamble) which EPA proposes to incorporate by reference. The ATPs and
EPA methods are available free of charge on their respective websites
(sgsaxys.com/wp-content/uploads/2022/09/SGS-AXYS-Method-16130-Rev-1.0.pdf, pacelabs.com and epa.gov/cwa-methods/approved-cwa-chemical-test-methods), therefore the ATPs and EPA methods incorporated by
reference are reasonably available.
V. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review Executive
Order 13563: Improving Regulation and Regulatory Review
This action is not a significant regulatory action and was
therefore not submitted to the Office of Management and Budget (OMB)
for review.
B. Paperwork Reduction Act
This action does not impose an information collection burden under
the Paperwork Reduction Act. This rule does not impose any information
collection, reporting, or recordkeeping requirements. This proposal
would merely add or revise CWA test procedures.
C. Regulatory Flexibility Act
The Agency certifies that this action would not have a significant
economic impact on a substantial number of small entities under the
Regulatory Flexibility Act. This action would not impose any
requirements on small entities. This action would approve new and
revised versions of CWA testing procedures. Generally, these changes
would have a positive impact on small entities by increasing method
flexibility, thereby allowing entities to reduce costs by choosing more
cost-effective methods. In general, EPA expects the proposed revisions
would lead to few, if any, increased costs. The proposed changes
clarify or improve the instructions in the method, update the
technology used in the method, improve the QC instructions, make
editorial corrections, or reflect the most recent approval year of an
already approved method. In some cases, the proposal would add
alternatives to currently approved methods for a particular analyte
(e.g., ASTM Method D7511). Because these methods would be alternatives
rather than requirements, there are no direct costs associated with
this proposal. EPA proposes methods that would be incorporated by
reference. If a permittee elected to use these methods, they could
incur a small cost associated with obtaining these methods from the
listed sources. See Section IV of this preamble.
D. Unfunded Mandates Reform Act
This action does not contain any unfunded mandate as described in
the Unfunded Mandates Reform Act, 2 U.S.C. 1531-1538, and does not
significantly or uniquely affect small governments. The action imposes
no enforceable duty on any state, local or tribal governments or the
private sector.
E. Executive Order 13132: Federalism
This proposed rule does not have federalism implications. It would
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.
F. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments
This proposed rule does not have tribal implications as specified
in Executive Order 13175. This rule would merely approve new and
revised versions of test procedures. EPA does not expect the proposal
would lead to any costs to any tribal governments, and if incurred, EPA
projects they would be minimal. Thus, Executive Order 13175 does not
apply to this action.
G. Executive Order 13045: Protection of Children From Environmental
Health Risks and Safety Risks
EPA interprets Executive Order 13045 as applying only to those
regulatory actions that concern environmental health or safety risks
that EPA has reason to believe may disproportionately affect children,
per the definition of ``covered regulatory action'' in section 2-202 of
the Executive Order. This action is not subject to Executive Order
13045 because it does not concern an environmental health risk or
safety risk.
H. Executive Order 13211: Actions That Significantly Affect Energy
Supply, Distribution, or Use
This action is not subject to Executive Order 13211 because it is
not a
[[Page 10741]]
significant regulatory action under Executive Order 12866.
I. National Technology Transfer and Advancement Act of 1995
This action involves technical standards. EPA proposes to approve
the use of technical standards developed and recommended by the
Standard Methods Committee and ASTM International for use in compliance
monitoring where EPA determined that those standards meet the needs of
CWA programs. As described above, this proposal is consistent with the
NTTAA.
J. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations
Executive Order 12898 (59 FR 7629, February 16, 1994) directs
Federal agencies, to the greatest extent practicable and permitted by
law, to make environmental justice part of their mission by identifying
and addressing, as appropriate, disproportionately high and adverse
human health or environmental effects of their programs, policies, and
activities on minority populations (people of color) and low-income
populations.
EPA believes that this type of action does not concern human health
or environmental conditions and therefore cannot be evaluated with
respect to potentially disproportionate and adverse effects on people
of color, low-income populations and/or indigenous peoples. This action
has no effect on human health or the environment because this action
would approve new and revised versions of CWA testing procedures. The
proposed changes clarify or improve the instructions in the method,
update the technology used in the method, improve the QC instructions,
make editorial corrections, or reflect the most recent approval year of
an already approved method. These proposed changes would provide
increased flexibility for the regulated community in meeting monitoring
requirements while improving data quality. In addition, this proposed
update to the CWA methods would incorporate technological advances in
analytical technology.
List of Subjects in 40 CFR Part 136
Environmental protection, Incorporation by reference, Reporting and
recordkeeping requirements, Test procedures, Water pollution control.
Michael S. Regan,
Administrator.
For the reasons set out in the preamble, the EPA proposes to amend
40 CFR part 136 as follows:
PART 136--GUIDELINES ESTABLISHING TEST PROCEDURES FOR THE ANALYSIS
OF POLLUTANTS
0
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).
0
2. Amend Sec. 136.3 as follows:
0
a. Revise tables IA, IB, IC, ID, and IH in paragraph (a);
0
b. Revise the introductory text to paragraph (b) and paragraphs
(b)(8)(ii) through (v), (b)(10)(i), (viii) through (xiv), (xvi) through
(xxvi), (xxviii) through (xxxv), (xxxvii), (xxxix) through (li), (lv)
through (lxiii), and (lxvii), (b)(15)(xi), (xx), (xxx), (xxxii), (lix),
(lxv) through (lxvii), and (lxix);
0
c. Redesignate paragraphs (b)(33) through (39) as paragraphs (b)(35)
through (41);
0
d. Add new paragraphs (b)(33) and (34); and
0
e. In paragraph (e), table II, revise Footnote ``5''.
The revisions and additions read as follows:
Sec. 136.3 Identification of test procedures.
* * * * *
Table IA--List of Approved Biological Methods for Wastewater and Sewage Sludge
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter and units Method \1\ EPA Standard methods AOAC, ASTM, USGS Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Bacteria
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Coliform (fecal), number per Most Probable p. 132; \3\ 1680; 9221 E-2014........
gram dry weight. Number (MPN), 5 \11\ \15\ 1681
tube, 3 dilution, \11\ \20\.
or
Membrane filter p. 124 \3\......... 9222 D-2015 \29\...
(MF),\2\ \5\
single step.
2. Coliform (fecal), number per MPN, 5 tube, 3 p. 132 \3\......... 9221 E-2014; 9221 F-
100 mL. dilution, or. 2014 \33\.
Multiple tube/ ................... ................... ........................ Colilert-18[supreg].\13\ \18\
multiple well, or. \28\
MF,\2\ \5\ single p. 124 \3\......... 9222 D-2015 \29\... B-0050-85 \4\...........
step \5\.
3. Coliform (total), number per MPN, 5 tube, 3 p. 114 \3\......... 9221 B-2014........
100 mL. dilution, or.
MF,\2\ \5\ single p. 108 \3\......... 9222 B-2015 \30\... B-0025-85 \4\...........
step or.
MF,\2\ \5\ two step p. 111 \3\......... 9222 B-2015 \30\...
with enrichment.
4. E. coli, number per 100 mL... MPN \6\ \8\ \16\ ................... 9221 B2014/9221 F-
multiple tube, or. 2014 \12\ \14\
\33\.
multiple tube/ ................... 9223 B-2016 \13\... 991.15 \10\............. Colilert[supreg].\13\ \18\
multiple well, or. Colilert-18[supreg].\13\ \17\
\18\
MF,\2\ \5\ \6\ \7\ ................... 9222 B-2015/9222 I-
\8\ two step, or. 2015 \31\.
Single step........ 1603.1 \21\........ ................... ........................ m-ColiBlue24[supreg].\19\
5. Fecal streptococci, number MPN, 5 tube, 3 p. 139 \3\......... 9230 B-2013........
per 100 mL. dilution, or.
MF,\2\ or.......... p. 136 \3\......... 9230 C-2013 \32\... B-0055-85 \4\...........
Plate count........ p. 143 \3\.........
6. Enterococci, number per 100 MPN, 5 tube, 3 p. 139 \3\......... 9230 B-2013........
mL. dilution, or.
[[Page 10742]]
MPN,\6\ \8\ ................... 9230 D-2013........ D6503-99 \9\............ Enterolert[supreg].\13\ \23\
multiple tube/
multiple well, or.
MF \2\ \5\ \6\ \7\ 1600.1 \24\........ 9230 C-2013 \32\...
\8\ single step or.
Plate count........ p. 143 \3\.........
7. Salmonella, number per gram MPN multiple tube.. 1682 \22\..........
dry weight \11\.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Aquatic Toxicity
--------------------------------------------------------------------------------------------------------------------------------------------------------
8. Toxicity, acute, fresh water Water flea, 2002.0 \25\........
organisms, LC50, percent Cladoceran,
effluent. Ceriodaphnia dubia
acute.
Water fleas, 2021.0 \25\........
Cladocerans,
Daphnia pulex and
Daphnia magna
acute.
Fish, Fathead 2000.0 \25\........
minnow, Pimephales
promelas, and
Bannerfin shiner,
Cyprinella leedsi,
acute.
Fish, Rainbow 2019.0 \25\........
trout,
Oncorhynchus
mykiss, and brook
trout, Salvelinus
fontinalis, acute.
9. Toxicity, acute, estuarine Mysid, Mysidopsis 2007.0 \25\.
and marine organisms of the bahia, acute. ...................
Atlantic Ocean and Gulf of Fish, Sheepshead 2004.0 \25\........
Mexico, LC50, percent effluent. minnow, Cyprinodon
variegatus, acute.
Fish, Silverside, 2006.0 \25\........
Menidia beryllina,
Menidia menidia,
and Menidia
peninsulae, acute.
10. Toxicity, chronic, fresh Fish, Fathead 1000.0 \26\........
water organisms, NOEC or IC25, minnow, Pimephales
percent effluent. promelas, larval
survival and
growth.
Fish, Fathead 1001.0 \26\........
minnow, Pimephales
promelas, embryo-
larval survival
and teratogenicity.
Water flea, 1002.0 \26\........
Cladoceran,
Ceriodaphnia
dubia, survival
and reproduction.
Green alga, 1003.0 \26\........
Selenastrum
capricornutum,
growth.
11. Toxicity, chronic, estuarine Fish, Sheepshead 1004.0 \27\........
and marine organisms of the minnow, Cyprinodon
Atlantic Ocean and Gulf of variegatus, larval
Mexico, NOEC or IC25, percent survival and
effluent. growth.
[[Page 10743]]
Fish, Sheepshead 1005.0 \27\........
minnow, Cyprinodon
variegatus, embryo-
larval survival
and teratogenicity.
Fish, Inland 1006.0 \27\........
silverside,
Menidia beryllina,
larval survival
and growth.
Mysid, Mysidopsis 1007.0 \27\........
bahia, survival,
growth, and
fecundity.
Sea urchin, Arbacia 1008.0 \27\........
punctulata,
fertilization.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IA notes:
\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\ Microbiological Methods for Monitoring the Environment, Water and Wastes, EPA/600/8-78/017. 1978. U.S. EPA.
\4\ 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. 1989. USGS.
\5\ 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.
\6\ 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.
\7\ When the MF method has been used previously to test waters with high turbidity, large numbers 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.
\8\ 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.
\9\ Annual Book of ASTM Standards-Water and Environmental Technology, Section 11.02. 2000, 1999, 1996. ASTM International.
\10\ Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998. AOAC International.
\11\ Recommended for enumeration of target organism in sewage sludge.
\12\ The multiple-tube fermentation test is used in 9221B.2-2014. 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.
\14\ After prior enrichment in a presumptive medium for total coliform using 9221B.2-2014, 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-2014. Commercially available EC-MUG media or EC media
supplemented in the laboratory with 50 [mu]g/mL of MUG may be used.
\15\ Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using Lauryl-Tryptose Broth (LTB) and EC Medium, EPA-821-R-
14-009. September 2014. U.S. EPA.
\16\ 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[supreg] may be enumerated with
the multiple-well procedures, Quanti-Tray[supreg] or Quanti-Tray[supreg]/2000 and the MPN calculated from the table provided by the manufacturer.
\17\ Colilert-18[supreg] is an optimized formulation of the Colilert[supreg] 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[supreg] test and is recommended for marine water samples.
\18\ Descriptions of the Colilert[supreg], Colilert-18[supreg], Quanti-Tray[supreg], and Quanti-Tray[supreg]/2000 may be obtained from IDEXX
Laboratories, Inc.
\19\ A description of the mColiBlue24[supreg] test is available from Hach Company.
\20\ Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using A-1 Medium, EPA-821-R-06-013. July 2006. U.S. EPA.
\21\ Method 1603.1: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified Membrane-Thermotolerant Escherichia coli Agar (modified
mTEC), [in draft as of 2023]. U.S. EPA.
\22\ Method 1682: Salmonella in Sewage Sludge (Biosolids) by Modified Semisolid Rappaport-Vassiliadis (MSRV) Medium, EPA-821-R-14-012. September 2014.
U.S. EPA.
\23\ A description of the Enterolert[supreg] test may be obtained from IDEXX Laboratories Inc.
\24\ Method 1600.1: Enterococci in Water by Membrane Filtration Using Membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI), [in draft as of
2023]. U.S. EPA.
\25\ Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms, EPA-821-R-02-012. Fifth Edition,
October 2002. U.S. EPA; and U.S. EPA Whole Effluent Toxicity Methods Errata Sheet, EPA 821-R-02-012-ES. December 2016.
\26\ Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms, EPA-821-R-02-013. Fourth Edition,
October 2002. U.S. EPA; and U.S. EPA Whole Effluent Toxicity Methods Errata Sheet, EPA 821-R-02-012-ES. December 2016.
