[Federal Register Volume 89, Number 74 (Tuesday, April 16, 2024)]
[Rules and Regulations]
[Pages 27288-27327]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 2024-07412]
[[Page 27287]]
Vol. 89
Tuesday,
No. 74
April 16, 2024
Part IV
Environmental Protection Agency
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40 CFR Part 136
Clean Water Act Methods Update Rule for the Analysis of Effluent; Final
Rule
Federal Register / Vol. 89 , No. 74 / Tuesday, April 16, 2024 / Rules
and Regulations
[[Page 27288]]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 136
[EPA-HQ-OW-2022-0901; FRL 9346-02-OW]
RIN 2040-AG25
Clean Water Act Methods Update Rule for the Analysis of Effluent
AGENCY: Environmental Protection Agency (EPA).
ACTION: Final rule.
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SUMMARY: The U.S. Environmental Protection Agency (EPA) is finalizing
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 the
EPA's National Pollutant Discharge Elimination System permit program.
The Clean Water Act requires the EPA to promulgate these test
procedures (analytical methods) for analysis of pollutants. The EPA
anticipates that these changes will provide increased flexibility for
the regulated community in meeting monitoring requirements while
improving data quality. In addition, this update to the CWA methods
will incorporate technological advances in analytical technology and
make a series of minor changes and corrections to existing approved
methods. As such, the EPA expects that these changes will not result in
any negative economic impacts.
DATES: This final rule is effective on June 17, 2024. The incorporation
by reference of certain material listed in this rule and is approved by
the Director of the Federal Register as of June 17, 2024.
ADDRESSES: The EPA has established a docket for this action under
Docket ID No. EPA-OW-HQ-2022-0901. All documents in the docket are
listed on the http://www.regulations.gov website. Although listed in
the index, some information is not publicly available, e.g., CBI or
other information whose disclosure is restricted by statute. Certain
other material, such as copyrighted material, is not placed on the
internet and will be publicly available only in hard copy form.
Publicly available docket materials are available electronically
through http://www.regulations.gov.
FOR FURTHER INFORMATION CONTACT: Tracy Bone, Engineering and Analysis
Division, Office of Water (4303T), 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. General Information
II. Background
III. Corrections or Amendments to the Text and Tables of 40 CFR Part
136
IV. Incorporation by Reference
V. Statutory and Executive Order Reviews
I. General Information
This preamble describes the abbreviations and acronyms; reasons for
the rule; and a summary of the changes and clarifications; the legal
authority for the rule; methods incorporated by reference; and a
summary of the changes and clarifications.
A. Does this action apply to me?
Entities potentially affected by the requirements of this action
include:
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Examples of potentially affected
Category entities
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State, Territorial, and Indian States authorized to administer the
Tribal Governments. National Pollutant Discharge
Elimination System 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 or
other municipality-owned facilities
that must conduct monitoring to
comply with NPDES permits.
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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 the 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 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, the EPA updates the approved methods in 40 CFR part
136. In general, the changes in this action fall into four 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 that are
similar to methods previously adopted as EPA-approved methods in 40 CFR
part 136. The third category is methods the EPA has reviewed under the
agency's national Alternate Test Procedure program and preliminarily
concluded are appropriate for nationwide use. The fourth category is
corrections or amendments to the text and tables of 40 CFR part 136.
The EPA is finalizing 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 revisions.
C. What is the Agency's authority for taking this action?
The EPA is promulgating 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 the 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].'' The EPA generally
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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).
II. Background
Abbreviations and Acronyms Used in the Preamble
ASTM: ASTM International \1\
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\1\ Formerly known as the American Society for Testing and
Materials (ASTM).
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ATP: Alternate Test Procedure
BHI: Brain heart infusion
CATC: Cyanide Amenable to Chlorination
CFR: Code of Federal Regulations
CNCl: Cyanogen Chloride
CWA: Clean Water Act
EC-MUG: EC broth with 4-methylumbelliferyl-[beta]-D-glucuronide
EDTA: Ethylenediaminetetraacetic acid
EPA: the U.S. 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
IBR: Incorporation by Reference
ICP/AES: Inductively Coupled Plasma-Atomic Emission Spectroscopy
NED: N-(1-naphthyl)-ethylenediamine dihydrochloride
NPDES: National Pollutant Discharge Elimination System
m/z: Mass to Charge Ratio
MF: Membrane Filtration
MPN: Most Probable Number
nm: Nanometer
NTTAA: National Technology Transfer and Advancement Act
POTW: Publicly Owned Treatment Works
QC: Quality Control
TKN: Total Kjeldahl Nitrogen
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
the EPA has approved the use of more than one method.\2\
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\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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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 the EPA's General Pretreatment Regulations for Existing
and New Sources of Pollution, 40 CFR 136.1 and 40 CFR 403.12(b)(5)(v).
On February 21, 2023, the EPA proposed to update the approved
methods in 40 CFR part 136. The EPA received 20 comments on the
proposed rulemaking (February 21, 2023, 88 FR 10724) from laboratory
associations, state environmental agencies, trade associations and
citizens. All commenters supported finalizing this rule and approving
each proposed method.
There were some specific comments that are outside the scope of
this rulemaking. As stated in the proposed rule (88 FR 10725, February
21, 2023,), the EPA only considered new or revised methods that were
submitted to the EPA. Method withdrawals, methods for new parameters,
methods based on new technologies (except methods approved through the
alternate test procedure program) and VCSB methods not submitted from
VCSBs were not considered for this routine update. Commenters
requesting changes to VCSB, or vender methods should work through the
method owner to revise the method and submit any supporting data to the
EPA for consideration.
Commenters noted that there was a format error in the proposed
rulemaking language on Table IC, footnotes 15, 16 and 17, (88 FR 10763,
February 21, 2023). The new footnote 16 was inadvertently added to the
end of footnote 15. The information in the new footnotes is correctly
described in the preamble (88 FR 10738, February 21, 2023). This
typographical error of the order and numbering of the footnotes has
been corrected in the final rule. In addition, the following parameters
were missing from the preamble discussions of the revision of Standard
Methods method 6410B-2020: 2,2'-oxybis(1-chloropropane) (also referred
to as bis[2-Chloro-1-methylethyl] ether); hexachloroethane; and N-
nitrosodimethylamine. The revised 6410B-2020 discussion in Section
IV.C.35 of this preamble is correct.
III. Corrections or Amendments to the Text and Tables of 40 CFR Part
136
In addition to the method revision incorporated by reference as
discussed in Section IV of this preamble, Standard Methods has revised
a few of their general quality control sections (2020, 3020, 4020 and
5020). The EPA is updating the year of the current references to these
sections in 136.3 Table IB footnote 85. The EPA is also adding a
reference to an additional Standard Methods Quality Control section:
Part 6000 Individual Organic Compounds, 6020. These Quality Control
Standards are available for download at www.standardmethods.org at no
charge. The EPA is correcting several minor errors or inconsistencies
in the tables of approved methods. The EPA is making the following
changes to 40 CFR 136.3, Tables IA, IB, IC, ID or IH:
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 United States Geologic Survey 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 into two parameters to eliminate confusion as to which methods
were approved for biosolids.
3. Table IA parameter 3 and IH parameter 2. Moving the phrase
``two-step'' 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. Adding footnote 86 to Method 419D. Method 419D is
listed as an approved method for of 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. Adding footnote 15 to the Standard Methods
column header and adding footnote 15 to refer to Quality Control
Section: Part 6000 Individual Organic Compounds, 6020 (2019).
8. Table IC. Changing parameter 39, dichlorodifluoromethane, to
refer to Method 6200 B rather than 6200 C for the GC/MS method.
9. Table IC. Adding footnote 10 to parameters 66-72, 95, 96 and 97
which
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were 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. Moving method B-0025-85 down one row
because it was inadvertently moved in an earlier rulemaking. This
method is a single step membrane filtration method rather than a most
probable number method.
11. Table II. Revising footnote 5 for the preservation and holding
time requirements for cyanide to add the year (2015) of the ASTM method
D7365-09a (15).
The recommended sampling and preservation procedures in the ASTM
method have not changed since 2009, but the change to footnote 5
simplifies 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 incorporated by reference
section and in footnote 5 to Table II.
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 rule contains revisions to VCSB methods that are currently
incorporated by reference, (see Sections IV.B, IV.C, and IV.E of this
preamble). Two VCSBs have made such revisions: Standard Methods and
ASTM. The VCSB methods are consistent with the requirements of the
National Technology Transfer and Advancement Act, 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. This rule also includes two vendor ATPs (see Section
IV.D of this preamble) and four revised EPA methods (see Section IV.A
of this preamble) which the EPA is incorporating by reference.
The rule incorporates by reference the methods added in an earlier
Methods Update Rule (86 FR 27226, May 19, 2021). The EPA inadvertently
failed to complete the incorporation by reference review process for
that final rule. The EPA proposed 68 methods for incorporation by
reference into 40 CFR 136.3 (84 FR 56590, October 22, 2019). Other than
ASTM D7365-09a (Reapproved 2015) and the EPA Method 1623.1, the methods
are described in the 2019 proposal as well as the 2021 final rule. ASTM
D7365-09a (Reapproved 2015) and Method 1623.1 are summarized in this
preamble.
The EPA is also incorporating by reference an errata sheet in Table
IA, footnotes 25, 26, 27. The U.S. EPA Whole Effluent Toxicity (WET)
Methods Errata Sheet, EPA 821-R-02-012-ES, corrects and clarifies the
WET methods referenced in those footnotes. The errata sheet was
described and promulgated as part of the 2017 Clean Water Act Methods
Update Rule for the Analysis of Effluent (see 82 FR 40841, August 28,
2017; docket number EPA-HQ-OW-2014-0797). The EPA inadvertently failed
to incorporate by reference the errata sheet in the 2017 final rule.
