80 FR 8956 - Clean Water Act Methods Update Rule for the Analysis of Effluent
ENVIRONMENTAL PROTECTION AGENCY
Federal Register Volume 80, Issue 33 (February 19, 2015)
Page Range
8956-9075
FR Document
2015-02841
EPA proposes changes to pollutant analysis methods that are used by industries and municipalities to analyze the chemical, physical, and biological components of wastewater and other environmental samples that are required by regulations under the Clean Water Act. EPA designed the proposed changes to increase flexibility for the regulated community, improve data quality, and update CWA methods to keep current with technology advances and analytical methods science. EPA updates and revises the CWA analytical methods from time to time, the most recent updates being completed in 2012. The new set of proposed changes described in this notice include revisions to current EPA methods and new and/or revised methods published by voluntary consensus standard bodies, such as ASTM International and the Standard Methods Committee. EPA also proposes to approve certain methods reviewed under the alternate test procedures program and clarify the procedures for EPA approval of nationwide and limited use alternate test procedures. Further, EPA proposes amendments to the procedure for determination of the method detection limit to address laboratory contamination and to better account for intra-laboratory variability.
Federal Register, Volume 80 Issue 33 (Thursday, February 19, 2015)
[Federal Register Volume 80, Number 33 (Thursday, February 19, 2015)]
[Proposed Rules]
[Pages 8956-9075]
From the Federal Register Online [www.thefederalregister.org]
[FR Doc No: 2015-02841]
[[Page 8955]]
Vol. 80
Thursday,
No. 33
February 19, 2015
Part II
Environmental Protection Agency
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40 CFR Part 136
Clean Water Act Methods Update Rule for the Analysis of Effluent;
Proposed Rule
Federal Register / Vol. 80 , No. 33 / Thursday, February 19, 2015 /
Proposed Rules
[[Page 8956]]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 136
[EPA-HQ-OW-2014-0797; FRL-9920-55-OW]
RIN 2040-AF48
Clean Water Act Methods Update Rule for the Analysis of Effluent
AGENCY: Environmental Protection Agency (EPA).
ACTION: Proposed rule.
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SUMMARY: EPA proposes changes to pollutant analysis methods that are
used by industries and municipalities to analyze the chemical,
physical, and biological components of wastewater and other
environmental samples that are required by regulations under the Clean
Water Act. EPA designed the proposed changes to increase flexibility
for the regulated community, improve data quality, and update CWA
methods to keep current with technology advances and analytical methods
science. EPA updates and revises the CWA analytical methods from time
to time, the most recent updates being completed in 2012. The new set
of proposed changes described in this notice include revisions to
current EPA methods and new and/or revised methods published by
voluntary consensus standard bodies, such as ASTM International and the
Standard Methods Committee. EPA also proposes to approve certain
methods reviewed under the alternate test procedures program and
clarify the procedures for EPA approval of nationwide and limited use
alternate test procedures. Further, EPA proposes amendments to the
procedure for determination of the method detection limit to address
laboratory contamination and to better account for intra-laboratory
variability.
DATES: Comments on this proposed rule must be received on or before
April 20, 2015.
ADDRESSES: Submit your comments, identified by Docket ID No. EPA-HQ-OW-
2014-0797, by one of the following methods:
www.regulations.gov: Follow the on-line instructions for
submitting comments.
Email: [email protected], Attention Docket ID number EPA-
HQ-OW-2014-0797.
Mail: Water Docket, Environmental Protection Agency, Mail
code: 4203M, 1200 Pennsylvania Ave. NW., Washington, DC 20460.
Attention Docket ID number EPA-HQ-OW-2014-0797. Please include a total
of 3 copies.
Hand Delivery: Water Docket, EPA Docket Center, EPA West
Building, Room 3334, 1301 Constitution Ave. NW., Washington, DC,
Attention Docket ID number EPA-HQ-OW-2014-0797. Such deliveries are
only accepted during the Docket's normal hours of operation, and
special arrangements should be made for deliveries of boxed information
by calling 202-566-2426.