\27\ Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms, EPA-821-R-02-014. Third
Edition, October 2002. U.S. EPA; and U.S. EPA Whole Effluent Toxicity Methods Errata Sheet, EPA 821-R-02-012-ES. December 2016.
\28\ To use Colilert-18[supreg] to assay for fecal coliforms, the incubation temperature is 44.5 0.2 [deg]C, and a water bath incubator is
used.
\29\ On a monthly basis, at least ten blue colonies from positive samples must be verified using Lauryl Tryptose Broth and EC broth, followed by count
adjustment based on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications
should be done from randomized sample sources.
\30\ On a monthly basis, at least ten sheen colonies from positive samples must be verified using lauryl tryptose broth and brilliant green lactose bile
broth, followed by count adjustment based on these results; and representative non-sheen colonies should be verified using lauryl tryptose broth.
Where possible, verifications should be done from randomized sample sources.
[[Page 10744]]
\31\ Subject coliform positive samples determined by 9222 B-2015 or other membrane filter procedure to 9222 I-2015 using NA-MUG media.
\32\ Verification of colonies by incubation of BHI agar at 10 0.5 [deg]C for 48 3 h is optional. As per the Errata to the 23rd
Edition of Standard Methods for the Examination of Water and Wastewater ``Growth on a BHI agar plate incubated at 10 0.5 [deg]C for 48
3 h is further verification that the colony belongs to the genus Enterococcus.''
\33\ 9221F. 2-2014 allows for simultaneous detection of E. coli and thermotolerant fecal coliforms by adding inverted vials to EC-MUG; the inverted
vials collect gas produced by thermotolerant fecal coliforms.
Table IB--List of Approved Inorganic Test Procedures
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter Methodology \58\ EPA \52\ Standard methods \84\ ASTM USGS/AOAC/other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acidity, as CaCO3, mg/L......... Electrometric endpoint ...................... 2310 B-2020.......... D1067-16............. I-1020-85.\2\
or phenolphthalein
endpoint.
2. Alkalinity, as CaCO3, mg/L...... Electrometric or ...................... 2320 B-2021.......... D1067-16............. 973.43,\3\ I-1030-
Colorimetric 85.\2\
titration to pH 4.5,
Manual.
Automatic............. 310.2 (Rev. 1974) \1\. ..................... ..................... I-2030-85.\2\
3. Aluminum--Total, \4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 D-2019 or 3111 E- ..................... I-3051-85.\2\
\36\. 2019.
AA furnace............ ...................... 3113 B-2020..........
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003),\68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
Direct Current Plasma ...................... ..................... D4190-15............. See footnote.\34\
(DCP) \36\.
Colorimetric ...................... 3500-Al B-2020.......
(Eriochrome cyanine
R).
4. Ammonia (as N), mg/L............ Manual distillation 350.1, Rev. 2.0 (1993) 4500-NH3 B-2021...... ..................... 973.49.\3\
\6\ or gas diffusion
(pH > 11), followed
by any of the
following:
Nesslerization........ ...................... ..................... D1426-15 (A)......... 973.49,\3\ I-3520-
85.\2\
Titration............. ...................... 4500-NH3 C-2021......
Electrode............. ...................... 4500-NH3 D-2021 or E- D1426-15 (B).........
2021.
Manual phenate, ...................... 4500-NH3 F-2021...... ..................... See footnote.\60\
salicylate, or other
substituted phenols
in Berthelot reaction-
based methods.
Automated phenate, 350.1,\30\ Rev. 2.0 4500-NH3 G-2021 4500- ..................... I-4523-85,\2\ I-2522-
salicylate, or other (1993). NH3 H-2021. 90.\80\
substituted phenols
in Berthelot reaction-
based methods.
Automated electrode... ...................... ..................... ..................... See footnote.\7\
Ion Chromatography.... ...................... ..................... D6919-17.............
Automated gas ...................... ..................... ..................... Timberline Ammonia-
diffusion, followed 001.\74\
by conductivity cell
analysis.
Automated gas ...................... ..................... ..................... FIAlab100.\82\
diffusion followed by
fluorescence detector
analysis.
5. Antimony--Total, \4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019..........
\36\.
AA furnace............ ...................... 3113 B-2020..........
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 (2003); 3120 B-2020.......... D1976-20.............
\68\ 200.7, Rev. 4.4
(1994).
[[Page 10745]]
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
6. Arsenic--Total,\4\ mg/L......... Digestion,\4\ followed 206.5 (Issued 1978)
by any of the \1\.
following:
AA gaseous hydride.... ...................... 3114 B-2020 or 3114 C- D2972-15 (B)......... I-3062-85.\2\
2020.
AA furnace............ ...................... 3113 B-2020.......... D2972-15 (C)......... I-4063-98.\49\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 (2003); 3120 B-2020.......... D1976-20.............
\68\ 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-
05.\70\
Colorimetric (SDDC)... ...................... 3500-As B-2020....... D2972-15 (A)......... I-3060-85.\2\
7. Barium--Total,\4\ mg/L.......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 D-2019.......... ..................... I-3084-85.\2\
\36\.
AA furnace............ ...................... 3113 B-2020.......... D4382-18.............
ICP/AES \36\.......... 200.5, Rev 4.2 (2003); 3120 B-2020.......... ..................... I-4471-97.\50\
\68\ 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
DCP \36\.............. ...................... ..................... ..................... See footnote.\34\
8. Beryllium--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 D-2019 or 3111 E- D3645-15 (A)......... I-3095-85.\2\
2019.
AA furnace............ ...................... 3113 B-2020.......... D3645-15 (B).........
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES............... 200.5, Rev 4.2 (2003); 3120 B-2020.......... D1976-20............. I-4471-97.\50\
\68\ 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
DCP................... ...................... ..................... D4190-15............. See footnote.\34\
Colorimetric ...................... See footnote.\61\....
(aluminon).
9. Biochemical oxygen demand Dissolved Oxygen ...................... 5210 B-2016 \85\..... ..................... 973.44,\3\ p. 17,\9\
(BOD5), mg/L. Depletion. I-1578-78,\8\ See
footnote.\10\ \63\
10. Boron--Total,\37\ mg/L......... Colorimetric ...................... 4500-B B-2011........ ..................... I-3112-85.\2\
(curcumin).
ICP/AES............... 200.5, Rev 4.2 (2003); 3120 B-2020.......... D1976-20............. I-4471-97.\50\
\68\ 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
DCP................... ...................... ..................... D4190-15............. See footnote.\34\
11. Bromide, mg/L.................. Electrode............. ...................... ..................... D1246-16............. I-1125-85.\2\
Ion Chromatography.... 300.0, Rev 2.1 (1993) 4110 B-2020, C-2020 D4327-17............. 993.30,\3\ I-2057-
and 300.1, Rev 1.0 or D-2020. 85.\79\
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
12. Cadmium--Total,\4\ mg/L........ Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019 or 3111 C- D3557-17 (A or B).... 974.27,\3\ p. 37,\9\
\36\. 2019. I-3135-85 \2\ or I-
3136-85.\2\
AA furnace............ ...................... 3113 B-2020.......... D3557-17 (D)......... I-4138-89.\51\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 (2003); 3120 B-2020.......... D1976-20............. I-1472-85 \2\ or I-
\68\ 200.7, Rev. 4.4 4471-97.\50\
(1994).
[[Page 10746]]
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
Voltammetry \11\...... ...................... ..................... D3557-17 (C).........
Colorimetric ...................... 3500-Cd-D-1990.......
(Dithizone).
13. Calcium--Total,\4\ mg/L........ Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019 or 3111 D- D511-14 (B).......... I-3152-85.\2\
2019.
ICP/AES............... 200.5, Rev 4.2 (2003); 3120 B-2020.......... ..................... I-4471-97.\50\
\68\ 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
DCP................... ...................... ..................... ..................... See footnote.\34\
Titrimetric (EDTA).... ...................... 3500-Ca B-2020....... D511-14 (A)..........
Ion Chromatography.... ...................... ..................... D6919-17.............
14. Carbonaceous biochemical oxygen Dissolved Oxygen ...................... 5210 B-2016 \85\..... ..................... See footnote.\35\
demand (CBOD5), mg/L \12\. Depletion with \63\
nitrification
inhibitor.
15. Chemical oxygen demand (COD), Titrimetric........... 410.3 (Rev. 1978) \1\. 5220 B-2011 or C-2011 D1252-06(12) (A)..... 973.46,\3\ p. 17,\9\
mg/L. I-3560-85.\2\
Spectrophotometric, 410.4, Rev. 2.0 (1993) 5220 D-2011.......... D1252-06(12) (B)..... See footnotes,\13\
manual or automatic. \14\ \83\ I-3561-
85.\2\
16. Chloride, mg/L................. Titrimetric: (silver ...................... 4500-Cl- B-2021...... D512-12 (B).......... I-1183-85.\2\
nitrate).
(Mercuric nitrate).... ...................... 4500-Cl- C-2021...... D512-12 (A).......... 973.51,\3\ I-1184-
85.\2\
Colorimetric: manual.. ...................... ..................... ..................... I-1187-85.\2\
Automated ...................... 4500-Cl- E-2021...... ..................... I-2187-85.\2\
(ferricyanide).
Potentiometric ...................... 4500-Cl- D-2021......
Titration.
Ion Selective ...................... ..................... D512-12 (C)..........
Electrode.
Ion Chromatography.... 300.0, Rev 2.1 (1993) 4110 B-2020 or 4110 C- D4327-17............. 993.30,\3\ I-2057-
and 300.1, Rev 1.0 2020. 90.\51\
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
17. Chlorine--Total residual, mg/L. Amperometric direct... ...................... 4500-Cl D-2011....... D1253-14.............
Amperometric direct ...................... 4500-Cl E-2011.......
(low level).
Iodometric direct..... ...................... 4500-Cl B-2011.......
Back titration ether ...................... 4500-Cl C-2011.......
end-point \15\.
DPD-FAS............... ...................... 4500 Cl F-2011.......
Spectrophotometric, ...................... 4500-Cl G-2011.......
DPD.
Electrode............. ...................... ..................... ..................... See footnote.\16\
17A. Chlorine-Free Available, mg/L. Amperometric direct... ...................... 4500-Cl D-2011....... D1253-14.............
Amperometric direct ...................... 4500-Cl E-2011.......
(low level).
DPD-FAS............... ...................... 4500-Cl F-2011.......
Spectrophotometric, ...................... 4500-Cl G-2011.......
DPD.
18. Chromium VI dissolved, mg/L.... 0.45-micron filtration
followed by any of
the following:
AA chelation- ...................... 3111 C-2019.......... ..................... I-1232-85.\2\
extraction.
Ion Chromatography.... 218.6, Rev. 3.3 (1994) 3500-Cr C-2020....... D5257-17............. 993.23.\3\
Colorimetric (diphenyl- ...................... 3500-Cr B-2020....... D1687-17 (A)......... I-1230-85.\2\
carbazide).
[[Page 10747]]
19. Chromium--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019.......... D1687-17 (B)......... 974.27,\3\ I-3236-
\36\. 85.\2\
AA chelation- ...................... 3111 C-2019..........
extraction.
AA furnace............ ...................... 3113 B-2020.......... D1687-17 (C)......... I-3233-93.\46\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 3120 B-2020.......... D1976-20.............
(2003),\68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-05
\70\ I-4472-97.\81\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
Colorimetric (diphenyl- ...................... 3500-Cr B-2020.......
carbazide).
20. Cobalt--Total,\4\ mg/L......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019 or 3111 C- D3558-15 (A or B).... p. 37,\9\ I-3239-
2019. 85.\2\
AA furnace............ ...................... 3113 B-2020.......... D3558-15 (C)......... I-4243-89.\51\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES............... 200.7, Rev. 4.4 (1994) 3120 B-2020.......... D1976-20............. I-4471-97.\50\
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-05
\70\ I-4472-97.\81\
DCP................... ...................... ..................... D4190-15............. See footnote.\34\
21. Color, platinum cobalt units or Colorimetric (ADMI)... ...................... 2120 F-2021 \78\.....
dominant wavelength, hue,
luminance purity.
Platinum cobalt visual ...................... 2120 B-2021.......... ..................... I-1250-85.\2\
comparison.
Spectrophotometric.... ...................... ..................... ..................... See footnote.\18\
22. Copper--Total,\4\ mg/L......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019 or 3111 C- D1688-17 (A or B).... 974.27,\3\ p. 37,\9\
\36\. 2019. I-3270-85 \2\ or I-
3271-85.\2\
AA furnace............ ...................... 3113 B-2020.......... D1688-17 (C)......... I-4274-89.\51\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 (2003); 3120 B-2020.......... D1976-20............. I-4471-97.\50\
\68\ 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-
05,\70\ I-4472-
97.\81\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
Colorimetric ...................... 3500-Cu B-2020.......
(Neocuproine).
Colorimetric ...................... 3500-Cu C-2020....... ..................... See footnote.\19\
(Bathocuproine).
23. Cyanide--Total, mg/L........... Automated UV digestion/ ...................... ..................... ..................... Kelada-01.\55\
distillation and
Colorimetry.
Segmented Flow ...................... 4500-CN- P-2021...... D7511-12(17).........
Injection, In-Line
Ultraviolet
Digestion, followed
by gas diffusion
amperometry.
Manual distillation 335.4, Rev. 1.0 (1993) 4500-CN- B-2021 and C- D2036-09(15)(A), 10-204-00-1-X.\56\
with MgCl2, followed \57\. 2021. D7284-20.
by any of the
following:
Flow Injection, gas ...................... ..................... D2036-09(15)(A) D7284-
diffusion amperometry. 20.