The following paragraphs provide details on the methods
incorporated by reference.
A. Changes to 40 CFR 136.3 To Include New Versions of Previously
Approved EPA Methods
The EPA is adding 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 EPA is also
summarizing method 1623.1 that was added in the earlier rule (86 FR
27226, May 19, 2021) but not summarized. The revisions include
standardizing language between the related methods, updating to reflect
current lab practices and clarifying edits.
These methods each describe a membrane filter procedure for the
detection and enumeration of either enterococci or Escherichia coli
bacteria 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 membrane-
Enterococcus (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.
5. Cryptosporidium and Giardia. Method 1623.1 describes a method
for the detection of Cryptosporidium and Giardia in ambient water by
concentration immunomagnetic separation (IMS), and immunofluorescence
assay (FA) microscopy. A water sample is filtered and the oocysts,
cysts, and extraneous materials are retained on the filter. EPA Method
1623.1 includes updated acceptance criteria for IPR, OPR, and MS/MSD,
and clarifications and revisions based on the use of EPA Method.
The EPA methods are available free of charge on our websites
(epa.gov/cwa-methods/approved-cwa-microbiological-test-methods),
therefore the EPA methods incorporated by reference are reasonably
available.
B. Changes to 40 CFR 136.3 To Include New Versions of Approved ASTM
Methods
The EPA is adding 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
changes will affect the performance of the method. The following
describes the changes to current ASTM methods that the EPA is including
in 40 CFR part 136. Each entry contains (in the following order):
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the parameter, the ASTM method number (the last two digits in the
method number represent the year ASTM published the method), 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.
ASTM methods can be purchased from astm.org. The price of ASTM
standards is not fixed. The price generally ranges between $50 and $100
per method. ASTM also offers memberships or subscriptions that allow
unlimited access to their methods. The ASTM methods incorporated by
reference are reasonably available.
The EPA is adding the following 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 DO in
the sample. Standard D888-18B measures DO in the sample with an
electrochemical probe that produces an electrical potential which is
logarithmically proportional to the concentration of DO in the sample.
Standard D888-18C measures DO with a luminescence-based sensor probe
that employs frequency domain lifetime-based luminescence quenching and
signal processing.
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.
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 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.
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. The
concentration of methylene blue active substances is determined in
comparison to a standard curve.
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.
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 the EPA anticipates will improve data
quality. There are no other procedural changes.
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 the hydrogen cyanide
diffuses through a hydrophobic gas diffusion membrane into an alkaline
solution and is detected amperometrically with a silver electrode.
8. Cyanide. D7365-09a (Reapproved 2015) 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.
9. 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.
C. Changes to 40 CFR 136.3 To Include New Versions of Approved
``Standard Methods'' Methods
The EPA is approving 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.
Each entry contains the Standard Method number and date, the
parameter, and a brief description of the analytical method. The EPA
lists only one version of a method. The date indicates the specific
version approved for use under the CWA. The methods listed below are
organized according to the table at 40 CFR part 136 in the order in
which they appear.
Methods approved under Standard Methods can be purchased from
standardmethods.org. The price generally ranges between from $60 to $80
per method. Standard Methods also offers memberships or subscriptions
that allow unlimited access to their
[[Page 27292]]
methods. The methods incorporated by reference are reasonably
available.
The EPA is adding the following methods to Tables IB, IC, and ID 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.
2120 F-2021, American Dye Manufacturers Institute (ADMI) Weighted-
Ordinate Spectrophotometric Method. This method calculates single-
number color difference values (i.e., uniform color differences) in
accordance with the Adams-Nickerson chromatic value formula. 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.
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.
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.
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.
5. Hardness.
a. In 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.
b. In 2340 C-2021, Ethylenediaminetetraacetic acid 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 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.
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.
7. Residue-Total.
a. 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.
b. 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 three
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.
c. 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.
d. 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.
e. 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 one liter 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
[[Page 27293]]
mL/L. When applicable, the recorded volume is corrected for
interference from pockets of liquid volume.
8. Multiple metals by flame atomic absorption spectrometry.
a. 3111 B-2019, Direct Air-Acetylene Flame Method. The method 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 method is approved in Table IB
for determination of cadmium, chromium, cobalt, copper, iron, lead,
nickel, silver, and zinc. The EPA is also approving 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 method is approved in Table IB for determination of
aluminum, barium, beryllium, molybdenum, osmium, titanium, and
vanadium. In addition, the EPA is approving 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 method 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 method is
approved in Table IB for determination of mercury.
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 method 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.
a. 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 method is approved in Table IB for
determination of arsenic and selenium.
b. 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 method 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 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 method 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
[[Page 27294]]
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-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 undergoes 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 method
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 method 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
method 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 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 method
is approved in Table IB for determination of calcium.
d. Chromium. 3500-Cr B-2020, Colorimetric Method measures total
chromium and dissolved hexavalent chromium, (chromium VI). For total
chromium, an unfiltered sample must first be digested using an approved
digestion procedure (see Table IB, footnote 4). For dissolved
hexavalent chromium, a sample is filtered, and the hexavalent chromium
is determined colorimetrically by reaction with diphenylcarbazide in
acid solution. A red-violet colored complex of unknown composition is
produced. The method is approved in Table IB for determination of total
chromium after digestion of the sample, and for dissolved hexavalent
chromium (chromium VI).
In 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 method 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 method 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 method 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
[[Page 27295]]
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 method 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 method 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
method 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 method 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, 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 method 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 method 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
method 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 method 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 to 10, as
opposed to 7 to 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 method 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 extends the range of measurable chloride
concentrations.
[[Page 27296]]
The method 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 method 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 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 samples containing
sulfides, fatty acids, oxidizing agents, nitrites, and nitrates. The
method 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 method 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 method 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 less than
8 without hydrolyzing to cyanate (CNO-). After 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 method 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 method 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
less than 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 method 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 method 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 method 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 method 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. method is approved in Table IB for
determination of fluoride.
20. 4500 Hydrogen ion (pH). In 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
[[Page 27297]]
is used. The electromotive force 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 Total (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 method 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 method 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 TKN in the original sample. The method is
approved in Table IB for determination of TKN.
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 method 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 method is approved in Table IB for determination of
ammonia as well as for determination of TKN 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 method is approved in Table IB for determination of
ammonia, as well as for determination of TKN 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 method is approved in
Table IB for determination of ammonia, as well as for determination of
TKN 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 method is approved in
Table IB for determination of ammonia, as well as for determination of
TKN 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 method is approved in
Table IB for determination of ammonia, as well as for determination of
TKN 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 method is approved in Table IB for
determination of ammonia, as well as for determination of TKN after
appropriate digestion/distillation of the sample.
23. 4500-NO2- Nitrite as Nitrogen. 4500-
NO2- B-2021,
[[Page 27298]]
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 method 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 method 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 method 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 method 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.
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 method 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 method 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 method is approved in Table IB for determination of DO.
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 DO 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 DO 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 method is approved in Table IB for determination of DO.
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
method is approved in Table IB for determination of DO.
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 method is approved in Table IB
for determination of DO.
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
method is approved in Table IB for determination of DO.
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 method is approved in Table IB
for determination of DO.
g. 4500-O H-2021, Luminescence-based Method. The optical probe uses
luminescence-based oxygen sensors to measure the light-emission
[[Page 27299]]
characteristics of a luminescent reaction; oxygen quantitatively
quenches the luminescence. The change in the luminescence signal's
lifetime correlates to the DO concentration. The method is approved in
Table IB for determination of DO.
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 method is 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 evaluated when reporting concentrations less
than 10 [micro]g/L. The method 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 method 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 method 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 method 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 method 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
method 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. The
method 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
one mg/L if interferences are absent and if loss of H2S is
avoided. The method 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 method 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 method 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 method 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
[[Page 27300]]
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 method 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 method 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 method 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 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 method 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
method 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 methylthymol blue
(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 method 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 method 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 method 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 method 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 method 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 method 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. In 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 to methylene blue active substances at concentrations down
to about 0.025 mg/L. The method is approved in Table IB for
determination of surfactants.
34. 6200 Volatile Organic Compounds Series.
a. 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
backflushed 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
method is approved in Table IC for determination of
[[Page 27301]]
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 purging is
complete, the trap is heated and backflushed 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 method 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, the EPA is
approving method 6410-B for endrin aldehyde in Table ID. This parameter
was inadvertently left off the 2007 MUR rulemaking (72 FR 11200, March
12, 2007). The method 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, hexachloroethane, indeno(1,2,3-c,d) pyrene,
isophorone, 2-methyl-4,6-dinitrophenol, naphthalene, nitrobenzene, 2-
nitrophenol, 4-nitrophenol, N-nitrosodimethylamine, n-nitrosodi-n-
propylamine, n-nitrosodiphenylamine, 2,2'-oxybis(1-chloropropane), 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 method 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 method 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
[[Page 27302]]
regarding preparation of packed columns, replaces information regarding
the 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 method 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. In this procedure, 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 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 method is approved in Table ID for determination of
aldrin, [alpha]-BHC, [beta]-BHC, [delta]-BHC, [gamma]-BHC (lindane),
chlordane, 4,4[acute]-DDD, 4,4[acute]-DDE, 4,4[acute]-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 chlorophenoxy
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
method 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, the EPA maintains a program that
allows method developers to apply for the 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. The EPA is approving 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 the 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 rule.