Instructions: Direct your comments to Docket ID number EPA-HQ-OW-
2014-0797. EPA's policy is that all comments received will be included
in the public docket without change and may be made available online at
www.regulations.gov, including any personal information provided,
unless the comment includes information claimed to be Confidential
Business Information (CBI) or other information whose disclosure is
restricted by statute. Do not submit information that you consider to
be CBI or otherwise protected through www.regulations.gov or email. The
www.regulations.gov Web site is an ``anonymous access'' system, which
means EPA will not know your identity or contact information unless you
provide it in the body of your comment. If you send an email comment
directly to EPA without going through www.regulations.gov your email
address will be automatically captured and included as part of the
comment that is placed in the public docket and made available on the
Internet. If you submit an electronic comment, EPA recommends that you
include your name and other contact information in the body of your
comment and with any disk or CD-ROM you submit. If EPA cannot read your
comment due to technical difficulties and cannot contact you for
clarification, EPA may not be able to consider your comment. Electronic
files should avoid the use of special characters, any form of
encryption, and be free of any defects or viruses.
Docket: All documents in the docket are listed in the
www.regulations.gov index. Although listed in the index, some
information in the docket is not publicly available, e.g., CBI or other
information whose disclosure is restricted by statute. Certain other
material, such as copyrighted material, will be publicly available only
in hard copy. Publicly available docket materials are available either
electronically in www.regulations.gov or in hard copy at the Water
Docket in EPA Docket Center, EPA/DC, EPA West William J. Clinton
Building, Room 3334, 1301 Constitution Ave. NW., Washington, DC. The
Public Reading Room is open from 8:30 a.m. to 4:30 p.m., Monday through
Friday, excluding legal holidays. The telephone number for the Public
Reading Room is 202-566-1744 and the telephone number for the Water
Docket is 202-566-2426.
FOR FURTHER INFORMATION CONTACT: Adrian Hanley, Engineering and
Analysis Division (4303T), Office of Water, Environmental Protection
Agency, 1200 Pennsylvania Ave. NW., Washington, DC 20460-0001;
telephone: 202-564-1564; email: [email protected].
SUPPLEMENTARY INFORMATION:
Table of Contents
I. General Information
II. Overview
III. Statutory Authority
IV. Purpose and Summary of Proposed Rule
V. Statutory and Executive Order Reviews
I. General Information
A. Does this Action apply to me?
Entities potentially affected by the requirements of this proposed
action include:
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Examples of potentially affected
Category entities
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State, Territorial, and Indian States, territories, and tribes
Tribal Governments. authorized to administer the
National Pollutant Discharge
Elimination System (NPDES)
permitting program; states,
territories, and tribes providing
certification under CWA section
401; state, territorial, and tribal
owned facilities that must conduct
monitoring to comply with NPDES
permits.
Industry.......................... Facilities that must conduct
monitoring to comply with NPDES
permits.
Municipalities.................... Publicly Owned Treatment Works
(POTWs) or other municipality owned
facilities that must conduct
monitoring to comply with NPDES
permits.
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[[Page 8957]]
This table is not exhaustive, but rather provides a guide for
readers regarding entities likely to be affected by this action. This
table lists types of entities that EPA is now aware of that could
potentially be affected by this action. Other types of entities not
listed in the table could also be affected. To determine whether your
facility is affected by this action, you should carefully examine the
applicability language at 40 CFR 122.1 (NPDES purpose and scope), 40
CFR 136.1 (NPDES permits and CWA) and 40 CFR 403.1 (pretreatment
standards purpose 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 should I consider as I prepare my comments for EPA?
1. Submitting CBI. Do not submit CBI to EPA through
www.regulations.gov or email. Clearly mark the part or all of the
information that you claim to be CBI. For CBI information in a disk
that you mail to EPA, mark the outside of the disk as CBI and then
identify electronically within the disk the specific information that
is claimed as CBI. In addition to one complete version of the comment
that includes information claimed as CBI, a copy of the comment that
does not contain the information claimed as CBI must be submitted for
inclusion in the public docket. Information so marked will not be
disclosed except in accordance with procedures for handling and
protection of CBI set forth in 40 CFR part 2.
2. Tips for Preparing Your Comments. When submitting comments,
remember to:
Identify the rulemaking by Docket ID number and other
identifying information (subject heading, Federal Register date and
page number).