[[Page 10748]]
Titrimetric........... ...................... 4500-CN- D-2021...... D2036-09(15)(A)...... p. 22.\9\
Spectrophotometric, ...................... 4500-CN- E-2021...... D2036-09(15)(A)...... I-3300-85.\2\
manual.
Semi-Automated \20\... 335.4, Rev. 1.0 (1993) 4500-CN- N-2021...... ..................... 10-204-00-1-X,\56\ I-
\57\. 4302-85.\2\
Ion Chromatography.... ...................... ..................... D2036-09(15)(A)......
Ion Selective ...................... 4500-CN- F-2021...... D2036-09(15)(A)......
Electrode.
24. Cyanide-Available, mg/L........ Cyanide Amenable to ...................... 4500-CN- G-2021...... D2036-09(15)(B)......
Chlorination (CATC);
Manual distillation
with MgCl2, followed
by Titrimetric or
Spectrophotometric.
Flow injection and ...................... 4500-CN- Q-2021...... D6888-16............. OIA-1677-09.\44\
ligand exchange,
followed by gas
diffusion amperometry
\59\.
Automated Distillation ...................... ..................... ..................... Kelada-01.\55\
and Colorimetry (no
UV digestion).
24. A Cyanide-Free, mg/L........... Flow Injection, ...................... 4500-CN- R-2021...... D7237-18 (A)......... OIA-1677-09.\44\
followed by gas
diffusion amperometry.
Manual micro-diffusion ...................... ..................... D4282-15.............
and colorimetry.
25. Fluoride--Total, mg/L.......... Manual ...................... 4500-F- B-2021....... D1179-16 (A).........
distillation,\6\
followed by any of
the following:
Electrode, manual..... ...................... 4500-F- C-2021....... D1179-16 (B).........
Electrode, automated.. ...................... 4500-F- G-2021....... ..................... I-4327-85.\2\
Colorimetric, (SPADNS) ...................... 4500-F- D-2021.......
Automated complexone.. ...................... 4500-F- E-2021.......
Ion Chromatography.... 300.0, Rev 2.1 (1993) 4110 B-2020 or C-2020 D4327-17............. 993.30.\3\
and 300.1, Rev 1.0
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
26. Gold--Total,\4\ mg/L........... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019..........
AA furnace............ 231.2 (Issued 1978) 3113 B-2020..........
\1\.
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
DCP................... ...................... ..................... ..................... See footnote.\34\
27. Hardness--Total, as CaCO3, mg/L Automated colorimetric 130.1 (Issued 1971)
\1\.
Titrimetric (EDTA).... ...................... 2340 C-2021.......... D1126-17............. 973.52B,\3\ I-1338-
85.\2\
Ca plus Mg as their ...................... 2340 B-2021..........
carbonates, by any
approved method for
Ca and Mg (See
Parameters 13 and
33), provided that
the sum of the lowest
point of quantitation
for Ca and Mg is
below the NPDES
permit requirement
for Hardness.
28. Hydrogen ion (pH), pH units.... Electrometric ...................... 4500-H\+\ B-2021..... D1293-18 (A or B).... 973.41,\3\ I-1586-
measurement. 85.\2\
Automated electrode... 150.2 (Dec. 1982) \1\. ..................... ..................... See footnote,\21\ I-
2587-85.\2\
[[Page 10749]]
29. Iridium--Total,\4\ mg/L........ Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019..........
AA furnace............ 235.2 (Issued 1978)
\1\.
ICP/MS................ ...................... 3125 B-2020..........
30. Iron--Total,\4\ mg/L........... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019 or 3111 C- D1068-15 (A)......... 974.27,\3\ I-3381-
\36\. 2019. 85.\2\
AA furnace............ ...................... 3113 B-2020.......... D1068-15 (B).........
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
Colorimetric ...................... 3500-Fe B-2011....... D1068-15 (C)......... See footnote.\22\
(Phenanthroline).
31. Kjeldahl Nitrogen \5\--Total, Manual digestion \20\ ...................... 4500-Norg B-2021 or C- D3590-17 (A)......... I-4515-91.\45\
(as N), mg/L. and distillation or 2021 and 4500-NH3 B-
gas diffusion, 2021.
followed by any of
the following:
Titration............. ...................... 4500-NH3 C-2021...... ..................... 973.48.\3\
Nesslerization........ ...................... ..................... D1426-15 (A).........
Electrode............. ...................... 4500-NH3 D-2021 or E- D1426-15 (B).........
2021.
Semi-automated phenate 350.1, Rev. 2.0 (1993) 4500-NH3 G-2021 or
4500-NH3 H-2021.
Manual phenate, ...................... 4500-NH3 F-2021...... ..................... See footnote.\60\
salicylate, or other
substituted phenols
in Berthelot reaction
based methods.
Automated gas ...................... ..................... ..................... Timberline Ammonia-
diffusion, followed 001.\74\
by conductivity cell
analysis.
Automated gas ...................... ..................... ..................... FIAlab 100.\82\
diffusion followed by
fluorescence detector
analysis.
Automated Methods for TKN that do not require manual distillation
Automated phenate, 351.1 (Rev. 1978) \1\. ..................... ..................... I-4551-78.\8\
salicylate, or other
substituted phenols
in Berthelot reaction-
based methods
colorimetric (auto
digestion and
distillation).
Semi-automated block 351.2, Rev. 2.0 (1993) 4500-Norg D-2021..... D3590-17 (B)......... I-4515-91.\45\
digestor colorimetric
(distillation not
required).
Block digester, ...................... ..................... ..................... See footnote.\39\
followed by Auto
distillation and
Titration.
Block digester, ...................... ..................... ..................... See footnote.\40\
followed by Auto
distillation and
Nesslerization.
Block Digester, ...................... ..................... ..................... See footnote.\41\
followed by Flow
injection gas
diffusion
(distillation not
required).
[[Page 10750]]
Digestion with ...................... ..................... ..................... Hach 10242.\76\
peroxdisulfate,
followed by
Spectrophotometric
(2,6-dimethyl phenol).
Digestion with ...................... ..................... ..................... NCASI TNTP
persulfate, followed W10900.\77\
by Colorimetric.
32. Lead--Total,\4\ mg/L........... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019 or 3111 C- D3559-15 (A or B).... 974.27,\3\ I-3399-
\36\. 2019. 85.\2\
AA furnace............ ...................... 3113 B-2020.......... D3559-15 (D)......... I-4403-89.\51\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
Voltammetry \11\...... ...................... ..................... D3559-15 (C).........
Colorimetric ...................... 3500-Pb B-2020.......
(Dithizone).
33. Magnesium--Total,\4\ mg/L...... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019.......... D511-14 (B).......... 974.27,\3\ I-3447-
85.\2\
ICP/AES............... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
DCP................... ...................... ..................... ..................... See footnote.\34\
Ion Chromatography.... ...................... ..................... D6919-17.............
34. Manganese--Total,\4\ mg/L...... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019 or 3111 C- D858-17 (A or B)..... 974.27,\3\ I-3454-
\36\. 2019. 85.\2\
AA furnace............ ...................... 3113 B-2020.......... D858-17 (C)..........
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
Colorimetric ...................... 3500-Mn B-2020....... ..................... 920.203.\3\
(Persulfate).
Colorimetric ...................... ..................... ..................... See footnote.\23\
(Periodate).
35. Mercury--Total, mg/L........... Cold vapor, Manual.... 245.1, Rev. 3.0 (1994) 3112 B-2020.......... D3223-17............. 977.22,\3\ I-3462-
85.\2\
Cold vapor, Automated. 245.2 (Issued 1974)
\1\.
Cold vapor atomic 245.7 Rev. 2.0 (2005) ..................... ..................... I-4464-01.\71\
fluorescence \17\.
spectrometry (CVAFS).
Purge and Trap CVAFS.. 1631E \43\............
36. Molybdenum--Total,\4\ mg/L..... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 D-2019.......... ..................... I-3490-85.\2\
AA furnace............ ...................... 3113 B-2020.......... ..................... I-3492-96.\47\
ICP/AES............... 200.7, Rev. 4.4 (1994) 3120 B-2020.......... D1976-20............. I-4471-97.\50\
[[Page 10751]]
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
DCP................... ...................... ..................... ..................... See footnote.\34\
37. Nickel--Total,\4\ mg/L......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019 or 3111 C- D1886-14 (A or B).... I-3499-85.\2\
\36\. 2019.
AA furnace............ ...................... 3113 B-2020.......... D1886-14 (C)......... I-4503-89.\51\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-
05,\70\ I-4472-
97.\81\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
38. Nitrate (as N), mg/L........... Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2020 or C-2020 D4327-17............. 993.30.\3\
and 300.1, Rev. 1.0
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
Ion Selective ...................... 4500-NO3- D-2019.....
Electrode.
Colorimetric (Brucine 352.1 (Issued 1971) ..................... ..................... 973.50,\3\ 419D,\86\
sulfate). \1\. p. 28.\9\
Spectrophotometric ...................... ..................... ..................... Hach 10206.\75\
(2,6-dimethylphenol).
Nitrate-nitrite N
minus Nitrite N (See
parameters 39 and 40).
39. Nitrate-nitrite (as N), mg/L... Cadmium reduction, ...................... 4500-NO3- E-2019..... D3867-16 (B).........
Manual.
Cadmium reduction, 353.2, Rev. 2.0 (1993) 4500-NO3- F-2019 or D3867-16 (A)......... I-2545-90.\51\
Automated. 4500-NO3- I-2019.
Automated hydrazine... ...................... 4500-NO3- H-2019.....
Reduction/Colorimetric ...................... ..................... ..................... See footnote.\62\
Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2020 or C-2020 D4327-17............. 993.30.\3\
and 300.1, Rev. 1.0
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
Enzymatic reduction, ...................... ..................... D7781-14............. I-2547-11,\72\ I-2548-
followed by automated 11,\72\ N07-
colorimetric 0003.\73\
determination.
Enzymatic reduction, ...................... 4500-NO3- J-2018.....
followed by manual
colorimetric
determination.
Spectrophotometric ...................... ..................... ..................... Hach 10206.\75\
(2,6-dimethylphenol).
40. Nitrite (as N), mg/L........... Spectrophotometric: ...................... 4500-NO2- B-2021..... ..................... See footnote.\25\
Manual.
Automated ...................... ..................... ..................... I-4540-85,\2\ See
(Diazotization). footnote.\62\ I-2540-
90.\80\
Automated (*bypass 353.2, Rev. 2.0 (1993) 4500-NO3- F-2019 4500- D3867-16 (A)......... I-4545-85.\2\
cadmium reduction). NO3- I-2019.
Manual (*bypass ...................... 4500-NO3- E-2019, D3867-16 (B).........
cadmium or enzymatic 4500-NO3- J-2018.
reduction).
Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2020 or C-2020 D4327-17............. 993.30.\3\
and 300.1, Rev. 1.0
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
Automated (*bypass ...................... ..................... D7781-14............. I-2547-11,\72\ I-2548-
Enzymatic reduction). 11,\72\ N07-
0003.\73\
[[Page 10752]]
41. Oil and grease--Total Hexane extractable 1664 Rev. A; 1664 Rev. 5520 B or G-2021 \38\
recoverable, mg/L. material (HEM): n- B \42\.
Hexane extraction and
gravimetry.
Silica gel treated HEM 1664 Rev. A; 1664 Rev. 5520 B or G-2021 \38\
(SGT-HEM): Silica gel B \42\. and 5520 F-2021 \38\.
treatment and
gravimetry.
42. Organic carbon--Total (TOC), mg/ Combustion............ ...................... 5310 B-2014.......... D7573-18a \e1\....... 973.47,\3\ p. 14 \24\
L.
Heated persulfate or ...................... 5310 C-2014 5310 D- D4839-03(17)......... 973.47,\3\ p. 14.\24\
UV persulfate 2011.
oxidation.
43. Organic nitrogen (as N), mg/L.. Total Kjeldahl N
(Parameter 31) minus
ammonia N (Parameter
4).
44. Ortho-phosphate (as P), mg/L... Ascorbic acid method:
Automated............. 365.1, Rev. 2.0 (1993) 4500-P F-2021 or G- ..................... 973.56,\3\ I-4601-
2021. 85,\2\ I-2601-
90.\80\
Manual, single-reagent ...................... 4500-P E-2021........ D515-88 (A).......... 973.55.\3\
Manual, two-reagent... 365.3 (Issued 1978)
\1\.
Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2020 or C-2020 D4327-17............. 993.30.\3\
and 300.1, Rev. 1.0
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
45. Osmium--Total,\4\ mg/L......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 D-2019..........
AA furnace............ 252.2 (Issued 1978)
\1\.
46. Oxygen, dissolved, mg/L........ Winkler (Azide ...................... 4500-O (B-F)-2021.... D888-18 (A).......... 973.45B,\3\ I-1575-
modification). 78.\8\
Electrode............. ...................... 4500-O G-2021........ D888-18 (B).......... I-1576-78.\8\
Luminescence-Based ...................... 4500-O H-2021........ D888-18 (C).......... See footnote.\63\ See
Sensor. footnote.\64\
47. Palladium--Total,\4\ mg/L...... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019..........
AA furnace............ 253.2 (Issued 1978)
\1\.
ICP/MS................ ...................... 3125 B-2020..........
DCP................... ...................... ..................... ..................... See footnote.\34\
48. Phenols, mg/L.................. Manual 420.1 (Rev. 1978) \1\. 5530 B-2021.......... D1783-01(12).........
distillation,\26\
followed by any of
the following:.
Colorimetric (4AAP) 420.1 (Rev. 1978) \1\. 5530 D-2021 \27\..... D1783-01(12) (A or B)
manual.
Automated colorimetric 420.4 Rev. 1.0 (1993).