These new methods are: SGS AXYS Method 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- 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 and Agilent Technologies,
and between Pace Analytical Services LLC and the instrument
manufacturer Shimadzu Scientific Instruments, Inc. These final methods
are heavily adapted from EPA 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.
The ATP methods are available free of charge on their respective
websites (sgsaxys.com or pacelabs.com), therefore the ATP methods
incorporated by reference are reasonably available.
In these two methods, referred to in the rule as SGS AXYS 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 (1613B) 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. Changes to 40 CFR 136.3 To Include New Standard Methods Committee
Methods Based on Previously Approved Technologies
The EPA is 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. As discussed in Section
IV. B and C of this preamble, these methods are reasonably available.
The EPA is adding 4500-CN- P-2021, 4500-CN-
Q-2021, 4500 CN- R-2021, and 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-
[[Page 27303]]
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
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.
V. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review and Executive
Order 14094: Modernizing Regulatory Review
This action is not a significant regulatory action as defined in
Executive Order 12866, as amended by Executive Order 14094, and was
therefore not subject to a requirement for Executive Order 12866
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 rule merely
revises or adds alternate CWA test procedures.
C. Regulatory Flexibility Act (RFA)
I certify that this action will not have a significant economic
impact on a substantial number of small entities under the RFA. This
action will not impose any requirements on small entities. This action
would approve new alternate 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, the EPA expects the revisions would lead to few, if any,
increased costs. The 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 rule
adds 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 the methods approved by the EPA and 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 Sections IV. A through D 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
[[Page 27304]]
enforceable duty on any state, local or tribal governments or the
private sector.
E. Executive Order 13132: Federalism
This final rule does not have federalism implications. It will not
have substantial direct effects on the states, on the relationship
between the national government and the states, or on the distribution
of power and responsibilities among the various levels of government.
F. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments
This action does not have tribal implications as specified in
Executive Order 13175. This rule would merely approve new alternate and
revised versions of test procedures. The EPA has concluded that the
final rule would not lead to any costs to any tribal governments, and
if incurred, the 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
The EPA interprets Executive Order 13045 as applying only to those
regulatory actions that concern environmental health or safety risks
that the EPA has reason to believe may disproportionately affect
children, per the definition of ``covered regulatory action'' in
section 2-202 of the Executive Order.
Therefore, this action is not subject to Executive Order 13045
because it does not concern an environmental health risk or safety
risk. Since this action does not concern human health, EPA's Policy on
Children's Health also does not apply.
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 significant regulatory action under Executive Order 12866.
I. National Technology Transfer and Advancement Act of 1995
This action involves technical standards. The EPA is approving the
use of technical standards developed and recommended by the Standard
Methods Committee and ASTM International for use in compliance
monitoring where the EPA determined that those standards meet the needs
of CWA programs. As described above, this final rule is consistent with
the NTTAA.
J. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations
The 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
communities with environmental justice concerns. This action has no
effect on communities because this action will approve new alternate
and revised versions of CWA testing procedures. These changes would
provide increased flexibility for the regulated community in meeting
monitoring requirements while improving data quality. In addition, this
update to the CWA methods will incorporate technological advances in
analytical technology. Although this action does not concern human
health or environmental conditions, the EPA identifies and addresses
environmental justice concerns 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.
K. Congressional Review Act
This action is subject to the Congressional Review Act and the EPA
will submit a rule report to each House of the Congress and to the
Comptroller General of the United States. This is not a ``major rule''
as defined by 5 U.S.C. 804(2).
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 forth in the preamble, the EPA amends 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 by:
0
a. In paragraph (a), revising tables IA, IB, IC, ID, and IH;
0
b. Revising paragraph (b) introductory text;
0
c. Revising and republishing paragraphs (b)(8), (10), (15), (19), (26),
and (27);
0
d. Redesignating paragraphs (b)(33) through (39) as paragraphs (b)(35)
through (41);
0
e. Adding new paragraphs (b)(33) and (34);
0
f. Revising the newly redesignated paragraphs (b)(40) introductory
text, (b)(40)(ii), (ix), and (xiv); and
0
g. In paragraph (e), table II, revising Footnote ``5''.
The revisions and additions read as follows:
Sec. 136.3 Identification of test procedures.
(a) * * *
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 Number p. 132,\3\ 1680,\11\ 9221 E-2014.
gram dry weight. (MPN), 5 tube, 3 \15\ 1681 \11\ \20\
dilution, or.
Membrane filter (MF),\2\ p. 124 \3\........... 9222 D-2015.\29\
\5\ single step.
2. Coliform (fecal), number per MPN, 5 tube, 3 dilution, p. 132 \3\........... 9221 E-2014, 9221 F-
100 mL. or. 2014.\33\
Multiple tube/multiple Colilert-
well, or. 18[supreg].\13\
\18\ \28\
MF,\2\ \5\ single step \5\ p. 124 \3\........... 9222 D-2015 \29\..... B-0050-85. \4\
3. Coliform (total), number per MPN, 5 tube, 3 dilution, p. 114 \3\........... 9221 B-2014.
100 mL. or.
MF,\2\ \5\ single step or. p. 108 \3\........... 9222 B-2015 \30\ B-0025-85.\4\
MF, \2\ \5\ two step with p. 111 \3\........... 9222 B-2015.\30\.....
enrichment.
[[Page 27305]]
4. E. coli, number per 100 mL..... MPN \6\ \8\ \16\ multiple 9221 B2014/9221 F-
tube, or. 2014.\12\ \14\ \33\
multiple tube/multiple ..................... 9223 B-2016 \13\..... 991.15 \10\......... Colilert[supreg].\13
well, or. \ \18\
Colilert-
18[supreg].\13\
\17\ \18\
MF,\2\ \5\ \6\ \7\ \8\ two ..................... 9222 B-2015/9222 I-
step, or. 2015.\31\
Single step............... 1603.1 \21\.......... ..................... .................... m-
ColiBlue24[supreg].
\19\
5. Fecal streptococci, number per MPN, 5 tube, 3 dilution, p. 139 \3\........... 9230 B-2013.
100 mL. 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 mL. MPN, 5 tube, 3 dilution, p. 139 \3\........... 9230 B-2013.
or.
MPN,\6\ \8\ multiple tube/ 9230 D-2013.......... D6503-99 \9\........ Enterolert[supreg].\
multiple well, or. 13\ \23\
MF \2\ \5\ \6\ \7\ \8\ 1600.1 \24\.......... 9230 C-2013.\32\
single step or.
Plate count............... p. 143.\3\
7. Salmonella, number per gram dry MPN multiple tube......... 1682.\22\............
weight \11\.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Aquatic Toxicity
--------------------------------------------------------------------------------------------------------------------------------------------------------
8. Toxicity, acute, fresh water Water flea, Cladoceran, 2002.0.\25\
organisms, LC50, percent effluent. Ceriodaphnia dubia acute.
Water flea, Cladocerans, 2021.0.\25\
Daphnia pulex and Daphnia
magna acute.
Fish, Fathead minnow, 2000.0.\25\
Pimephales promelas, and
Bannerfin shiner,
Cyprinella leedsi, acute.
Fish, Rainbow trout, 2019.0.\25\
Oncorhynchus mykiss, and
brook trout, Salvelinus
fontinalis, acute.
9. Toxicity, acute, estuarine and Mysid, Mysidopsis bahia, 2007.0.\25\
marine organisms of the Atlantic acute.
Ocean and Gulf of Mexico, LC50,
percent effluent.
Fish, Sheepshead minnow, 2004.0.\25\
Cyprinodon variegatus,
acute.
Fish, Silverside, Menidia 2006.0.\25\
beryllina, Menidia
menidia, and Menidia
peninsulae, acute.
10. Toxicity, chronic, fresh water Fish, Fathead minnow, 1000.0.\26\
organisms, NOEC or IC25, percent Pimephales promelas,
effluent. larval survival and
growth.
Fish, Fathead minnow, 1001.0.\26\
Pimephales promelas,
embryo-larval survival
and teratogenicity.
Water flea, Cladoceran, 1002.0.\26\
Ceriodaphnia dubia,
survival and reproduction.
Green alga, Selenastrum 1003.0.\26\
capricornutum, growth.
11. Toxicity, chronic, estuarine Fish, Sheepshead minnow, 1004.0.\27\
and marine organisms of the Cyprinodon variegatus,
Atlantic Ocean and Gulf of larval survival and
Mexico, NOEC or IC25, percent growth..
effluent.
Fish, Sheepshead minnow, 1005.0.\27\
Cyprinodon variegatus,
embryo-larval survival
and teratogenicity.
Fish, Inland silverside, 1006.0.\27\
Menidia beryllina, larval
survival and growth.
Mysid, Mysidopsis bahia, 1007.0.\27\
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-[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\ 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.
[[Page 27306]]
\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 [micro]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), EPA-821-R-23-008. September 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), EPA-821-R-23-006.
September 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.
\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 or ..................... 2310 B-2020.......... D1067-16............ I-1020-85.\2\
phenolphthalein endpoint.
2. Alkalinity (as CaCO3), mg/L.... Electrometric or ..................... 2320 B-2021.......... D1067-16............ 973.43,\3\ I-1030-
Colorimetric titration to 85.\2\
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 \36\. ..................... 3111 D-2019 or 3111 E- .................... I-3051-85.\2\
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 3125 B-2020.......... D5673-16............ 993.14,\3\ I-4472-
(1994). 97,\81\
Direct Current Plasma ..................... ..................... D4190-15............ See footnote.\34\
(DCP) \36\.
Colorimetric (Eriochrome ..................... 3500-Al B-2020. ....................
cyanine R).
4. Ammonia (as N), mg/L........... Manual distillation \6\ or 350.1 Rev. 2.0 (1993) 4500-NH3 B-2021...... .................... 973.49.\3\
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 diffusion, ..................... ..................... .................... Timberline Ammonia-
followed by conductivity 001.\74\
cell analysis.
Automated gas diffusion ..................... ..................... .................... FIAlab100.\82\
followed by fluorescence
detector analysis.
5. Antimony--Total,\4\ mg/L....... Digestion,\4\ followed by
any of the following:
[[Page 27307]]
AA direct aspiration \36\. ..................... 3111 B-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.
(2003),\68\ 200.7
Rev. 4.4 (1994).
ICP/MS.................... 200.8, Rev. 5.4 3125 B-2020.......... D5673-16............ 993.14,\3\ I-4472-
(1994). 97.\81\
6. Arsenic--Total,\4\ mg/L........ Digestion,\4\ followed by 206.5 (Issued
any of the following: 1978).\1\
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 3120 B-2020.......... D1976-20. ....................
(2003),\68\ 200.7
Rev. 4.4 (1994).
ICP/MS.................... 200.8, Rev. 5.4 3125 B-2020.......... D5673-16............ 993.14,\3\ I-4020-
(1994). 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 \36\. ..................... 3111 D-2019.......... .................... I-3084-85.\2\
AA furnace................ 3113 B-2020.......... D4382-18. ....................
ICP/AES \36\.............. 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\ 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 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....................... ..................... ..................... D4190-15............ See footnote.\34\
Colorimetric (aluminon)... ..................... See footnote \61\.... .................... ....................
9. Biochemical oxygen demand Dissolved Oxygen Depletion ..................... 5210 B-2016 \85\..... .................... 973.44 \3\ p. 17,\9\
(BOD5), mg/L. I-1578-78,\8\ see
footnote.\10\ \63\
10. Boron--Total,\37\ mg/L........ Colorimetric (curcumin)... ..................... 4500-B B-2011........ .................... I-3112-85.\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....................... ..................... ..................... 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 \36\. ..................... 3111 B-2019 or 3111 C- D3557-17 (A or B)... 974.27 \3\ p. 37,\9\
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 3120 B-2020.......... D1976-20............ I-1472-85 \2\ or I-
(2003),\68\ 200.7 4471-97.\50\
Rev. 4.4 (1994).
ICP/MS.................... 200.8, Rev. 5.4 3125 B-2020.......... D5673-16............ 993.14,\3\ I-4472-
(1994). 97.\81\
DCP \36\.................. ..................... ..................... D4190-15............ See footnote.\34\
Voltammetry \11\.......... ..................... ..................... D3557-17 (C).
Colorimetric (Dithizone).. ..................... 3500-Cd D-1990.
13. Calcium--Total,\4\ mg/L....... Digestion \4\ followed by
any of the following:
[[Page 27308]]
AA direct aspiration...... ..................... 3111 B-2019 or 3111 D- D511-14 (B)......... I-3152-85.\2\
2019.
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 3125 B-2020.......... D5673-16............ 993.14.\3\
(1994).
DCP....................... ..................... ..................... .................... See footnote.\34\
Titrimetric (EDTA)........ ..................... 3500-Ca B-2020....... D511-14 (A).
Ion Chromatography........ ..................... ..................... D6919-17.
14. Carbonaceous biochemical Dissolved Oxygen Depletion ..................... 5210 B-2016 \85\..... .................... See footnotes.\35
oxygen demand (CBOD5), mg/L\12\. with nitrification 63\
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, manual 410.4 Rev. 2.0 (1993) 5220 D-2011.......... D1252-06(12) (B).... See footnotes,\13\
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 (ferricyanide).. ..................... 4500-Cl- E-2021...... .................... I-2187-85.\2\
Potentiometric Titration ..................... 4500-Cl- D-2021.
Ion Selective Electrode... ..................... ..................... D512-12 (C).
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 (low ..................... 4500-Cl E-2011.
level).
Iodometric direct......... ..................... 4500-Cl B-2011.
Back titration ether end- ..................... 4500-Cl C-2011.
point \15\.
DPD-FAS................... ..................... 4500-Cl F-2011.
Spectrophotometric, DPD... ..................... 4500-Cl G-2011.
Electrode................. ..................... ..................... .................... See footnote.\16\
17A. Chlorine--Free Available, mg/ Amperometric direct....... ..................... 4500-Cl D-2011....... D1253-14............
L.
Amperometric direct (low ..................... 4500-Cl E-2011.
level).
DPD-FAS................... ..................... 4500-Cl F-2011.
Spectrophotometric, DPD... ..................... 4500-Cl G-2011.
18. Chromium VI dissolved, mg/L... 0.45-micron filtration
followed by any of the
following:
AA chelation-extraction... ..................... 3111 C-2019.......... .................... I-1232-85.\2\
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).
19. Chromium--Total,\4\ mg/L...... Digestion,\4\ followed by
any of the following:
AA direct aspiration \36\. ..................... 3111 B-2019.......... D1687-17 (B)........ 974.27,\3\ I-3236-
85.\2\
AA chelation-extraction... ..................... 3111 C-2019.
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-
2019. 323985.\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 Colorimetric (ADMI)....... ..................... 2120 F-2021.\78\
or 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:
[[Page 27309]]
AA direct aspiration \36\. ..................... 3111 B-2019 or 3111 C- D1688-17 (A or B)... 974.27,\3\ p. 37,\9\
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 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 (Neocuproine) ..................... 3500-Cu B-2020.
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 Injection, ..................... 4500-CN- P-2021...... D7511-12 (17).......
In-Line Ultraviolet
Digestion, followed by
gas diffusion amperometry.
Manual distillation with 335.4 Rev. 1.0 (1993) 4500-CN- B-2021 and C- D2036-09(15)(A), 10-204-00-1-X.\56\
MgCl2, followed by any of \57\. 2021. D7284-20.
the following:
Flow Injection, gas ..................... ..................... D2036-09(15)(A)
diffusion amperometry. D7284-20.
Titrimetric............... ..................... 4500-CN- D-2021...... D2036-09(15)(A)..... See footnote \9\ p.
22.
Spectrophotometric, manual ..................... 4500-CN- E-2021...... D2036-09(15)(A)..... I-3300-85.\2\
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 Electrode... ..................... 4500-CN- F-2021...... D2036-09(15)(A).
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 ligand ..................... 4500-CN- Q-2021...... D6888-16............ OIA-1677-09.\44\
exchange, followed by gas
diffusion amperometry
\59\.
Automated Distillation and ..................... ..................... .................... Kelada-01.\55\
Colorimetry (no UV
digestion).
24A. Cyanide--Free, mg/L.......... Flow Injection, followed ..................... 4500-CN- R-2021...... D7237-18 (A)........ OIA-1677-09.\44\
by gas diffusion
amperometry.
Manual micro-diffusion and ..................... ..................... D4282-15.
colorimetry.
25. Fluoride--Total, mg/L......... Manual distillation,\6\ ..................... 4500-F- B-2021....... D1179-16 (A).
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 3125 B-2020.......... D5673-16............ 993.14.\3\
(1994).
DCP....................... ..................... ..................... .................... See footnote.\34\
27. Hardness--Total (as CaCO(3), Automated colorimetric.... 130.1 (Issued
mg/L. 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 measurement. ..................... 4500-H\+\ B-2021..... D1293-18 (A or B)... 973.41,\3\ I-1586-
85.\2\
Automated electrode....... 150.2 (Dec. 1982) \1\ ..................... .................... See footnote \21\ I-
2587-85.\2\
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 \36\. ..................... 3111 B-2019 or 3111 C- D1068-15 (A)........ 974.27,\3\ I-3381-
2019. 85.\2\
AA furnace................ ..................... 3113 B-2020.......... D1068-15 (B).
STGFAA.................... 200.9, Rev. 2.2
(1994).
[[Page 27310]]
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 3125 B-2020.......... D5673-16............ 993.14.\3\
(1994).
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\ and ..................... 4500-Norg B-2021 or C- D3590-17 (A)........ I-4515-91.\45\
(as N), mg/L. distillation or gas 2021 and 4500-NH3 B-
diffusion, followed by 2021.
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 diffusion, ..................... ..................... .................... Timberline Ammonia-
followed by conductivity 001.\74\
cell analysis.
Automated gas diffusion ..................... ..................... .................... FIAlab 100.\82\
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, followed ..................... ..................... .................... See footnote.\39\
by Auto distillation and
Titration.
Block digester, followed ..................... ..................... .................... See footnote.\40\
by Auto distillation and
Nesslerization.
Block Digester, followed ..................... ..................... .................... See footnote.\41\
by Flow injection gas
diffusion (distillation
not required).
Digestion with ..................... ..................... .................... Hach 10242.\76\
peroxdisulfate, followed
by Spectrophotometric
(2,6-dimethyl phenol).
Digestion with persulfate, ..................... ..................... .................... NCASI TNTP
followed by Colorimetric. W10900.\77\
32. Lead--Total,\4\ mg/L.......... Digestion,\4\ followed by
any of the following:
AA direct aspiration \36\. ..................... 3111 B-2019 or 3111 C- D3559-15 (A or B)... 974.27,\3\ I-3399-
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 (Dithizone).. ..................... 3500-Pb B-2020.
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 \36\. ..................... 3111 B-2019 or 3111 C- D858-17 (A or B).... 974.27,\3\ I-3454-
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 (Persulfate). ..................... 3500-Mn B-2020....... .................... 920.203.\3\
Colorimetric (Periodate).. ..................... ..................... .................... See footnote.\23\
[[Page 27311]]
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 spectrometry \17\.