(4AAP).
49. Phosphorus (elemental), mg/L... Gas-liquid ...................... ..................... ..................... See footnote.\28\
chromatography.
50. Phosphorus--Total, mg/L........ Digestion,\20\ ...................... 4500-P B (5)-2021.... ..................... 973.55.\3\
followed by any of
the following:
Manual................ 365.3 (Issued 1978) 4500-P E-2021........ D515-88 (A)..........
\1\.
Automated ascorbic 365.1 Rev. 2.0 (1993). 4500-P (F-H)-2021.... ..................... 973.56,\3\ I-4600-
acid reduction. 85.\2\
ICP/AES \4\ \36\...... 200.7, Rev. 4.4 (1994) 3120 B-2020.......... ..................... I-4471-97.\50\
Semi-automated block 365.4 (Issued 1974) ..................... D515-88 (B).......... I-4610-91.\48\
digestor (TKP \1\.
digestion).
Digestion with ...................... ..................... ..................... NCASI TNTP
persulfate, followed W10900.\77\
by Colorimetric.
51. Platinum--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019..........
[[Page 10753]]
AA furnace............ 255.2 (Issued 1978)
\1\.
ICP/MS................ ...................... 3125 B-2020..........
DCP................... ...................... ..................... ..................... See footnote.\34\
52. Potassium--Total,\4\ mg/L...... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019.......... ..................... 973.53,\3\ I-3630-
85.\2\
ICP/AES............... 200.7, Rev. 4.4 (1994) 3120 B-2020..........
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
Flame photometric..... ...................... 3500-K B-2020........
Electrode............. ...................... 3500-K C-2020........
Ion Chromatography.... ...................... ..................... D6919-17.............
53. Residue--Total, mg/L........... Gravimetric, 103- ...................... 2540 B-2020.......... ..................... I-3750-85.\2\
105[deg].
54. Residue--filterable, mg/L...... Gravimetric, 180[deg]. ...................... 2540 C-2020.......... D5907-18 (B)......... I-1750-85.\2\
55. Residue--non-filterable (TSS), Gravimetric, 103- ...................... 2540 D-2020.......... D5907-18 (A)......... I-3765-85.\2\
mg/L. 105[deg] post-washing
of residue.
56. Residue--settleable, mg/L...... Volumetric (Imhoff ...................... 2540 F-2020..........
cone), or gravimetric.
57. Residue--Volatile, mg/L........ Gravimetric, 550[deg]. 160.4 (Issued 1971) 2540 E-2020.......... ..................... I-3753-85.\2\
\1\.
58. Rhodium--Total,\4\ mg/L........ Digestion,\4\ followed
by any of the
following:
AA direct aspiration, ...................... 3111 B-2019..........
or.
AA furnace............ 265.2 (Issued 1978)
\1\.
ICP/MS................ ...................... 3125 B-2020..........
59. Ruthenium--Total,\4\ mg/L...... Digestion,\4\ followed
by any of the
following:
AA direct aspiration, ...................... 3111 B-2019..........
or.
AA furnace............ 267.2 \1\.............
ICP/MS................ ...................... 3125 B-2020..........
60. Selenium--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA furnace............ ...................... 3113 B-2020.......... D3859-15 (B)......... I-4668-98.\49\
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 (2003); 3120 B-2020.......... D1976-20.............
\68\ 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-
05,\70\ I-4472-
97.\81\
AA gaseous hydride.... ...................... 3114 B-2020, or 3114 D3859-15 (A)......... I-3667-85.\2\
C-2020.
61. Silica--Dissolved,\37\ mg/L.... 0.45-micron filtration
followed by any of
the following:
Colorimetric, Manual.. ...................... 4500-SiO2 C-2021..... D859-16.............. I-1700-85.\2\
Automated ...................... 4500-SiO2 E-2021 or F- ..................... I-2700-85.\2\
(Molybdosilicate). 2021.
ICP/AES............... 200.5, Rev. 4.2 3120 B-2020.......... ..................... I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
62. Silver--Total,\4\ \31\ mg/L.... Digestion,\4\ \29\
followed by any of
the following:
AA direct aspiration.. ...................... 3111 B-2019 or 3111 C- ..................... 974.27,\3\ p. 37,\9\
2019. I-3720-85.\2\
AA furnace............ ...................... 3113 B-2020.......... ..................... I-4724-89.\51\
STGFAA................ 200.9, Rev. 2.2 (1994)
[[Page 10754]]
ICP/AES............... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4472-
97.\81\
DCP................... ...................... ..................... ..................... See footnote.\34\
63. Sodium--Total,\4\ mg/L......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019.......... ..................... 973.54,\3\ I-3735-
85.\2\
ICP/AES............... 200.5, Rev. 4.2 3120 B-2020.......... ..................... I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
DCP................... ...................... ..................... ..................... See footnote.\34\
Flame photometric..... ...................... 3500-Na B-2020.......
Ion Chromatography.... ...................... ..................... D6919-17.............
64. Specific conductance, micromhos/ Wheatstone bridge..... 120.1 (Rev. 1982) \1\. 2510 B-2021.......... D1125-95(99) (A)..... 973.40,\3\ I-2781-
cm at 25 [deg]C. 85.\2\
65. Sulfate (as SO4), mg/L......... Automated colorimetric 375.2, Rev. 2.0 (1993) 4500-SO42- F-2021 or
G-2021.
Gravimetric........... ...................... 4500-SO42- C-2021 or ..................... 925.54. \3\
D-2021.
Turbidimetric......... ...................... 4500-SO42- E-2021.... D516-16..............
Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2020 or C-2020 D4327-17............. 993.30,\3\ I-4020-
and 300.1, Rev. 1.0 05.\70\
(1997).
CIE/UV................ ...................... 4140 B-2020.......... D6508-15............. D6508, Rev. 2.\54\
66. Sulfide (as S), mg/L........... Sample Pretreatment... ...................... 4500-S2- B, C-2021...
Titrimetric (iodine).. ...................... 4500-S2- F-2021...... ..................... I-3840-85.\2\
Colorimetric ...................... 4500-S2- D-2021......
(methylene blue).
Ion Selective ...................... 4500-S2- G-2021...... D4658-15.............
Electrode.
67. Sulfite (as SO3), mg/L......... Titrimetric (iodine- ...................... 4500-SO32- B-2021....
iodate).
68. Surfactants, mg/L.............. Colorimetric ...................... 5540 C-2021.......... D2330-20.............
(methylene blue).
69. Temperature, [deg]C............ Thermometric.......... ...................... 2550 B-2010.......... ..................... See footnote.\32\
70. Thallium--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019..........
AA furnace............ 279.2 (Issued 1978) 3113 B-2020..........
\1\.
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES............... 200.7, Rev. 4.4 (1994) 3120 B-2020.......... D1976-20.............
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4471-
97,\50\ I-4472-
97.\81\
71. Tin--Total,\4\ mg/L............ Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2019.......... ..................... I-3850-78.\8\
AA furnace............ ...................... 3113 B-2020..........
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES............... 200.5, Rev. 4.2
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
72. Titanium--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 D-2019..........
AA furnace............ 283.2 (Issued 1978)
\1\.
ICP/AES............... 200.7, Rev. 4.4 (1994)
[[Page 10755]]
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14.\3\
DCP................... ...................... ..................... ..................... See footnote.\34\
73. Turbidity, NTU \53\............ Nephelometric......... 180.1, Rev. 2.0 (1993) 2130 B-2020.......... D1889-00............. I-3860-85.\2\ See
footnote.\65\ See
footnote.\66\ See
footnote.\67\
74. Vanadium--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 D-2019..........
AA furnace............ ...................... 3113 B-2020.......... D3373-17.............
ICP/AES............... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-
05.\70\
DCP................... ...................... ..................... D4190-15............. See footnote.\34\
Colorimetric (Gallic ...................... 3500-V B-2011........
Acid).
75. Zinc--Total,\4\ mg/L........... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2019 or 3111 C- D1691-17 (A or B).... 974.27,\3\ p. 37,\9\
\36\. 2019. I-3900-85.\2\
AA furnace............ 289.2 (Issued 1978)
\1\.
ICP/AES \36\.......... 200.5, Rev. 4.2 3120 B-2020.......... D1976-20............. I-4471-97.\50\
(2003); \68\ 200.7,
Rev. 4.4 (1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2020.......... D5673-16............. 993.14,\3\ I-4020-
05,\70\ I-4472-
97.\81\
DCP \36\.............. ...................... ..................... D4190-15............. See footnote.\34\
Colorimetric (Zincon). ...................... 3500 Zn B-2020....... ..................... See footnote.\33\
76. Acid Mine Drainage............. ...................... 1627 \69\.............
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IB Notes:
\1\ Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020. Revised March 1983 and 1979, where applicable. U.S. EPA.
\2\ Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resource Investigations of the U.S. Geological
Survey, Book 5, Chapter A1., unless otherwise stated. 1989. USGS.
\3\ Official Methods of Analysis of the Association of Official Analytical Chemists, Methods Manual, Sixteenth Edition, 4th Revision, 1998. AOAC
International.
\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 (as specified in
Section 4.1.3 of Methods for Chemical Analysis of Water and Wastes) 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 (FLAA) determinations, a
combination acid (nitric and hydrochloric acids) digestion is preferred, prior to analysis. The approved 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 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
of this section); 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 or other catalysts that have been found suitable may 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. In general, the analytical method should be
consulted regarding the need for distillation. If the method is not clear, the laboratory may compare a minimum of 9 different sample matrices to
evaluate the need for distillation. For each matrix, a matrix spike and matrix spike duplicate are analyzed both with and without the distillation
step (for a total of 36 samples, assuming 9 matrices). If results are comparable, the laboratory may dispense with the distillation step for future
analysis. Comparable is defined as <20% RPD for all tested matrices). Alternatively, the two populations of spike recovery percentages may be compared
using a recognized statistical test.
\7\ Industrial Method Number 379-75 WE Ammonia, Automated Electrode Method, Technicon Auto Analyzer II. February 19, 1976. Bran & Luebbe Analyzing
Technologies Inc.
\8\ The approved method is that cited in Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resources
Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1979. USGS.
\9\ American National Standard on Photographic Processing Effluents. April 2, 1975. American National Standards Institute.
\10\ In-Situ Method 1003-8-2009, Biochemical Oxygen Demand (BOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.
\11\ The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable.
[[Page 10756]]
\12\ Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test method which measures ``total 5-day 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. 1978. Oceanography International Corporation.
\14\ Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company.
\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. 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\ Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-05-001. Revision 2.0, February 2005. US EPA.
\18\ National Council of the Paper Industry for Air and Stream Improvement (NCASI) Technical Bulletin 253 (1971) and Technical Bulletin 803, May 2000.
\19\ Method 8506, Bicinchoninate Method for Copper, Hach Handbook of Water Analysis. 1979. Hach Company.
\20\ When using a method with block digestion, this treatment is not required.
\21\ Industrial Method Number 378-75WA, Hydrogen ion (pH) Automated Electrode Method, Bran & Luebbe (Technicon) Autoanalyzer II. October 1976. Bran &
Luebbe Analyzing Technologies.
\22\ Method 8008, 1,10-Phenanthroline Method using FerroVer Iron Reagent for Water. 1980. Hach Company.
\23\ Method 8034, Periodate Oxidation Method for Manganese, Hach Handbook of Wastewater Analysis. 1979. Hach Company.
\24\ 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, (1972 Revised 1987). 1987. USGS.
\25\ Method 8507, Nitrogen, Nitrite-Low Range, Diazotization Method for Water and Wastewater. 1979. Hach Company.
\26\ Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH.
\27\ The colorimetric reaction must be conducted at a pH of 10.0 0.2.
\28\ Addison, R.F., and R.G. Ackman. 1970. Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography, Journal of Chromatography,
47(3):421-426.
\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 use of EDTA decreases method sensitivity. Analysts may omit EDTA or replace with another suitable complexing reagent provided that all method-
specified quality control acceptance criteria are met.
\31\ For samples known or suspected to contain high levels of silver (e.g., in excess of 4 mg/L), cyanogen iodide should be used to keep the silver in
solution for analysis. Prepare a cyanogen iodide solution by adding 4.0 mL of concentrated NH4OH, 6.5 g of KCN, and 5.0 mL of a 1.0 N solution of I2
to 50 mL of reagent water in a volumetric flask and dilute to 100.0 mL. After digestion of the sample, adjust the pH of the digestate to >7 to prevent
the formation of HCN under acidic conditions. Add 1 mL of the cyanogen iodide solution to the sample digestate and adjust the volume to 100 mL with
reagent water (NOT acid). If cyanogen iodide is added to sample digestates, then silver standards must be prepared that contain cyanogen iodide as
well. Prepare working standards by diluting a small volume of a silver stock solution with water and adjusting the pH >7 with NH4OH. Add 1 mL of the
cyanogen iodide solution and let stand 1 hour. Transfer to a 100-mL volumetric flask and dilute to volume with water.
\32\ ``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. USGS.
\33\ Method 8009, Zincon Method for Zinc, Hach Handbook of Water Analysis, 1979. Hach Company.
\34\ Method AES0029, Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes. 1986-Revised
1991. Thermo Jarrell Ash Corporation.
\35\ In-Situ Method 1004-8-2009, Carbonaceous Biochemical Oxygen Demand (CBOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.
\36\ Microwave-assisted digestion may be employed for this metal, when analyzed by this methodology. Closed Vessel Microwave Digestion of Wastewater
Samples for Determination of Metals. April 16, 1992. 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 (n-Hexane--85% minimum purity, 99.0% min. saturated C6 isomers, residue less than 1 mg/L) extraction solvent when determining Oil
and Grease parameters--Hexane Extractable Material (HEM), or Silica Gel Treated HEM (analogous to EPA Methods 1664 Rev. A and 1664 Rev. B). Use of
other extraction solvents is prohibited.
\39\ Method PAI-DK01, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Titrimetric Detection. Revised December 22, 1994. OI Analytical.
\40\ Method PAI-DK02, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Colorimetric Detection. Revised December 22, 1994. OI Analytical.
\41\ Method PAI-DK03, Nitrogen, Total Kjeldahl, Block Digestion, Automated FIA Gas Diffusion. Revised December 22, 1994. OI Analytical.
\42\ Method 1664 Rev. B is the revised version of EPA Method 1664 Rev. A. U.S. EPA. February 1999, Revision A. Method 1664, 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. U.S. EPA. February 2010, Revision B. Method 1664, 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-10-001.
\43\ Method 1631, Revision E, Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-02-019. Revision
E. August 2002, U.S. EPA. The application of clean techniques described in EPA's 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\ Method OIA-1677-09, Available Cyanide by Ligand Exchange and Flow Injection Analysis (FIA). 2010. OI Analytical.
\45\ Open File Report 00-170, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Ammonium Plus
Organic Nitrogen by a Kjeldahl Digestion Method and an Automated Photometric Finish that Includes Digest Cleanup by Gas Diffusion. 2000. USGS.
\46\ Open File Report 93-449, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Chromium in Water by
Graphite Furnace Atomic Absorption Spectrophotometry. 1993. USGS.
\47\ Open File Report 97-198, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Molybdenum by
Graphite Furnace Atomic Absorption Spectrophotometry. 1997. USGS.
\48\ Open File Report 92-146, 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. 1992. USGS.
\49\ Open File Report 98-639, 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. 1999. USGS.
\50\ Open File Report 98-165, 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. 1998. USGS.
\51\ Open File Report 93-125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Inorganic and
Organic Constituents in Water and Fluvial Sediments. 1993. USGS.
[[Page 10757]]
\52\ Unless otherwise indicated, all EPA methods, excluding EPA Method 300.1, are published in U.S. EPA. May 1994. Methods for the Determination of
Metals in Environmental Samples, Supplement I, EPA/600/R-94/111; or U.S. EPA. August 1993. Methods for the Determination of Inorganic Substances in
Environmental Samples, EPA/600/R-93/100. EPA Method 300.1 is U.S. EPA. Revision 1.0, 1997, including errata cover sheet April 27, 1999. Determination
of Inorganic Ions in Drinking Water by Ion Chromatography.
\53\ Styrene divinyl benzene beads (e.g., AMCO-AEPA-1 or equivalent) and stabilized formazin (e.g., Hach StablCal \TM\ or equivalent) are acceptable
substitutes for formazin.
\54\ Method D6508-15, Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and Chromate
Electrolyte. 2015. ASTM.
\55\ Kelada-01, Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, and Thiocyanate, EPA 821-B-01-009, Revision 1.2, August 2001.
US EPA. Note: A 450-W UV lamp may be used in this method instead of the 550-W lamp specified if it provides performance within the quality control
(QC) acceptance criteria of the method in a given instrument. Similarly, modified flow cell configurations and flow conditions may be used in the
method, provided that the QC acceptance criteria are met.
\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. Revision 2.2, March 2005. Lachat Instruments.
\57\ When using sulfide removal test procedures described in EPA 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\ Samples analyzed for available cyanide using OI Analytical method OIA-1677-09 or ASTM method D6888-16 that contain particulate matter may be
filtered only after the ligand exchange reagents have been added to the samples, because the ligand exchange process converts complexes containing
available cyanide to free cyanide, which is not removed by filtration. Analysts are further cautioned to limit the time between the addition of the
ligand exchange reagents and sample filtration to no more than 30 minutes to preclude settling of materials in samples.
\60\ Analysts should be aware that pH optima and chromophore absorption maxima might differ when phenol is replaced by a substituted phenol as the color
reagent in Berthelot Reaction (``phenol-hypochlorite reaction'') colorimetric ammonium determination methods. For example, when phenol is used as the
color reagent, pH optimum and wavelength of maximum absorbance are about 11.5 and 635 nm, respectively--see, Patton, C.J. and S.R. Crouch. March 1977.
Anal. Chem. 49:464-469. These reaction parameters increase to pH > 12.6 and 665 nm when salicylate is used as the color reagent--see, Krom, M.D. April
1980. The Analyst 105:305-316.
\61\ If atomic absorption or ICP instrumentation is not available, the aluminon colorimetric method detailed in the 19th Edition of Standard Methods for
the Examination of Water and Wastewater may be used. This method has poorer precision and bias than the methods of choice.
\62\ Easy (1-Reagent) Nitrate Method, Revision November 12, 2011. Craig Chinchilla.
\63\ Hach Method 10360, Luminescence Measurement of Dissolved Oxygen in Water and Wastewater and for Use in the Determination of BOD5 and CBOD5.
Revision 1.2, October 2011. Hach Company. This method may be used to measure dissolved oxygen when performing the methods approved in Table IB of this
section for measurement of biochemical oxygen demand (BOD) and carbonaceous biochemical oxygen demand (CBOD).
\64\ In-Situ Method 1002-8-2009, Dissolved Oxygen (DO) Measurement by Optical Probe. 2009. In-Situ Incorporated.
\65\ Mitchell Method M5331, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.
\66\ Mitchell Method M5271, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.
\67\ Orion Method AQ4500, Determination of Turbidity by Nephelometry. Revision 5, March 12, 2009. Thermo Scientific.
\68\ EPA Method 200.5, Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry, EPA/
600/R-06/115. Revision 4.2, October 2003. US EPA.
\69\ Method 1627, Kinetic Test Method for the Prediction of Mine Drainage Quality, EPA-821-R-09-002. December 2011. US EPA.
\70\ Techniques and Methods Book 5-B1, Determination of Elements in Natural-Water, Biota, Sediment and Soil Samples Using Collision/Reaction Cell
Inductively Coupled Plasma-Mass Spectrometry, Chapter 1, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis,
2006. USGS.
\71\ Water-Resources Investigations Report 01-4132, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination
of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural Water with Cold Vapor-Atomic Fluorescence Spectrometry, 2001. USGS.
\72\ USGS Techniques and Methods 5-B8, Chapter 8, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis, 2011 USGS.
\73\ NECi Method N07-0003, ``Nitrate Reductase Nitrate-Nitrogen Analysis,'' Revision 9.0, March 2014, The Nitrate Elimination Co., Inc.
\74\ Timberline Instruments, LLC Method Ammonia-001, ``Determination of Inorganic Ammonia by Continuous Flow Gas Diffusion and Conductivity Cell
Analysis,'' June 2011, Timberline Instruments, LLC.
\75\ Hach Company Method 10206, ``Spectrophotometric Measurement of Nitrate in Water and Wastewater,'' Revision 2.1, January 2013, Hach Company.
\76\ Hach Company Method 10242, ``Simplified Spectrophotometric Measurement of Total Kjeldahl Nitrogen in Water and Wastewater,'' Revision 1.1, January
2013, Hach Company.
\77\ National Council for Air and Stream Improvement (NCASI) Method TNTP-W10900, ``Total (Kjeldahl) Nitrogen and Total Phosphorus in Pulp and Paper
Biologically Treated Effluent by Alkaline Persulfate Digestion,'' June 2011, National Council for Air and Stream Improvement, Inc.
\78\ The pH adjusted sample is to be adjusted to 7.6 for NPDES reporting purposes.
\79\ I-2057-85 U.S. Geological Survey Techniques of Water-Resources Investigations, Book 5, Chap. A11989, Methods for Determination of Inorganic
Substances in Water and Fluvial Sediments, 1989.
\80\ Methods I-2522-90, I-2540-90, and I-2601-90 U.S. Geological Survey Open-File Report 93-125, Methods of Analysis by the U.S. Geological Survey
National Water Quality Laboratory--Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments, 1993.
\81\ Method I-1472-97, U.S. Geological Survey Open-File Report 98-165, Methods of Analysis by the U.S. Geological Survey National Water Quality
Laboratory--Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments, 1998.
\82\ FIAlab Instruments, Inc. Method FIAlab 100, ``Determination of Inorganic Ammonia by Continuous Flow Gas Diffusion and Fluorescence Detector
Analysis'', April 4, 2018, FIAlab Instruments, Inc.
\83\ MACHEREY-NAGEL GmbH and Co. Method 036/038 NANOCOLOR[supreg] COD LR/HR, ``Spectrophotometric Measurement of Chemical Oxygen Demand in Water and
Wastewater'', Revision 1.5, May 2018, MACHEREY-NAGEL GmbH and Co. KG.
\84\ Please refer to the following applicable Quality Control Sections: Part 2000 Methods, Physical and Aggregate Properties 2020 (2021); Part 3000
Methods, Metals, 3020 (2021); Part 4000 Methods, Inorganic Nonmetallic Constituents, 4020 (2022); Part 5000 Methods, and Aggregate Organic
Constituents, 5020 (2022). These Quality Control Standards are available for download at www.standardmethods.org at no charge.
\85\ Each laboratory may establish its own control limits by performing at least 25 glucose-glutamic acid (GGA) checks over several weeks or months and
calculating the mean and standard deviation. The laboratory may then use the mean 3 standard deviations as the control limit for future
GGA checks. However, GGA acceptance criteria can be no wider than 198 30.5 mg/L for BOD5. GGA acceptance criteria for CBOD must be either
198 30.5 mg/L, or the lab may develop control charts under the following conditions: dissolved oxygen uptake from the seed contribution
is between 0.6-1.0 mg/L; control charts are performed on at least 25 GGA checks with three standard deviations from the derived mean; the RSD must not
exceed 7.5%; and any single GGA value cannot be less than 150 mg/L or higher than 250 mg/L.
\86\ The approved method is that cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition, 1976.
[[Page 10758]]
Table IC--List of Approved Test Procedures for Non-Pesticide Organic Compounds
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter \1\ Method EPA \2\ \7\ Standard methods \15\ ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acenaphthene.................... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
2. Acenaphthylene.................. GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
3. Acrolein........................ GC.................... 603...................
GC/MS................. 624.1,\4\ 1624B.......
4. Acrylonitrile................... GC.................... 603...................
GC/MS................. 624.1,\4\ 1624B....... ..................... ..................... O-4127-96.\13\
5. Anthracene...................... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440B-2021........... D4657-92 (98)........
6. Benzene......................... GC.................... 602................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
7. Benzidine....................... Spectro-photometric... ...................... ..................... ..................... See footnote,\3\ p.
1.
GC/MS................. 625.1,\5\ 1625B....... 6410 B-2020..........
HPLC.................. 605...................
8. Benzo(a)anthracene.............. GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
9. Benzo(a)pyrene.................. GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
10. Benzo(b)fluoranthene........... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
11. Benzo(g,h,i)perylene........... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
12. Benzo(k)fluoranthene........... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
13. Benzyl chloride................ GC.................... ...................... ..................... ..................... See footnote,\3\ p.
130.
GC/MS................. ...................... ..................... ..................... See footnote,\6\ p.
S102.
14. Butyl benzyl phthalate......... GC.................... 606...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
15. bis(2-Chloroethoxy) methane.... GC.................... 611...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
16. bis(2-Chloroethyl) ether....... GC.................... 611...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
17. bis(2-Ethylhexyl) phthalate.... GC.................... 606...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
18. Bromodichloromethane........... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
19. Bromoform...................... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
20. Bromomethane................... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
21. 4-Bromophenyl phenyl ether..... GC.................... 611...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
22. Carbon tetrachloride........... GC.................... 601................... 6200 C-2020.......... ..................... See footnote,\3\ p.
130.
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
[[Page 10759]]
23. 4-Chloro-3-methyl phenol....... GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
24. Chlorobenzene.................. GC.................... 601, 602.............. 6200 C-2020.......... ..................... See footnote,\3\ p.
130.
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
25. Chloroethane................... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96.\13\
26. 2-Chloroethylvinyl ether....... GC.................... 601...................
GC/MS................. 624.1, 1624B..........
27. Chloroform..................... GC.................... 601................... 6200 C-2020.......... ..................... See footnote,\3\ p.
130.
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
28. Chloromethane.................. GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
29. 2-Chloronaphthalene............ GC.................... 612...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
30. 2-Chlorophenol................. GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
31. 4-Chlorophenyl phenyl ether.... GC.................... 611...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
32. Chrysene....................... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
33. Dibenzo(a,h)anthracene......... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
34. Dibromochloromethane........... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
35. 1,2-Dichlorobenzene............ GC.................... 601, 602.............. 6200 C-2020..........
GC/MS................. 624.1, 1625B.......... 6200 B-2020.......... ..................... See footnote,\9\ p.
27 O-4127-96,\13\ O-
4436-16.\14\
36. 1,3-Dichlorobenzene............ GC.................... 601, 602.............. 6200 C-2020..........
GC/MS................. 624.1, 1625B.......... 6200 B-2020.......... ..................... See footnote,\9\ p.
27 O-4127-96.\13\
37. 1,4-Dichlorobenzene............ GC.................... 601, 602.............. 6200 C-2020..........
GC/MS................. 624.1, 1625B.......... 6200 B-2020.......... ..................... See footnote,\9\ p.
27 O-4127-96,\13\ O-
4436-16.\14\
38. 3,3'-Dichlorobenzidine......... GC/MS................. 625.1, 1625B.......... 6410 B-2020..........
HPLC.................. 605...................
39. Dichlorodifluoromethane........ GC.................... 601...................
GC/MS................. ...................... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
40. 1,1-Dichloroethane............. GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
41. 1,2-Dichloroethane............. GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
42. 1,1-Dichloroethene............. GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
43. trans-1,2-Dichloroethene....... GC.................... 601................... 6200 C-2020..........