(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\
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 \36\. ..................... 3111 B-2019 or 3111 C- D1886-14 (A or B)... I-3499-85.\2\
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 3125 B-2020.......... D5673-16............ 993.14,\3\ I-4020-
(1994). 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 Electrode... ..................... 4500-NO3- D-2019.....
Colorimetric (Brucine 352.1 (Issued 1971) ..................... .................... 973.50,\3\ 419D,\86\
sulfate). \1\. p. 28.\9\
Spectrophotometric (2,6- ..................... ..................... .................... Hach 10206.\75\
dimethylphenol).
Nitrate-nitrite N minus
Nitrite N (see parameters
39 and 40).
39. Nitrate-nitrite (as N), mg/L.. Cadmium reduction, Manual. ..................... 4500-NO3- E-2019..... D3867-16 (B).
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-
followed by automated 2548-11,\72\ N07-
colorimetric 0003.\73\
determination.
Enzymatic reduction, ..................... 4500-NO3- J-2018.
followed by manual
colorimetric
determination.
Spectrophotometric (2,6- ..................... ..................... .................... Hach 10206.\75\
dimethylphenol).
40. Nitrite (as N), mg/L.......... Spectrophotometric: Manual ..................... 4500-NO2- B-2021..... .................... See footnote.\25\
Automated (Diazotization). ..................... ..................... .................... I-4540-85 \2\ see
footnote,\62\ I-
2540-90.\80\
Automated (*bypass cadmium 353.2 Rev. 2.0 (1993) 4500-NO3- F-2019, D3867-16 (A)........ I-4545-85.\2\
reduction). 4500-NO3- I-2019.
Manual (*bypass cadmium or ..................... 4500-NO3- E-2019, D3867-16 (B). ....................
enzymatic reduction). 4500-NO3- J-2018.
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-
Enzymatic reduction). 2548-11,\72\ N07-
0003.\73\
41. Oil and grease--Total Hexane extractable 1664 Rev. A 1664 Rev. 5520 B or G-2021.\38\
recoverable, mg/L. material (HEM): n-Hexane B \42\.
extraction and gravimetry.
Silica gel treated HEM 1664 Rev. A, 1664 5520 B or G-2021 \38\
(SGT-HEM): Silica gel Rev. B \42\. and 5520 F-2021.\38\
treatment and gravimetry.
42. Organic carbon--Total (TOC), Combustion................ ..................... 5310 B-2014.......... D7573-18a\e1\....... 973.47,\3\ p.
mg/L. 14.\24\
[[Page 27312]]
Heated persulfate or UV ..................... 5310 C-2014, 5310 D- D4839-03(17)........ 973.47,\3,\ p.
persulfate oxidation. 2011. 14.\24\
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 Sensor. ..................... 4500-O H-2021........ D888-18 (C)......... See footnotes. 63 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 distillation,\26\ 420.1 (Rev. 1978) \1\ 5530 B-2021.......... D1783-01(12)........
followed by any of the
following:.
Colorimetric (4AAP) manual 420.1 (Rev. 1978) \1\ 5530 D-2021 \27\..... D1783-01(12) (A or
B).
Automated colorimetric 420.4 Rev. 1.0
(4AAP). (1993).
49. Phosphorus (elemental), mg/L.. Gas-liquid chromatography. ..................... ..................... .................... See footnote.\28\
50. Phosphorus--Total, mg/L....... Digestion,\20\ followed by ..................... 4500-P B (5)-2021.... .................... 973.55.\3\
any of the following:.
Manual.................... 365.3 (Issued 1978) 4500-P E-2021........ D515-88 (A).
\1\.
Automated ascorbic acid 365.1 Rev. 2.0 (1993) 4500-P (F-H)-2021.... .................... 973.56,\3\ I-4600-
reduction. 85.\2\
ICP/AES \4\ \36\.......... 200.7Rev. 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 digestion). \1\.
Digestion with persulfate, ..................... ..................... .................... NCASI TNTP
followed by Colorimetric. W10900.\77\
51. Platinum--Total,\4\ mg/L...... Digestion,\4\ followed by
any of the following:
AA direct aspiration...... ..................... 3111 B-2019.
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.......... .................... 973.5,\3\ I-3630-
85.\2\
ICP/AES................... 200.7 Rev. 4.4 (1994) 3120 B-2020.
ICP/MS.................... 200.8, Rev. 5.4 3125 B-2020.......... D5673-16............ 993.14.\3\
(1994).
Flame photometric......... ..................... 3500-K B-2020.
Electrode................. ..................... 3500-K C-2020.
Ion Chromatography........ ..................... ..................... D6919-17.
53. Residue--Total, mg/L.......... Gravimetric, 103-105[deg]. ..................... 2540 B-2020.......... .................... I-3750-85.\2\
54. Residue--filterable, mg/L..... Gravimetric, 180[deg]..... ..................... 2540 C-2020.......... D5907-18 (B)........ I-1750-85.\2\
55. Residue--non-filterable (TSS), Gravimetric, 103-105[deg] ..................... 2540 D-2020.......... D5907-18 (A)........ I-3765-85.\2\
mg/L. post-washing of residue.
56. Residue--settleable, mg/L..... Volumetric (Imhoff cone), ..................... 2540 F-2020.
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, or.. ..................... 3111 B-2019.
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, or.. ..................... 3111 B-2019.
AA furnace................ 267.2.\1\
[[Page 27313]]
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 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\
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).
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, Wheatstone bridge......... 120.1 (Rev. 1982) \1\ 2510 B-2021.......... D1125-95(99) (A).... 973.40,\3\ I-2781-
micromhos/cm at 25 [deg]C. 85.\2\
65. Sulfate (as SO4), mg/L........ Automated colorimetric.... 375.2 Rev. 2.0 (1993) 4500-SO4\2\- F-2021
or G-2021.
Gravimetric............... ..................... 4500-SO4\2\- C-2021 .................... 925.54.\3\
or D-2021.
Turbidimetric............. ..................... 4500-SO4\2\- 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-S\2\- B, C-2021.
Titrimetric (iodine)...... ..................... 4500-S\2\- F-2021.... .................... I-3840-85.\2\
Colorimetric (methylene ..................... 4500-S\2\- D-2021.
blue).
Ion Selective Electrode... ..................... 4500-S\2\- G-2021.... D4658-15.
67. Sulfite (as SO3), mg/L........ Titrimetric (iodine- ..................... 4500-SO3\2\- B-2021.
iodate).
68. Surfactants, mg/L............. Colorimetric (methylene ..................... 5540 C-2021.......... D2330-20.
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 3125 B-2020.......... D5673-16............ 993.14,\3\ I-4471-97
(1994). \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\
[[Page 27314]]
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).
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 2130 B-2020.......... D1889-00............ I-3860-85,\2\ see
(1993). footnotes.\65\ \66\
\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 Acid) ..................... 3500-V B-2011.
75. Zinc--Total,\4\ mg/L.......... Digestion,\4\ followed by
any of the following:
AA direct aspiration \36\. ..................... 3111 B-2019 or 3111 C- D1691-17 (A or B)... 974.27 \3\ p. 37,\9\
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 this table
IB); the total recoverable digestion procedures in EPA Methods 200.7, 200.8, and 200.9 may be used for those respective methods. Regardless of the
digestion procedure, the results of the analysis after digestion procedure are reported as ``total'' metals.
\5\ Copper sulfate 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.
\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.
[[Page 27315]]
\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.
\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\ Waters Corp. Now included in ASTM D6508-15, Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion
Electrophoresis and Chromate Electrolyte. 2015.
\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 this table IB
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.
[[Page 27316]]
\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 in U.S. Geological Survey Techniques of Water-Resources Investigations, Book 5, Chap. A1, Methods for Determination of Inorganic
Substances in Water and Fluvial Sediments, 1989.
\80\ Methods I-2522-90, I-2540-90, and I-2601-90 in 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-4472-97 in 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 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.
Table IC--List of Approved Test Procedures for Non-Pesticide Organic Compounds
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter \1\ Method EPA \2\ \7\ Standard methods \17\ 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.................... 6440 B-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\
[[Page 27317]]
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\
23. 4-Chloro-3-methyl phenol.... GC..................... 604.................... 6420 B-2021.
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-2021.
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.
GC/MS.................. 624.1, 1624B........... 6200 B-2020............ ....................... O-4127-96 \13\, O-
4436-16.\14\
44. 2,4-Dichlorophenol.......... GC..................... 604.................... 6420 B-2021.
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-2021.
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-2021............ ....................... 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.
[[Page 27318]]
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\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
61. 1,2,3,4,7,8,9-Heptachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
62. 1,2,3,4,6,7,8- Heptachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzo-p-dioxin. \15\, PAM 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\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
67. 1,2,3,6,7,8-Hexachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
68. 1,2,3,7,8,9-Hexachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
69. 2,3,4,6,7,8-Hexachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
70. 1,2,3,4,7,8-Hexachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzo-p-dioxin. \15\, PAM 16130-
SSI.\16\
71. 1,2,3,6,7,8-Hexachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzo-p-dioxin. \15\, PAM 16130-
SSI.\16\
72. 1,2,3,7,8,9-Hexachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzo-p-dioxin. \15\, PAM 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-2021.
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-2021.
GC/MS.................. 625.1, 1625B........... 6410 B-2020............ ....................... See footnote \9\
p. 27.
81. 4-Nitrophenol............... GC..................... 604.................... 6420 B-2021.
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\............. ....................... ....................... SGS AXYS 16130
\15\, PAM 16130-
SSI.\16\
86. Octachlorodibenzo-p-dioxin.. GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 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.