[[Page 10760]]
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
44. 2,4-Dichlorophenol............. GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
45. 1,2-Dichloropropane............ GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
46. cis-1,3-Dichloropropene........ GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
47. trans-1,3-Dichloropropene...... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
48. Diethyl phthalate.............. GC.................... 606...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
49. 2,4-Dimethylphenol............. GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
50. Dimethyl phthalate............. GC.................... 606...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
51. Di-n-butyl phthalate........... GC.................... 606...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
52. Di-n-octyl phthalate........... GC.................... 606...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
53. 2, 4-Dinitrophenol............. GC.................... 604................... 6420 B-2020.......... ..................... See footnote,\9\ p.
27.
GC/MS................. 625.1, 1625B.......... 6410 B-2020..........
54. 2,4-Dinitrotoluene............. GC.................... 609...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
55. 2,6-Dinitrotoluene............. GC.................... 609...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
56. Epichlorohydrin................ GC.................... ...................... ..................... ..................... See footnote,\3\ p.
130.
GC/MS................. ...................... ..................... ..................... See footnote,\6\ p.
S102.
57. Ethylbenzene................... GC.................... 602................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
58. Fluoranthene................... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
59. Fluorene....................... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
60. 1,2,3,4,6,7,8-Heptachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
61. 1,2,3,4,7,8,9-Heptachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
62. 1,2,3,4,6,7,8- Heptachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzo-p-dioxin. 16130-SSI.\16\
63. Hexachlorobenzene.............. GC.................... 612...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
64. Hexachlorobutadiene............ GC.................... 612...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27 O-4127-96.\13\
65. Hexachlorocyclopentadiene...... GC.................... 612...................
GC/MS................. 625.1,\5\ 1625B....... 6410 B-2020.......... ..................... See footnote,\9\ p.
27 O-4127-96.\13\
66. 1,2,3,4,7,8-Hexachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
[[Page 10761]]
67. 1,2,3,6,7,8-Hexachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
68. 1,2,3,7,8,9-Hexachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
69. 2,3,4,6,7,8-Hexachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
70. 1,2,3,4,7,8-Hexachloro-dibenzo- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
p-dioxin. 16130-SSI,\16\ G
BHTYHGTGB B VB B5
BV.
71. 1,2,3,6,7,8-Hexachloro-dibenzo- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
p-dioxin. 16130-SSI.\16\
72. 1,2,3,7,8,9-Hexachloro-dibenzo- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
p-dioxin. 16130-SSI.\16\
73. Hexachloroethane............... GC.................... 612...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27 O-4127-96.\13\
74. Indeno(1,2,3-c,d) pyrene....... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
75. Isophorone..................... GC.................... 609...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
76. Methylene chloride............. GC.................... 601................... 6200 C-2020.......... ..................... See footnote,\3\ p.
130.
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
77. 2-Methyl-4,6-dinitrophenol..... GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
78. Naphthalene.................... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021..........
79. Nitrobenzene................... GC.................... 609...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. ...................... ..................... D4657-92 (98)........
80. 2-Nitrophenol.................. GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
81. 4-Nitrophenol.................. GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
82. N-Nitrosodimethylamine......... GC.................... 607...................
GC/MS................. 625.1,\5\ 1625B....... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
83. N-Nitrosodi-n-propylamine...... GC.................... 607...................
GC/MS................. 625.1,\5\ 1625B....... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
84. N-Nitrosodiphenylamine......... GC.................... 607...................
GC/MS................. 625.1,\5\ 1625B....... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
85. Octachlorodibenzofuran......... GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
16130-SSI.\16\
86. Octachlorodibenzo-p-dioxin..... GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
16130-SSI.\16\
87. 2,2'-oxybis(1-chloropropane) GC.................... 611...................
\12\ [also known as bis(2-Chloro-1-
methylethyl) ether].
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
88. PCB-1016....................... GC.................... 608.3................. ..................... ..................... See footnote,\3\ p.
43; See footnote.\8\
GC/MS................. 625.1................. 6410 B-2020..........
[[Page 10762]]
89. PCB-1221....................... GC.................... 608.3................. ..................... ..................... See footnote,\3\ p.
43; See footnote.\8\
GC/MS................. 625.1................. 6410 B-2020..........
90. PCB-1232....................... GC.................... 608.3................. ..................... ..................... See footnote,\3\ p.
43; See footnote.\8\
GC/MS................. 625.1................. 6410 B-2020..........
91. PCB-1242....................... GC.................... 608.3................. ..................... ..................... See footnote,\3\ p.
43; See footnote.\8\
GC/MS................. 625.1................. 6410 B-2020..........
92. PCB-1248....................... GC.................... 608.3................. ..................... ..................... See footnote,\3\ p.
43; See footnote.\8\
GC/MS................. 625.1................. 6410 B-2020..........
93. PCB-1254....................... GC.................... 608.3................. ..................... ..................... See footnote,\3\ p.
43; See footnote.\8\
GC/MS................. 625.1................. 6410 B-2020..........
94. PCB-1260....................... GC.................... 608.3................. ..................... ..................... See footnote,\3\ p.
43; See footnote.\8\
GC/MS................. 625.1................. 6410 B-2020..........
95. 1,2,3,7,8-Pentachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
96. 2,3,4,7,8-Pentachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
97. 1,2,3,7,8-Pentachloro-dibenzo-p- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dioxin. 16130-SSI.\16\
98. Pentachlorophenol.............. GC.................... 604................... 6420 B-2020.......... ..................... See footnote,\3\ p.
140.
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
99. Phenanthrene................... GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
100. Phenol........................ GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
101. Pyrene........................ GC.................... 610...................
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
HPLC.................. 610................... 6440 B-2021.......... D4657-92 (98)........
102. 2,3,7,8-Tetrachloro- GC/MS................. 1613B \10\............ ..................... ..................... ATM 16130,\15\ PAM
dibenzofuran. 16130-SSI.\16\
103. 2,3,7,8-Tetrachloro-dibenzo-p- GC/MS................. 613, 625.1,\5a\ 1613B. ..................... ..................... ATM 16130,\15\ PAM
dioxin. 16130-SSI.\16\
104. 1,1,2,2-Tetrachloroethane..... GC.................... 601................... 6200 C-2020.......... ..................... See footnote,\3\ p.
130.
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96.\13\
105. Tetrachloroethene............. GC.................... 601................... 6200 C-2020.......... ..................... See footnote,\3\ p.
130.
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
106. Toluene....................... GC.................... 602................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
107. 1,2,4-Trichlorobenzene........ GC.................... 612................... ..................... ..................... See footnote,\3\ p.
130.
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27 O-4127-96,\13\ O-
4436-16.\14\
108. 1,1,1-Trichloroethane......... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
109. 1,1,2-Trichloroethane......... GC.................... 601................... 6200 C-2020.......... ..................... See footnote,\3\ p.
130.
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
110. Trichloroethene............... GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
111. Trichlorofluoromethane........ GC.................... 601................... 6200 C-2020..........
[[Page 10763]]
GC/MS................. 624.1................. 6200 B-2020.......... ..................... O-4127-96.\13\
112. 2,4,6-Trichlorophenol......... GC.................... 604................... 6420 B-2020..........
GC/MS................. 625.1, 1625B.......... 6410 B-2020.......... ..................... See footnote,\9\ p.
27.
113. Vinyl chloride................ GC.................... 601................... 6200 C-2020..........
GC/MS................. 624.1, 1624B.......... 6200 B-2020.......... ..................... O-4127-96,\13\ O-4436-
16.\14\
114. Nonylphenol................... GC/MS................. ...................... ..................... D7065-17.............
115. Bisphenol A (BPA)............. GC/MS................. ...................... ..................... D7065-17.............
116. p-tert-Octylphenol (OP)....... GC/MS................. ...................... ..................... D7065-17.............
117. Nonylphenol Monoethoxylate GC/MS................. ...................... ..................... D7065-17.............
(NP1EO).
118. Nonylphenol Diethoxylate GC/MS................. ...................... ..................... D7065-17.............
(NP2EO).
119. Adsorbable Organic Halides Adsorption and 1650 \11\.............
(AOX). Coulometric Titration.
120. Chlorinated Phenolics......... In Situ Acetylation 1653 \11\.............
and GC/MS.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IC notes:
\1\ All parameters are expressed in micrograms per liter ([micro]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, 1613B, 1624B, and 1625B are provided at appendix A, Test Procedures for Analysis of Organic Pollutants. The
standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at appendix B of this part,
Definition and Procedure for the Determination of the Method Detection Limit. These methods are available at: https://www.epa.gov/cwa-methods as
individual PDF files.
\3\ Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA.
\4\ Method 624.1 may be used for quantitative determination of acrolein and acrylonitrile, provided that the laboratory has documentation to
substantiate the ability to detect and quantify these analytes at levels necessary to comply with any associated regulations. In addition, the use of
sample introduction techniques other than simple purge-and-trap may be required. QC acceptance criteria from Method 603 should be used when analyzing
samples for acrolein and acrylonitrile in the absence of such criteria in Method 624.1.
\5\ Method 625.1 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, N-nitrosodi-n-propylamine, 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\ Method 625.1 screening only.
\6\ Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency, Supplement to the 15th Edition of Standard
Methods for the Examination of Water and Wastewater. 1981. American Public Health Association (APHA).
\7\ Each analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601-603,
1624B, and 1625B in accordance with procedures 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 624.1 and 625.1 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 quality control (QC) acceptance
criteria in the pertinent method, analytical results for that parameter in the unspiked sample are suspect. The results should be reported but cannot
be used to demonstrate regulatory compliance. If the method does not contain QC acceptance criteria, control limits of three standard
deviations around the mean of a minimum of five replicate measurements must be used. 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. Revised October 28, 1994. 3M Corporation.
\9\ Method O-3116-87 is in Open File Report 93-125, Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory--Determination of
Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. USGS.
\10\ Analysts may use Fluid Management Systems, Inc. Power-Prep system in place of manual cleanup provided the analyst meets the requirements of Method
1613B (as specified in Section 9 of the method) and permitting authorities. Method 1613, Revision B, Tetra- through Octa-Chlorinated Dioxins and
Furans by Isotope Dilution HRGC/HRMS. Revision B, 1994. U.S. EPA. The full text of this method is provided in appendix A to this part and at https://www.epa.gov/cwa-methods/approved-cwa-test-methods-organic-compounds.
\11\ Method 1650, Adsorbable Organic Halides by Adsorption and Coulometric Titration. Revision C, 1997 U.S. EPA. Method 1653, Chlorinated Phenolics in
Wastewater by In Situ Acetylation and GCMS. Revision A, 1997 U.S. EPA. The full text for both of these methods is provided at appendix A in part 430
of this chapter, The Pulp, Paper, and Paperboard Point Source Category.
\12\ The compound was formerly inaccurately labeled as 2,2'-oxybis(2-chloropropane) and bis(2-chloroisopropyl) ether. Some versions of Methods 611, and
1625 inaccurately list the analyte as ``bis(2-chloroisopropyl) ether,'' but use the correct CAS number of 108-60-1.
\13\ Method O-4127-96, U.S. Geological Survey Open-File Report 97-829, Methods of analysis by the U.S. Geological Survey National Water Quality
Laboratory--Determination of 86 volatile organic compounds in water by gas chromatography/mass spectrometry, including detections less than reporting
limits, 1998, USGS.
\14\ Method O-4436-16 U.S. Geological Survey Techniques and Methods, book 5, chap. B12, Determination of heat purgeable and ambient purgeable volatile
organic compounds in water by gas chromatography/mass spectrometry, 2016, USGS.
\15\ Please refer to the following Quality Control Section: Part 6000 Individual Organic Compounds, 6020 (2019) \16\ SGS AXYS Method ATM 16130,
``Determination of 2,3,7,8-Substituted Tetra- through Octa-Chlorinated Dibenzo-p-Dioxins and Dibenzofurans (CDDs/CDFs) Using Waters and Agilent Gas
Chromatography-Tandem-Mass Spectrometry (GC/MS/MS), Revision 1.0, '' is available at: https://www.sgsaxys.com/wp-content/uploads/2022/09/SGS-AXYS-Method-16130-Rev-1.0.pdf.
\16\ Pace Analytical Method PAM-16130-SSI, ``Determination of 2,3,7,8-Substituted Tetra- through Octa-Chlorinated Dibenzo-p-Dioxins and Dibenzofurans
(CDDs/CDFs) Using Shimadzu Gas Chromatography Mass Spectrometry (GC-MS/MS), Revision 1.1,'' is available at: www.pacelabs.com.
[[Page 10764]]
Table ID--List of Approved Test Procedures for Pesticides \1\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter Method EPA \2\ \7\ \10\ Standard methods \15\ ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Aldrin.......................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812-96 See footnote,\3\ p.
(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
2. Ametryn......................... GC.................... 507, 619.............. ..................... ..................... See footnote,\3\ p.
83; See footnote,\9\
O-3106-93; See
footnote,\6\ p. S68.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\14\ O-
1121-91.
3. Aminocarb....................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94; See footnote,\6\
p. S60.
HPLC.................. 632...................
4. Atraton......................... GC.................... 619................... ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68.
GC/MS................. 625.1.................
5. Atrazine........................ GC.................... 507, 619, 608.3....... ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
GC/MS................. 525.1, 525.2, 625.1... ..................... ..................... See footnote,\11\ O-
1126-95.
6. Azinphos methyl................. GC.................... 614, 622, 1657........ ..................... ..................... See footnote,\3\ p.
25; See footnote,\6\
p. S51.
GC-MS................. 625.1................. ..................... ..................... See footnote,\11\ O-
1126-95.