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\
[[Page 27319]]
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\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
96. 2,3,4,7,8-Pentachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
97. 1,2,3,7,8-Pentachloro- GC/MS.................. 1613B \10\............. ....................... ....................... SGS AXYS 16130
dibenzo-p-dioxin. \15\, PAM 16130-
SSI.\16\
98. Pentachlorophenol........... GC..................... 604.................... 6420 B-2021............ ....................... 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-2021.
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\............. ....................... ....................... SGS AXYS 16130
dibenzofuran. \15\, PAM 16130-
SSI.\16\
103. 2,3,7,8-Tetrachloro-dibenzo- GC/MS.................. 613, 625.1 \5\, 1613B.. ....................... ....................... SGS AXYS 16130
p-dioxin. \15\, PAM 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.
GC/MS.................. 624.1.................. 6200 B-2020............ ....................... O-4127-96.\13\
112. 2,4,6-Trichlorophenol...... GC..................... 604.................... 6420 B-2021.
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 and 1653.\11\
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. Method 625.1 may be applied to 2,3,7,8-Tetrachloro-dibenzo-p-dioxin for screening purposes 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.
[[Page 27320]]
\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\ SGS AXYS Method 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: pacelabs.com.
\17\ Please refer to the following applicable Quality Control Section: Part 6000 Individual Organic Compounds, 6020 (2019). The Quality Control
Standards are available for download at standardmethods.org at no charge.
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 (02) See footnote \3\
p. 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, D5812-96(02). See footnote \3\
p. 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, D5812-96(02). See footnote \8\
3M0222.
GC/MS.................. 625.1.................. 6410 B-2020.
10. [delta]-BHC................. GC..................... 617, 608.3............. 6630 B-2021 & C-2021... D3086-90, D5812-96(02). See footnote \8\
3M0222.
GC/MS.................. 625.1.................. 6410 B-2020............
11. [gamma]-BHC (Lindane)....... 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.
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, D5812-96(02). See footnote \3\
p. 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.
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.
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, D5812-96(02). See footnote \3\
p. 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, D5812-96(02). See footnote \3\
p. 7, see
footnote \4\, O-
3104-83, see
footnote \8\
3M0222.
GC/MS.................. 625.1.................. 6410 B-2020............ ....................... See footnote \11\
O-1126-95.
[[Page 27321]]
20. 4,4'-DDT.................... 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.
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, D5812-96(02). See footnote \3\
p. 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.
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, D5812-96(02). See footnote \3\
p. 7, see
footnote \4\ O-
3104-83, see
footnote \8\
3M0222.
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, D5812-96(02). See footnote \3\
p. 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, D5812-96(02). See footnote \3\
608.3. p. 7, see
footnote \4\ O-
3104-83, see
footnote \8\
3M0222.
GC/MS.................. 525.1, 525.2, 625.1 \5\ 6410 B-2020.
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, D5812-96(02). See footnote \3\
608.3. p. 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, D5812-96(02). See footnote \3\
p. 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.
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, D5812-96(02). See footnote \3\
1656, 608.3. p. 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.
[[Page 27322]]
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, D5812-96(02). See footnote \3\
p. 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, D5812-96(02). See footnote \3\
p. 7.
55. Perthane.................... GC..................... 617, 608.3............. ....................... D3086-90, D5812-96(02). See footnote \4\ O-
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. 10, see
footnote \6\ p.
S64.
HPLC................... 632.
HPLC/MS................ ....................... ....................... ....................... See footnote \12\
O-2060-01.
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\
608.3. p. 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, D5812-96(02). See footnote \3\
608.3. p. 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\
608.3. p. 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 to this
part, Definition and Procedure for the Determination of the Method Detection Limit.
[[Page 27323]]
\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.
\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 Most Probable Number p. 132 \3\........... 9221 E-2014, 9221 F-
100 mL. (MPN), 5 tube, 3 2014.\32\
dilution, or.
Membrane filter (MF) \2\, p. 124 \3\........... 9222 D-2015 \26\..... B-0050-85.\4\
single step.
2. Coliform (total), number per MPN, 5 tube, 3 dilution, p. 114 \3\........... 9221 B-2014.
100 mL. or.
MF \2\, single step or.... p. 108 \3\........... 9222 B-2015 \27\..... B-0025-85.\4\
MF \2\, two step with p. 111 \3\........... 9222 B-2015.\27\
enrichment.
3. E. coli, number per 100 mL..... MPN \5\ \7\ \13\, multiple ..................... 9221 B.3-2014/9221 F-
tube, or. 2014.\10\ \12\ \32\
Multiple tube/multiple ..................... 9223 B-2016 \11\..... 991.15 \9\.......... Colilert[supreg]
well, or. \11\ \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 ..................... .................... m-ColiBlue24[supreg]
\20\. \16\, KwikCountTM
EC.\28\ \29\
4. Fecal streptococci, number per MPN, 5 tube, 3 dilution, p. 139 \3\........... 9230 B-2013.
100 mL. 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 tube/ ..................... 9230 D-2013.......... D6503-99 \8\........ Enterolert[supreg].\
multiple well, or. 11\ \21\
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.
[[Page 27324]]
\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.
\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), EPA-821-R-23-
009. September 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), EPA-821-R-23-008. September 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), EPA-821-R-23-007. September
2023. US EPA.
\23\ Method 1600.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI), EPA-821-R-21-006.
September 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 Roth Bioscience, 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
incorporation by reference (IBR) 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 or email [email protected]. The
material may be obtained from the following sources in this paragraph
(b).
* * * * *
(8) Office of Water, U.S. Environmental Protection Agency (U.S.
EPA), mail code 4303T, 1301 Constitution Avenue NW, Washington, DC
20460; website: www.epa.gov/cwa-methods.
(i) Method 245.7, Mercury in Water by Cold Vapor Atomic
Fluorescence Spectrometry. Revision 2.0, February 2005. EPA-821-R-05-
001. Table IB, Note 17.
(ii) Method 1103.2: Escherichia coli (E. coli) in Water by Membrane
Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC),
EPA-821-R-23-009. September 2023. Table IH, Note 18.
(iii) Method 1106.2: Enterococci in Water by Membrane Filtration
Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA), EPA-821-R-23-
007. September 2023. Table IH, Note 22.
(iv) Method 1600.1: Enterococci in Water by Membrane Filtration
Using membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI), EPA-
821-R-23-006, September 2023. 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), EPA-821-R-23-008, September 2023. Table IA, Note 21;
Table IH, Note 19.
(vi) Method 1604: Total Coliforms and Escherichia coli (E. coli) in
Water by Membrane Filtration Using a Simultaneous Detection Technique
(MI Medium). September 2002. EPA-821-R-02-024. Table IH, Note 21.
(vii) Whole Effluent Toxicity Methods Errata Sheet, EPA 821-R-02-
012-ES. December 2016, Table IA, Notes 25, 26, and 27.
(viii) Method 1623: Cryptosporidium and Giardia in Water by
Filtration/IMS/FA. December 2005. EPA-821-R-05-002. Table IH, Note 26.
(ix) Method 1623.1: Cryptosporidium and Giardia in Water by
Filtration/IMS/FA. EPA 816-R-12-001. January 2012. U.S. EPA, Table IH,
Notes 25 and 31.
(x) Method 1627, Kinetic Test Method for the Prediction of Mine
Drainage Quality. December 2011. EPA-821-R-09-002. Table IB, Note 69.
(xi) Method 1664, n-Hexane Extractable Material (HEM; Oil and
Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM;
Nonpolar Material) by Extraction and Gravimetry. Revision A, February
1999. EPA-821-R-98-002. Table IB, Notes 38 and 42.
(xii) Method 1664, n-Hexane Extractable Material (HEM; Oil and
Grease) and Silica Gel Treated n-Hexane
[[Page 27325]]
Extractable Material (SGT-HEM; Nonpolar Material) by Extraction and
Gravimetry, Revision B, February 2010. EPA-821-R-10-001. Table IB,
Notes 38 and 42.
(xiii) Method 1669, Sampling Ambient Water for Trace Metals at EPA
Water Quality Criteria Levels. July 1996. Table IB, Note 43.
(xiv) Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by
Multiple-Tube Fermentation using Lauryl Tryptose Broth (LTB) and EC
Medium. September 2014. EPA-821-R-14-009.Table IA, Note 15.
(xv) Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by
Multiple-Tube Fermentation using A-1 Medium. July 2006. EPA 821-R-06-
013. Table IA, Note 20.
(xvi) Method 1682: Salmonella in Sewage Sludge (Biosolids) by
Modified Semisolid Rappaport-Vassiliadis (MSRV) Medium. September 2014.
EPA 821-R-14-012. Table IA, Note 23.
* * * * *
(10) American Public Health Association, 800 I Street, NW,
Washington, DC 20001; phone: (202)777-2742, website:
www.standardmethods.org.
(i) Standard Methods for the Examination of Water and Wastewater.
14th Edition, 1975. Table IB, Notes 27 and 86.
(ii) Standard Methods for the Examination of Water and Wastewater.
15th Edition, 1980, Table IB, Note 30; Table ID.
(iii) 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.
Table IC, Note 6; Table ID, Note 6.
(iv) Standard Methods for the Examination of Water and Wastewater.
18th Edition, 1992. Tables IA, IB, IC, ID, IE, and IH.
(v) Standard Methods for the Examination of Water and Wastewater.
19th Edition, 1995. Tables IA, IB, IC, ID, IE, and IH.
(vi) Standard Methods for the Examination of Water and Wastewater.
20th Edition, 1998. Tables IA, IB, IC, ID, IE, and IH.
(vii) Standard Methods for the Examination of Water and Wastewater.
21st Edition, 2005. Table IB, Notes 17 and 27.
(viii) 2120, Color. Revised September 4, 2021. Table IB.
(ix) 2130, Turbidity. Revised 2020. Table IB.
(x) 2310, Acidity. Revised 2020. Table IB.
(xi) 2320, Alkalinity. Revised 2021. Table IB.
(xii) 2340, Hardness. Revised 2021. Table IB.
(xiii) 2510, Conductivity. Revised 2021. Table IB.
(xiv) 2540, Solids. Revised 2020. Table IB.
(xv) 2550, Temperature. 2010. Table IB.
(xvi) 3111, Metals by Flame Atomic Absorption Spectrometry. Revised
2019. Table IB.
(xvii) 3112, Metals by Cold-Vapor Atomic Absorption Spectrometry.
Revised 2020. Table IB.
(xviii) 3113, Metals by Electrothermal Atomic Absorption
Spectrometry. Revised 2020. Table IB.
(xix) 3114, Arsenic and Selenium by Hydride Generation/Atomic
Absorption Spectrometry. Revised 2020, Table IB.
(xx) 3120, Metals by Plasma Emission Spectroscopy. Revised 2020.
Table IB.
(xxi) 3125, Metals by Inductively Coupled Plasma-Mass Spectrometry.
Revised 2020. Table IB.
(xxii) 3500-Al, Aluminum. Revised 2020. Table IB.
(xxiii) 3500-As, Arsenic. Revised 2020. Table IB.
(xxiv) 3500-Ca, Calcium. Revised 2020. Table IB.
(xxv) 3500-Cr, Chromium. Revised 2020. Table IB.
(xxvi) 3500-Cu, Copper. Revised 2020. Table IB.
(xxvii) 3500-Fe, Iron. 2011. Table IB.
(xxviii) 3500-Pb, Lead. Revised 2020. Table IB.
(xxix) 3500-Mn, Manganese. Revised 2020. Table IB.
(xxx) 3500-K, Potassium. Revised 2020. Table IB.
(xxxi) 3500-Na, Sodium. Revised 2020. Table IB.
(xxxii) 3500-V, Vanadium. 2011. Table IB.
(xxxiii) 3500-Zn, Zinc. Revised 2020. Table IB.
(xxxiv) 4110, Determination of Anions by Ion Chromatography.
Revised 2020. Table IB.
(xxxv) 4140, Inorganic Anions by Capillary Ion Electrophoresis.
Revised 2020. Table IB.
(xxxvi) 4500-B, Boron. 2011. Table IB.
(xxxvii) 4500 Cl-, Chloride. Revised 2021. Table IB.
(xxxviii) 4500-Cl, Chlorine (Residual). 2011. Table IB.
(xxxix) 4500-CN-, Cyanide. Revised 2021. Table IB.
(xl) 4500-F-, Fluoride. Revised 2021. Table IB.
(xli) 4500-H\+\, pH. 2021. Table IB.
(xlii) 4500-NH3, Nitrogen (Ammonia). Revised 2021. Table
IB.
(xliii) 4500-NO2-, Nitrogen (Nitrite).
Revised 2021. Table IB.
(xliv) 4500-NO3-, Nitrogen (Nitrate). Revised
2019. Table IB.
(xlv) 4500-N(org), Nitrogen (Organic). Revised 2021.
Table IB.
(xlvi) 4500-O, Oxygen (Dissolved). Revised 2021. Table IB.
(xlvii) 4500-P, Phosphorus. Revised 2021. Table IB.
(xlviii) 4500-SiO2, Silica. Revised 2021. Table IB.
(xlix) 4500-S2-, Sulfide. Revised 2021. Table IB.
(l) 4500-SO32-, Sulfite. Revised 2021. Table
IB.
(li) 4500-SO42-, Sulfate. Revised 2021. Table
IB.
(lii) 5210, Biochemical Oxygen Demand (BOD). Revised 2016. Table
IB.
(liii) 5220, Chemical Oxygen Demand (COD). 2011. Table IB.
(liv) 5310, Total Organic Carbon (TOC). Revised 2014. Table IB.
(lv) 5520, Oil and Grease. Revised 2021. Table IB.
(lvi) 5530, Phenols. Revised 2021. Table IB.
(lvii) 5540, Surfactants. Revised 2021. Table IB.
(lviii) 6200, Volatile Organic Compounds. Revised 2020. Table IC.
(lix) 6410, Extractable Base/Neutrals and Acids. Revised 2020.
Tables IC and ID.
(lx) 6420, Phenols. Revised 2021. Table IC.
(lxi) 6440, Polynuclear Aromatic Hydrocarbons. Revised 2021. Table
IC.
(lxii) 6630, Organochlorine Pesticides. Revised 2021. Table ID.
(lxiii) 6640, Acidic Herbicide Compounds. Revised 2021. Table ID.
(lxiv) 7110, Gross Alpha and Gross Beta Radioactivity (Total,
Suspended, and Dissolved). 2000. Table IE.
(lxv) 7500, Radium. 2001. Table IE.
(lxvi) 9213, Recreational Waters. 2007. Table IH.
(lxvii) 9221, Multiple-Tube Fermentation Technique for Members of
the Coliform Group. Approved 2014. Table IA, Notes 12, 14; and 33;
Table IH, Notes 10, 12, and 32.
(lxviii) 9222, Membrane Filter Technique for Members of the
Coliform Group. 2015. Table IA, Note 31; Table IH, Note 17.
(lxix) 9223 Enzyme Substrate Coliform Test. 2016. Table IA; Table
IH.
(lxx) 9230 Fecal Enterococcus/Streptococcus Groups. 2013. Table IA,
Note 32; Table IH.
* * * * *
(15) ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West
Conshohocken, PA 19428-2959; phone: (877)909-2786; website:
www.astm.org.
[[Page 27326]]
(i) Annual Book of ASTM Standards, Water, and Environmental
Technology, Section 11, Volumes 11.01 and 11.02. 1994. Tables IA, IB,
IC, ID, IE, and IH.
(ii) Annual Book of ASTM Standards, Water, and Environmental
Technology, Section 11, Volumes 11.01 and 11.02. 1996. Tables IA, IB,
IC, ID, IE, and IH.
(iii) Annual Book of ASTM Standards, Water, and Environmental
Technology, Section 11, Volumes 11.01 and 11.02. 1999. Tables IA, IB,
IC, ID, IE, and IH.
(iv) Annual Book of ASTM Standards, Water, and Environmental
Technology, Section 11, Volumes 11.01 and 11.02. 2000. Tables IA, IB,
IC, ID, IE, and IH.
(v) ASTM D511-14, Standard Test Methods for Calcium and Magnesium
in Water. Approved October 1, 2014. Table IB.
(vi) ASTM D512-12, Standard Test Methods for Chloride Ion in Water.
Approved June 15, 2012. Table IB.
(vii) ASTM D515-88, Test Methods for Phosphorus in Water, March
1989. Table IB.
(viii) ASTM D516-16, Standard Test Method for Sulfate Ion in Water.
Approved June 1, 2016. Table IB.
(ix) ASTM D858-17, Standard Test Methods for Manganese in Water.
Approved June 1, 2017. Table IB.
(x) ASTM D859-16, Standard Test Method for Silica in Water.
Approved June 15, 2016. Table IB.
(xi) ASTM D888-18, Standard Test Methods for Dissolved Oxygen in
Water. Approved May 1, 2018. Table IB.
(xii) ASTM D1067-16, Standard Test Methods for Acidity or
Alkalinity of Water. Approved June 15, 2016. Table IB.
(xiii) ASTM D1068-15, Standard Test Methods for Iron in Water.
Approved October 1, 2015. Table IB.
(xiv) ASTM D1125-95 (Reapproved 1999), Standard Test Methods for
Electrical Conductivity and Resistivity of Water. December 1995. Table
IB.
(xv) ASTM D1126-17, Standard Test Method for Hardness in Water.
Approved December 1, 2017. Table IB.
(xvi) ASTM D1179-16, Standard Test Methods for Fluoride Ion in
Water. Approved June 15, 2016. Table IB.
(xvii) ASTM D1246-16, Standard Test Method for Bromide Ion in
Water. June 15, 2016. Table IB.
(xviii) ASTM D1252-06 (Reapproved 2012), Standard Test Methods for
Chemical Oxygen Demand (Dichromate Oxygen Demand) of Water. Approved
June 15, 2012. Table IB.
(xix) ASTM D1253-14, Standard Test Method for Residual Chlorine in
Water. Approved January 15, 2014. Table IB.
(xx) ASTM D1293-18, Standard Test Methods for pH of Water. Approved
January 15, 2018. Table IB.
(xxi) ASTM D1426-15, Standard Test Methods for Ammonia Nitrogen in
Water. Approved March 15, 2015. Table IB.
(xxii) ASTM D1687-17, Standard Test Methods for Chromium in Water.
Approved June 1, 2017. Table IB.
(xxiii) ASTM D1688-17, Standard Test Methods for Copper in Water.
Approved June 1, 2017. Table IB.
(xxiv) ASTM D1691-17, Standard Test Methods for Zinc in Water.
Approved June 1, 2017. Table IB.
(xxv) ASTM D1783-01 (Reapproved 2012), Standard Test Methods for
Phenolic Compounds in Water. Approved June 15, 2012. Table IB.
(xxvi) ASTM D1886-14, Standard Test Methods for Nickel in Water.
Approved October 1, 2014. Table IB.
(xxvii) ASTM D1889-00, Standard Test Method for Turbidity of Water.
October 2000. Table IB.
(xxviii) ASTM D1890-96, Standard Test Method for Beta Particle
Radioactivity of Water. April 1996. Table IE.