7. Barban.......................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
GC/MS................. 625.1.................
8. [alpha]-BHC..................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\8\
3M0222.
GC/MS................. 625.1 \5\............. 6410 B-2020.......... ..................... See footnote,\11\ O-
1126-95.
9. [beta]-BHC...................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\8\
96(02). 3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
10. [delta]-BHC.................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\8\
96(02). 3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
11. [gamma]-BHC (Lindane).......... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1 \5\............. 6410 B-2020.......... ..................... See footnote,\11\ O-
1126-95.
12. Captan......................... GC.................... 617, 608.3............ 6630 B-2021.......... D3086-90, D5812- See footnote,\3\ p.
96(02). 7.
13. Carbaryl....................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94, See footnote,\6\
p. S60.
HPLC.................. 531.1, 632............
HPLC/MS............... 553................... ..................... ..................... See footnote,\12\ O-
2060-01.
GC/MS................. 625.1................. ..................... ..................... See footnote,\11\ O-
1126-95.
14. Carbophenothion................ GC.................... 617, 608.3............ 6630 B-2021.......... ..................... See footnote,\4\ page
27; See footnote,\6\
p. S73.
GC/MS................. 625.1.................
[[Page 10765]]
15. Chlordane...................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
16. Chloropropham.................. TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
GC/MS................. 625.1.................
17. 2,4-D.......................... GC.................... 615................... 6640 B-2021.......... ..................... See footnote,\3\ p.
115; See
footnote,\4\ O-3105-
83.
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
18. 4,4'-DDD....................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3105-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
19. 4,4'-DDE....................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2020.......... ..................... See footnote,\11\ O-
1126-95.
20. 4,4'-DDT....................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
21. Demeton-O...................... GC.................... 614, 622.............. ..................... ..................... See footnote,\3\ p.
25; See footnote,\6\
p. S51.
GC/MS................. 625.1.................
22. Demeton-S...................... GC.................... 614, 622.............. ..................... ..................... See footnote,\3\ p.
25; See footnote,\6\
p. S51.
GC/MS................. 625.1.................
23. Diazinon....................... GC.................... 507, 614, 622, 1657... ..................... ..................... See footnote,\3\ p.
25; See footnote,\4\
O-3104-83; See
footnote,\6\ p. S51.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\11\ O-
1126-95.
24. Dicamba........................ GC.................... 615................... ..................... ..................... See footnote,\3\ p.
115.
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
25. Dichlofenthion................. GC.................... 622.1................. ..................... ..................... See footnote,\4\ page
27; See footnote,\6\
p. S73.
26. Dichloran...................... GC.................... 608.2, 617, 608.3..... 6630 B-2021.......... ..................... See footnote,\3\ p.
7.
27. Dicofol........................ GC.................... 617, 608.3............ ..................... ..................... See footnote,\4\ O-
3104-83.
28. Dieldrin....................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2020.......... ..................... See footnote,\11\ O-
1126-95.
29. Dioxathion..................... GC.................... 614.1, 1657........... ..................... ..................... See footnote,\4\ page
27; See footnote,\6\
p. S73.
30. Disulfoton..................... GC.................... 507, 614, 622, 1657... ..................... ..................... See footnote,\3\ p.
25; See footnote,\6\
p. S51.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\11\ O-
1126-95.
31. Diuron......................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
[[Page 10766]]
HPLC.................. 632...................
HPLC/MS............... 553................... ..................... ..................... See footnote,\12\ O-
2060-01.
32. Endosulfan I................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M022).
GC/MS................. 625.1 \5\............. 6410 B-2020.......... ..................... See footnote,\13\ O-
2002-01.
33. Endosulfan II.................. GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\8\
3M0222.
GC/MS................. 625.1 \5\............. 6410 B-2020.......... ..................... See footnote,\13\ O-
2002-01.
34. Endosulfan Sulfate............. GC.................... 617, 608.3............ 6630 C-2021.......... ..................... See footnote,\8\
3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
35. Endrin......................... GC.................... 505, 508, 617, 1656, 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
608.3. 96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 525.1, 525.2, 625.1 6410 B-2020..........
\5\.
36. Endrin aldehyde................ GC.................... 617, 608.3............ 6630 C-2021.......... ..................... See footnote,\8\
3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
37. Ethion......................... GC.................... 614, 614.1, 1657...... ..................... ..................... See footnote,\4\ page
27; See footnote,\6\
p. S73.
GC/MS................. 625.1................. ..................... ..................... See footnote,\13\ O-
2002-01.
38. Fenuron........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
39. Fenuron-TCA.................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
40. Heptachlor..................... GC.................... 505, 508, 617, 1656, 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
608.3. 96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 525.1, 525.2, 625.1... 6410 B-2020..........
41. Heptachlor epoxide............. GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\6\ p. S73;
See footnote,\8\
3M0222.
GC/MS................. 625.1................. 6410 B-2020..........
42. Isodrin........................ GC.................... 617, 608.3............ 6630 B-2021 & C-2021. ..................... See footnote,\4\ O-
3104-83; See
footnote,\6\ p. S73.
GC/MS................. 625.1.................
43. Linuron........................ GC.................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... 553................... ..................... ..................... See footnote,\12\ O-
2060-01.
GC/MS................. ...................... ..................... ..................... See footnote,\11\ O-
1126-95.
44. Malathion...................... GC.................... 614, 1657............. 6630 B-2021.......... ..................... See footnote,\3\ p.
25; See footnote,\6\
p. S51.
GC/MS................. 625.1................. ..................... ..................... See footnote,\11\ O-
1126-95.
45. Methiocarb..................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94; See footnote,\6\
p. S60.
[[Page 10767]]
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
46. Methoxychlor................... GC.................... 505, 508, 608.2, 617, 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
1656, 608.3. 96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 525.1, 525.2, 625.1... ..................... ..................... See footnote,\11\ O-
1126-95.
47. Mexacarbate.................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94; See footnote,\6\
p. S60.
HPLC.................. 632...................
GC/MS................. 625.1.................
48. Mirex.......................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83.
GC/MS................. 625.1.................
49. Monuron........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
50. Monuron-TCA.................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
51. Neburon........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
52. Parathion methyl............... GC.................... 614, 622, 1657........ 6630 B-2021.......... ..................... See footnote,\4\ page
27; See footnote,\3\
p. 25.
GC/MS................. 625.1................. ..................... ..................... See footnote,\11\ O-
1126-95.
53. Parathion ethyl................ GC.................... 614................... 6630 B-2021.......... ..................... See footnote,\4\ page
27; See footnote,\3\
p. 25.
GC/MS................. ...................... ..................... ..................... See footnote,\11\ O-
1126-95.
54. PCNB........................... GC.................... 608.1, 617, 608.3..... 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
96(02). 7.
55. Perthane....................... GC.................... 617, 608.3............ ..................... D3086-90, D5812- See footnote,\4\ O-
96(02). 3104-83.
56. Prometon....................... GC.................... 507, 619.............. ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\11\ O-
1126-95.
57. Prometryn...................... GC.................... 507, 619.............. ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.1, 525.2, 625.1... ..................... ..................... See footnote,\13\ O-
2002-01.
58. Propazine...................... GC.................... 507, 619, 1656, 608.3. ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.1, 525.2, 625.1...
59. Propham........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
[[Page 10768]]
60. Propoxur....................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94; See footnote,\6\
p. S60.
HPLC.................. 632...................
61. Secbumeton..................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68.
GC.................... 619...................
62. Siduron........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
63. Simazine....................... GC.................... 505, 507, 619, 1656, ..................... ..................... See footnote,\3\ p.
608.3. 83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.1, 525.2, 625.1... ..................... ..................... See footnote,\11\ O-
1126-95.
64. Strobane....................... GC.................... 617, 608.3............ 6630 B-2021 & C-2021. ..................... See footnote,\3\ p.
7.
65. Swep........................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
66. 2,4,5-T........................ GC.................... 615................... 6640 B-2021.......... ..................... See footnote,\3\ p.
115; See
footnote,\4\ O-3105-
83.
67. 2,4,5-TP (Silvex).............. GC.................... 615................... 6640 B-2021.......... ..................... See footnote,\3\ p.
115; See
footnote,\4\ O-3105-
83.
68. Terbuthylazine................. GC.................... 619, 1656, 608.3...... ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68.
GC/MS................. ...................... ..................... ..................... See footnote,\13\ O-
2002-01.
69. Toxaphene...................... GC.................... 505, 508, 617, 1656, 6630 B-2021 & C-2021. D3086-90, D5812- See footnote,\3\ p.
608.3. 96(02). 7; See footnote; \8\
See footnote,\4\ O-
3105-83.
GC/MS................. 525.1, 525.2, 625.1... 6410 B-2020..........
70. Trifluralin.................... GC.................... 508, 617, 627, 1656, 6630 B-2021.......... ..................... See footnote,\3\ p.
608.3. 7; See footnote,\9\
O-3106-93.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\11\ O-
1126-95.
--------------------------------------------------------------------------------------------------------------------------------------------------------
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 IC of this
section, where entries are listed by chemical name.
\2\ 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.
\3\ Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA. This EPA
publication includes thin-layer chromatography (TLC) methods.
\4\ Methods for the Determination of Organic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S.
Geological Survey, Book 5, Chapter A3. 1987. USGS.
\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 United States Environmental Protection Agency, Supplement to the 15th Edition of Standard
Methods for the Examination of Water and Wastewater.1981. American Public Health Association (APHA).
\7\ Each analyst must make an initial, one-time, demonstration of their ability to generate acceptable precision and accuracy with Methods 608.3 and
625.1 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 608.3 or 5% of all samples analyzed with Method 625.1 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. Revised October 28, 1994. 3M Corporation.
\9\ Method O-3106-93 is in Open File Report 94-37, 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. 1994. USGS.
[[Page 10769]]
\10\ EPA Methods 608.1, 608.2, 614, 614.1, 615, 617, 619, 622, 622.1, 627, and 632 are found in Methods for the Determination of Nonconventional
Pesticides in Municipal and Industrial Wastewater, EPA 821-R-92-002, April 1992, U.S. EPA. EPA Methods 505, 507, 508, 525.1, 531.1 and 553 are in
Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume II, EPA 821-R-93-010B, 1993, U.S. EPA. EPA
Method 525.2 is in Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass
Spectrometry, Revision 2.0, 1995, U.S. EPA. EPA methods 1656 and 1657 are in Methods for The Determination of Nonconventional Pesticides In Municipal
and Industrial Wastewater, Volume I, EPA 821-R-93-010A, 1993, U.S. EPA. Methods 608.3 and 625.1 are available at: cwa-methods/approved-cwa-test-
methods-organic-compounds.
\11\ Method O-1126-95 is in Open-File Report 95-181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination
of pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring. 1995.
USGS.
\12\ Method O-2060-01 is in Water-Resources Investigations Report 01-4134, Methods of Analysis by the U.S. Geological Survey National Water Quality
Laboratory--Determination of Pesticides in Water by Graphitized Carbon-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass
Spectrometry. 2001. USGS.
\13\ Method O-2002-01 is in Water-Resources Investigations Report 01-4098, Methods of Analysis by the U.S. Geological Survey National Water Quality
Laboratory--Determination of moderate-use pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass
spectrometry. 2001. USGS.
\14\ Method O-1121-91 is in Open-File Report 91-519, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination
of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion
monitoring. 1992. USGS.
\15\ Please refer to the following applicable Quality Control Section: Part 6000 Methods, Individual Organic Compounds 6020 (2019). These Quality
Control Standards are available for download at www.standardmethods.org at no charge.
* * * * *
* * * * *
Table IH--List of Approved Microbiological Methods for Ambient Water
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter and units Method \1\ EPA Standard methods AOAC, ASTM, USGS Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Bacteria
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Coliform (fecal), number per 100 Most Probable Number p. 132 \3\........... 9221 E-2014, 9221 F-
mL. (MPN), 5 tube, 3 2014 \32\.
dilution, or
Membrane filter p. 124 \3\........... 9222 D-2015 \26\..... B-0050-85. \4\
(MF),\2\ single step.
2. Coliform (total), number per 100 MPN, 5 tube, 3 p. 114 \3\........... 9221 B-2014..........
mL. dilution, or.
MF,\2\ single step or p. 108 \3\........... 9222 B-2015 \27\ B-0025-85. \4\
two step.
MF \2\ with enrichment p. 111 \3\........... 9222 B.-2015. \27\
3. E. coli, number per 100 mL...... MPN,\5\ \7\ \13\ ..................... 9221 B.3-2014/9221 F-
multiple tube, or 2014. \10\ \12\ \32\
Multiple tube/multiple ..................... 9223 B-2016 \11\..... 991.15 \9\............ Colilert[supreg],\11\
well, or. \15\ Colilert-
18[supreg].\11\ \14\
\15\
MF,\2\ \5\ \6\ \7\ two 1103.2 \18\.......... 9222 B-2015/9222 I- D5392-93. \8\
step, or. 2015,\17\ 9213 D-
2007.
Single step........... 1603.1,\19\ 1604 \20\ ..................... ...................... m-
ColiBlue24[supreg],\
16\ KwikCount\TM\ EC
\28\ \ 29\
4. Fecal streptococci, number per MPN, 5 tube, 3 p. 139 \3\........... 9230 B-2013..........
100 mL. dilution, or.
MF,\2\ or............. p. 136 \3\ 9230 C-2013 \30\..... B-0055-85. \4\
Plate count........... p. 143. \3\
5. Enterococci, number per 100 mL.. MPN,\5\ \7\ multiple ..................... 9230 D-2013.......... D6503-99 \8\.......... Enterolert[supreg]
tube/multiple well, \11\ \21\
or
MF \2\ \5\ \6\ \7\ two 1106.2 \22\.......... 9230 C-2013 \30\..... D5259-92. \8\
step, or.
Single step, or....... 1600.1 \23\.......... 9230 C-2013. \30\
Plate count........... p. 143. \3\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Protozoa
--------------------------------------------------------------------------------------------------------------------------------------------------------
6. Cryptosporidium................. Filtration/IMS/FA..... 1622, \24\ 1623, \25\
1623.1. \25\ \31\
7. Giardia......................... Filtration/IMS/FA..... 1623, \25\ 1623.1.
\25\ \31\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table 1H notes:
\1\ The method must be specified when results are reported.
\2\ A 0.45-[micro]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\ Microbiological Methods for Monitoring the Environment, Water and Wastes. EPA/600/8-78/017. 1978. US EPA.
\4\ 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. 1989. USGS.
\5\ 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.
\6\ When the MF method has not been used previously to test waters with high turbidity, large numbers 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.
\7\ 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.
\8\ Annual Book of ASTM Standards--Water and Environmental Technology. Section 11.02. 2000, 1999, 1996. ASTM International.
\9\ Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. 1995. AOAC International.
\10\ The multiple-tube fermentation test is used in 9221B.3-2014. 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.
\11\ These tests are collectively known as defined enzyme substrate tests.
[[Page 10770]]
\12\ After prior enrichment in a presumptive medium for total coliform using 9221B.3-2014, 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-2014. Commercially available EC-MUG media or EC media
supplemented in the laboratory with 50 [micro]g/mL of MUG may be used.
\13\ 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[supreg] may be enumerated with
the multiple-well procedures, Quanti-Tray[supreg] or Quanti-Tray[supreg]/2000, and the MPN calculated from the table provided by the manufacturer.
\14\ Colilert-18[supreg] is an optimized formulation of the Colilert[supreg] 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[supreg] test and is recommended for marine water samples.
\15\ Descriptions of the Colilert[supreg], Colilert-18[supreg], Quanti-Tray[supreg], and Quanti-Tray[supreg]/2000 may be obtained from IDEXX
Laboratories Inc.
\16\ A description of the mColiBlue24[supreg] test may be obtained from Hach Company.
\17\ Subject coliform positive samples determined by 9222B-2015 or other membrane filter procedure to 9222I-2015 using NA-MUG media.
\18\ Method 1103.2: Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC), [in draft as
of 2023]. US EPA.
\19\ Method 1603.1: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar (Modified
mTEC), [in draft as of 2023]. US EPA.
\20\ Method 1604: Total Coliforms and Escherichia coli (E. coli) in Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI
Medium), EPA 821-R-02-024. September 2002. US EPA.
\21\ A description of the Enterolert[supreg] test may be obtained from IDEXX Laboratories Inc.
\22\ Method 1106.2: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA), [in draft as of 2023]. US EPA.
\23\ Method 1600.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI), [in draft as of
2023]. US EPA.
\24\ Method 1622 uses a 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.
Method 1622: Cryptosporidium in Water by Filtration/IMS/FA, EPA-821-R-05-001. December 2005. US EPA.
\25\ Methods 1623 and 1623.1 use a 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. Method 1623: Cryptosporidium and Giardia in Water by Filtration/IMS/FA. EPA-821-R-05-002.
December 2005. US EPA. Method 1623.1: Cryptosporidium and Giardia in Water by Filtration/IMS/FA. EPA 816-R-12-001. January 2012. US EPA.
\26\ On a monthly basis, at least ten blue colonies from positive samples must be verified using Lauryl Tryptose Broth and EC broth, followed by count
adjustment based on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications
should be done from randomized sample sources.
\27\ On a monthly basis, at least ten sheen colonies from positive samples must be verified using Lauryl Tryptose Broth and brilliant green lactose bile
broth, followed by count adjustment based on these results; and representative non-sheen colonies should be verified using Lauryl Tryptose Broth.
Where possible, verifications should be done from randomized sample sources.
\28\ A description of KwikCount\TM\ EC may be obtained from Micrology Laboratories LLC.
\29\ Approved for the analyses of E. coli in freshwater only.
\30\ Verification of colonies by incubation of BHI agar at 10 0.5 [deg]C for 48 3 h is optional. As per the Errata to the 23rd
Edition of Standard Methods for the Examination of Water and Wastewater ``Growth on a BHI agar plate incubated at 10 0.5 [deg]C for 48
3 h is further verification that the colony belongs to the genus Enterococcus.''
\31\ Method 1623.1 includes updated acceptance criteria for IPR, OPR, and MS/MSD and clarifications and revisions based on the use of Method 1623 for
years and technical support questions.
\32\ 9221 F.2-2014 allows for simultaneous detection of E. coli and thermotolerant fecal coliforms by adding inverted vials to EC-MUG; the inverted
vials collect gas produced by thermotolerant fecal coliforms.
(b) The material listed in this paragraph (b) is incorporated by
reference into this section with the approval of the Director of the
Federal Register under 5 U.S.C. 552(a) and 1 CFR part 51. All approved
material is available for inspection at the EPA and at the National
Archives and Records Administration (NARA). Contact the EPA at: EPA's
Water Docket, EPA West, 1301 Constitution Avenue NW, Room 3334,
Washington, DC 20004; telephone: 202-566-2426; email: [email protected]. For information on the availability of this
material at NARA, visit www.archives.gov/federal-register/cfr/ibr-locations.html or email [email protected]. The material may be
obtained from the following sources in this paragraph (b).
* * * * *
(8) * * *
(ii) Method 1103.2: Escherichia coli (E. coli) in Water by Membrane
Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar
(Modified mTEC). [in draft as of 2023]. EPA Table IH, Note 18.
(iii) Method 1106.2: Enterococci in Water by Membrane Filtration
Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA). [in draft as of
2023]. Table IH, Note 22.
(iv) Method 1600.1: Enterococci in Water by Membrane Filtration
Using membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI). [in
draft as of 2023]. EPA. Table 1A, Note 24; Table IH, Note 23.
(v) Method 1603.1: Escherichia coli (E. coli) in Water by Membrane
Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar
(Modified mTEC). [in draft as of 2023]. EPA. Table IA, Note 21; Table
IH, Note 19.
* * * * *
(10) * * *
(i) Standard Methods for the Examination of Water and Wastewater.
14th Edition, 1975. Table IB, Notes 27 and 86.
* * * * *
(viii) 2120, Color. 2021. Table IB.
(ix) 2130, Turbidity. 2020. Table IB.
(x) 2310, Acidity. 2020. Table IB.
(xi) 2320, Alkalinity. 2021. Table IB.
(xii) 2340, Hardness. 2021. Table IB.
(xiii) 2510, Conductivity. 2021. Table IB.
(xiv) 2540, Solids. 2020. Table IB.
* * * * *
(xvi) 3111, Metals by Flame Atomic Absorption Spectrometry. 2019.
Table IB.
(xvii) 3112, Metals by Cold-Vapor Atomic Absorption Spectrometry.
2020. Table IB.
(xviii) 3113, Metals by Electrothermal Atomic Absorption
Spectrometry. 2020. Table IB.
(xix) 3114, Arsenic and Selenium by Hydride Generation/Atomic
Absorption Spectrometry. 2020, Table IB.
(xx) 3120, Metals by Plasma Emission Spectroscopy. 2020. Table IB.
(xxi) 3125, Metals by Inductively Coupled Plasma-Mass Spectrometry.
2020. Table IB.
(xxii) 3500-Al, Aluminum. 2020. Table IB.
(xxiii) 3500-As, Arsenic. 2020. Table IB.
(xxiv) 3500-Ca, Calcium. 2020. Table IB.
(xxv) 3500-Cr, Chromium. 2020. Table IB.
(xxvi) 3500-Cu, Copper. 2020. Table IB.
* * * * *
(xxviii) 3500-Pb, Lead. 2020. Table IB.
(xxix) 3500-Mn, Manganese. 2020. Table IB.
(xxx) 3500-K, Potassium. 2020. Table IB.
(xxxi) 3500-Na, Sodium. 2020. Table IB.
* * * * *
(xxxiii) 3500-Zn, Zinc. 2020. Table IB.
(xxxiv) 4110, Determination of Anions by Ion Chromatography. 2020.
Table IB.
(xxxv) 4140, Inorganic Anions by Capillary Ion Electrophoresis.
2020. Table IB.
* * * * *
[[Page 10771]]
(xxxvii) 4500 Cl-, Chloride. 2021. Table IB.
* * * * *
(xxxix) 4500-CN-, Cyanide. 2021. Table IB.
(xl) 4500-F-, Fluoride. 2021. Table IB.
(xli) 4500-H\+\, pH Value. 2021. Table IB.
(xlii) 4500-NH3, Nitrogen (Ammonia). 2021. Table IB.
(xliii) 4500-NO2-, Nitrogen (Nitrite). 2021.
Table IB.
(xliv) 4500-NO3-, Nitrogen (Nitrate). 2019.
Table IB.
(xlv) 4500-N(org), Nitrogen (Organic). 2021. Table IB.
(xlvi) 4500-O, Oxygen (Dissolved). 2021. Table IB.
(xlvii) 4500-P, Phosphorus. 2021. Table IB.
(xlviii) 4500-SiO2, Silica. 2021. Table IB.
(xlix) 4500-S2-, Sulfide. 2021. Table IB.
(l) 4500-SO32-, Sulfite. 2021. Table IB.
(li) 4500-SO42-, Sulfate. 2021. Table IB.
* * * * *
(lv) 5520, Oil and Grease. 2021. Table IB.
(lvi) 5530, Phenols. 2021. Table IB.
(lvii) 5540, Surfactants. 2021. Table IB.
(lviii) 6200, Volatile Organic Compounds. 2020. Table IC.
(lix) 6410, Extractable Base/Neutrals and Acids. 2020. Tables IC
and ID.
(lx) 6420, Phenols. 2020. Table IC.
(lxi) 6440, Polynuclear Aromatic Hydrocarbons. 2021. Table IC.
(lxii) 6630, Organochlorine Pesticides. 2021. Table IC.
(lxiii) 6640, Acidic Herbicide Compounds. 2021. Table IC.
* * * * *
(lxvii) 9221, Multiple-Tube Fermentation Techniques for Members of
the Coliform Group. 2014. Table IA, Notes 12, 14 and 33; Table IH,
Notes 10, 12 and 32.
* * * * *
(15) * * *
(xi) ASTM D888-18, Standard Test Methods for Dissolved Oxygen in
Water. May 2018. Table IB.
* * * * *
(xx) ASTM D1293-18, Standard Test Methods for pH of Water. January
2018. Table IB.
* * * * *
(xxx) ASTM D1976-20, Standard Test Method for Elements in Water by
Inductively-Coupled Argon Plasma Atomic Emission Spectroscopy. June
2020. Table IB.
* * * * *
(xxxii) ASTM D2330-20, Standard Test Method for Methylene Blue
Active Substances. February 2020. Table 1B.
* * * * *
(lix) ASTM D5907-18, Standard Test Methods for Filterable Matter
(Total Dissolved Solids) and Nonfilterable Matter (Total Suspended
Solids) in Water. May 2018. Table IB.
* * * * *
(lxv) ASTM D7237-18, Standard Test Method for Free Cyanide with
Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and
Amperometric Detection. January 2019. Table IB.
(lxvi) ASTM D7284-20, Standard Test Method for Total Cyanide in
Water by Micro Distillation followed by Flow Injection Analysis with
Gas Diffusion Separation and Amperometric Detection. August 2020. Table
IB.
(lxvii) ASTM D7365-09a (Reapproved 2015), Standard Practice for
Sampling, Preservation and Mitigating Interferences in Water Samples
for Analysis of Cyanide. August 2015. Table II, Notes 5 and 6.
* * * * *
(lxix) ASTM D7573-18a\e1\, Standard Test Method for Total Carbon
and Organic Carbon in Water by High Temperature Catalytic Combustion
and Infrared Detection, January 2019. Table IB.
* * * * *
(33) Pace Analytical Services, LLC, 1800 Elm Street SE,
Minneapolis, MN 55414. Telephone: 612-656-2240.
(i) PAM-16130-SSI, Determination of 2,3,7,8-Substituted Tetra-
through Octa-Chlorinated Dibenzo-p-Dioxins and Dibenzofurans (CDDs/
CDFs) Using Shimadzu Gas Chromatography Mass Spectrometry (GC-MS/MS),
Revision 1.1, May 20, 2022. Table IC, Note 17.
(ii) [Reserved]
(34) SGS AXYS Analytical Services, Ltd., 2045 Mills Road, Sidney,
British Columbia, Canada, V8L 5X2. Telephone: 1-888-373-0881.
(i) ATM 16130, Determination of 2,3,7,8-Substituted Tetra- through
Octa-Chlorinated Dibenzo-p-Dioxins and Dibenzofurans (CDDs/CDFs) Using
Waters and Agilent Gas Chromatography-Tandem-Mass Spectrometry (GC/MS/
MS)., Revision 1.0, August 2020. Table IC, Note 16
(ii) [Reserved]
* * * * *
(e) * * *
Table II--Required Containers, Preservation Techniques, and Holding
Times
------------------------------------------------------------------------
-------------------------------------------------------------------------
* * * * * * *
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* * * * * * *
\5\ ASTM D7365-09a (15) specifies treatment options for samples
containing oxidants (e.g., chlorine) for cyanide analyses. Also,
Section 9060A of Standard Methods for the Examination of Water and
Wastewater (23rd edition) addresses dechlorination procedures for
microbiological analyses.
* * * * *
[FR Doc. 2023-02391 Filed 2-17-23; 8:45 am]
BILLING CODE 6560-50-P