(xxix) ASTM D1943-96, Standard Test Method for Alpha Particle
Radioactivity of Water. April 1996. Table IE.
(xxx) ASTM D1976-20, Standard Test Method for Elements in Water by
Inductively-Coupled Argon Plasma Atomic Emission Spectroscopy. Approved
May 1, 2020. Table IB.
(xxxi) ASTM D2036-09 (Reapproved 2015), Standard Test Methods for
Cyanides in Water. Approved July 15, 2015. Table IB.
(xxxii) ASTM D2330-20, Standard Test Method for Methylene Blue
Active Substances. Approved January 1, 2020. Table 1B.
(xxxiii) ASTM D2460-97, Standard Test Method for Alpha-Particle-
Emitting Isotopes of Radium in Water. October 1997. Table IE.
(xxxiv) ASTM D2972-15, Standard Tests Method for Arsenic in Water.
Approved February 1, 2015. Table IB.
(xxxv) ASTM D3223-17, Standard Test Method for Total Mercury in
Water. Approved June 1, 2017. Table IB.
(xxxvi) ASTM D3371-95, Standard Test Method for Nitriles in Aqueous
Solution by Gas-Liquid Chromatography, February 1996. Table IF.
(xxxvii) ASTM D3373-17, Standard Test Method for Vanadium in Water.
Approved June 1, 2017. Table IB.
(xxxviii) ASTM D3454-97, Standard Test Method for Radium-226 in
Water. February 1998. Table IE.
(xxxix) ASTM D3557-17, Standard Test Method for Cadmium in Water.
Approved June 1, 2017. Table IB.
(xl) ASTM D3558-15, Standard Test Method for Cobalt in Water.
Approved February 1, 2015. Table IB.
(xli) ASTM D3559-15, Standard Test Methods for Lead in Water.
Approved June 1, 2015. Table IB.
(xlii) ASTM D3590-17, Standard Test Methods for Total Kjeldahl
Nitrogen in Water. Approved June 1, 2017. Table IB.
(xliii) ASTM D3645-15, Standard Test Methods for Beryllium in
Water. Approved February 1, 2015. Table IB.
(xliv) ASTM D3695-95, Standard Test Method for Volatile Alcohols in
Water by Direct Aqueous-Injection Gas Chromatography. April 1995. Table
IF.
(xlv) ASTM D3859-15, Standard Test Methods for Selenium in Water.
Approved March 15, 2015. Table IB.
(xlvi) ASTM D3867-16, Standard Test Method for Nitrite-Nitrate in
Water. Approved June 1, 2016. Table IB.
(xlvii) ASTM D4190-15, Standard Test Method for Elements in Water
by Direct- Current Plasma Atomic Emission Spectroscopy. Approved
February 1, 2015. Table IB.
(xlviii) ASTM D4282-15, Standard Test Method for Determination of
Free Cyanide in Water and Wastewater by Microdiffusion. Approved July
15, 2015. Table IB.
(xlix) ASTM D4327-17, Standard Test Method for Anions in Water by
Suppressed Ion Chromatography. Approved December 1, 2017. Table IB.
(l) ASTM D4382-18, Standard Test Method for Barium in Water, Atomic
Absorption Spectrophotometry, Graphite Furnace. Approved February 1,
2018. Table IB.
(li) ASTM D4657-92 (Reapproved 1998), Standard Test Method for
Polynuclear Aromatic Hydrocarbons in Water. January 1993. Table IC.
(lii) ASTM D4658-15, Standard Test Method for Sulfide Ion in Water.
Approved March 15, 2015. Table IB.
(liii) ASTM D4763-88 (Reapproved 2001), Standard Practice for
Identification of Chemicals in Water by Fluorescence Spectroscopy.
September 1988. Table IF.
(liv) ASTM D4839-03 (Reapproved 2017), Standard Test Method for
Total Carbon and Organic Carbon in Water by Ultraviolet, or Persulfate
Oxidation, or Both, and Infrared Detection. Approved December 15, 2017.
Table IB.
(lv) ASTM D5257-17, Standard Test Method for Dissolved Hexavalent
Chromium in Water by Ion Chromatography. Approved December 1, 2017.
Table IB.
(lvi) ASTM D5259-92, Standard Test Method for Isolation and
Enumeration of Enterococci from Water by the Membrane Filter Procedure.
October 1992. Table IH, Note 9.
[[Page 27327]]
(lvii) ASTM D5392-93, Standard Test Method for Isolation and
Enumeration of Escherichia coli in Water by the Two-Step Membrane
Filter Procedure. September 1993. Table IH, Note 9.
(lviii) ASTM D5673-16, Standard Test Method for Elements in Water
by Inductively Coupled Plasma--Mass Spectrometry. Approved February 1,
2016. Table IB.
(lix) ASTM D5907-18, Standard Test Methods for Filterable Matter
(Total Dissolved Solids) and Nonfilterable Matter (Total Suspended
Solids) in Water. Approved May 1, 2018. Table IB.
(lx) ASTM D6503-99, Standard Test Method for Enterococci in Water
Using Enterolert. April 2000. Table IA Note 9, Table IH, Note 9.
(lxi) ASTM. D6508-15, Standard Test Method for Determination of
Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion
Electrophoresis and Chromate Electrolyte. Approved October 1, 2015.
Table IB, Note 54.
(lxii) ASTM. D6888-16, Standard Test Method for Available Cyanides
with Ligand Displacement and Flow Injection Analysis (FIA) Utilizing
Gas Diffusion Separation and Amperometric Detection. Approved February
1, 2016. Table IB, Note 59.
(lxiii) ASTM. D6919-17, Standard Test Method for Determination of
Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water and
Wastewater by Ion Chromatography. Approved June 1, 2017. Table IB.
(lxiv) ASTM. D7065-17, Standard Test Method for Determination of
Nonylphenol, Bisphenol A, p-tert-Octylphenol, Nonylphenol
Monoethoxylate and Nonylphenol Diethoxylate in Environmental Waters by
Gas Chromatography Mass Spectrometry. Approved December 15, 2017. Table
IC.
(lxv) ASTM D7237-18, Standard Test Method for Free Cyanide with
Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and
Amperometric Detection. Approved December 1, 2018. 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. Approved August 1,
2020. Table IB.
(lxvii) ASTM D7365-09a (Reapproved 2015), Standard Practice for
Sampling, Preservation and Mitigating Interferences in Water Samples
for Analysis of Cyanide. Approved July 15, 2015. Table II, Notes 5 and
6.
(lxviii) ASTM. D7511-12 (Reapproved 2017)\e1\, Standard Test Method
for Total Cyanide by Segmented Flow Injection Analysis, In-Line
Ultraviolet Digestion and Amperometric Detection. Approved July 1,
2017. Table IB.
(lxix) ASTM D7573-18a\e1\, Standard Test Method for Total Carbon
and Organic Carbon in Water by High Temperature Catalytic Combustion
and Infrared Detection. Approved December 15, 2018. Table IB.
(lxx) ASTM D7781-14, Standard Test Method for Nitrite-Nitrate in
Water by Nitrate Reductase, Approved April 1, 2014. Table IB.
* * * * *
(19) FIAlab Instruments, Inc., 334 2151 N. Northlake Way, Seattle,
WA 98103; phone: (425)376-0450; website: www.flowinjection.com/app-notes/epafialab100.
(i) FIAlab 100, Determination of Inorganic Ammonia by Continuous
Flow Gas Diffusion and Fluorescence Detector Analysis, April 4, 2018.
Table IB, Note 82.
(ii) [Reserved]
* * * * *
(26) MACHEREY-NAGEL GmbH and Co., 2850 Emrick Blvd., Bethlehem, PA
18020; Phone: (888)321-6224.
(i) Method 036/038 NANOCOLOR[supreg] COD LR/HR, Spectrophotometric
Measurement of Chemical Oxygen Demand in Water and Wastewater, Revision
1.5, May 2018. Table IB, Note 83.
(ii) [Reserved]
(27) Micrology Laboratories, LLC (now known as Roth Bioscience,
LLC), 1303 Eisenhower Drive, Goshen, IN 46526; phone: (574)533-3351.
(i) KwikCount\TM\ EC Medium E. coli enzyme substrate test, Rapid
Detection of E. coli in Beach Water By KwikCount\TM\ EC Membrane
Filtration. 2014. Table IH, Notes 28 and 29.
(ii) [Reserved]
* * * * *
(33) Pace Analytical Services, LLC, 1800 Elm Street, SE,
Minneapolis, MN 55414; phone: (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; phone: (888)373-0881.
(i) SGS AXYS Method 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-Mass
Spectrometry (GC/MS/MS)., Revision 1.0, revised August 2020. Table IC,
Note 16.
(ii) [Reserved]
* * * * *
(40) U.S. Geological Survey (USGS), U.S. Department of the
Interior, Reston, Virginia. Available from USGS Books and Open-File
Reports (OFR) Section, Federal Center, Box 25425, Denver, CO 80225;
phone: (703)648-5953; website: ww.usgs.gov.
* * * * *
(ii) Techniques and Methods--Book 5, Laboratory Analysis--Section
B, Methods of the National Water Quality Laboratory--Chapter 12,
Determination of Heat Purgeable and Ambient Purgeable Volatile Organic
Compounds in Water by Gas Chromatography/Mass Spectrometry 2016.
* * * * *
(ix) OFR 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. Table IB,
Notes 51 and 80; Table IC, Note 9.
* * * * *
(xiv) OFR 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. Table IC, Note 13.
* * * * *
(e) * * *
Table II--Required Containers, Preservation Techniques, and Holding
Times
* * * * *
\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. 2024-07412 Filed 4-15-24; 8:45 am]
BILLING CODE 6560-50-P