Explain why you agree or disagree, suggest alternatives,
and substitute language for your requested changes.
Describe any assumptions and provide any technical
information and/or data that you used.
If you estimate potential costs or burdens, explain how
you arrived at your estimate in sufficient detail to allow for it to be
reproduced.
Provide specific examples to illustrate your concerns, and
suggest alternatives.
Explain your views as clearly as possible, avoiding the
use of profanity or personal threats.
Make sure to submit your comments by the comment period
deadline identified.
II. Overview
This preamble describes the reasons for the proposed rule; the
legal authority for the proposed rule; a summary of the proposed
changes and clarifications; and explanation of the abbreviations and
acronyms used in this document. In addition, this preamble solicits
comment and data from the public.
Abbreviations and Acronyms Used in the Preamble and Proposed Rule Text
AA: Atomic Absorption
ADMI: American Dye Manufacturers Institute
ASTM: ASTM International
ATP: Alternate Test Procedure
CAS: Chemical Abstract Services
CFR: Code of Federal Regulations
CWA: Clean Water Act
EPA: Environmental Protection Agency
FLAA: Flame Atomic Absorption Spectroscopy
GC: Gas Chromatograph
ICP/AES: Inductively Coupled Plasma--Atomic Emission Spectroscopy
ICP/MS: Inductively Coupled Plasma--Mass Spectrometry
LCS: Laboratory Control Sample
MS: Mass Spectrometry
MS/MSD: Matrix Spike/Matrix Spike Duplicate
NPDES: National Pollutant Discharge Elimination System
POTW: Publicly Owned Treatment Works
QA: Quality Assurance
QC: Quality Control
SM: Standard Methods
STGFAA: Stabilized Temperature Graphite Furnace Atomic Absorption
Spectroscopy
USGS: United States Geological Survey
VCSB: Voluntary Consensus Standards Body
III. Statutory Authority
EPA proposes this regulation under the authorities of sections
301(a), 304(h), and 501(a) of the CWA, 33 U.S.C. 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, a NPDES permit issued under section 402 of the
CWA. Section 304(h) of the CWA requires the Administrator of the EPA to
``. . . promulgate guidelines establishing test procedures for the
analysis of pollutants that shall include the factors which must be
provided in any certification pursuant to [section 401 of the CWA] or
permit application pursuant to [section 402 of the CWA].'' Section
501(a) of the CWA authorizes the Administrator to ``. . . prescribe
such regulations as are necessary to carry out this function under [the
CWA].'' EPA generally has codified its test procedure regulations
(including analysis and sampling requirements) for CWA programs at 40
CFR part 136, though some requirements are codified in other parts
(e.g., 40 CFR Chapter I, Subchapters N and O).
IV. Purpose and Summary of Proposed Rule
The CWA requires EPA to promulgate test procedures (analytical
methods) for analyses required in NPDES permit applications and for
reports required under NPDES permits. EPA codifies these approved test
procedures at 40 CFR part 136. EPA regions, as well as authorized
states, territories and tribes issue NPDES permits. These permits must
include conditions designed to ensure compliance with the technology-
based and water quality-based requirements of the CWA, including in
many cases, restrictions on the quantity of specific pollutants that
can be discharged as well as pollutant measurement and reporting
requirements. Often, entities have a choice in deciding which approved
test procedure they will use for a specific pollutant because EPA has
approved the use of more than one.\1\
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\1\ 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 analytical methods must be used include,
among others, the following: (1) Applications for NPDES permits, (2)
sampling or other reports required under NPDES permits, (3) other
requests for quantitative or qualitative effluent data under the NPDES
regulations, (4) State CWA 401 certifications and (5) sampling and
analysis required under EPA's General Pre-Treatment Regulations for
Existing and New Sources of Pollution 40 CFR 136.1 and 40 CFR
403.12(b)(5)(v).
Periodically, EPA proposes to update the approved methods in 40 CFR
part 136. In general, the changes in this proposed action fall into the
following categories: new and revised EPA methods and new and revised
methods adopted by VCSBs; methods EPA has reviewed under EPA's national
alternate test procedures (ATP) program and preliminarily concluded are
appropriate for nationwide use; certain corrections to 40 CFR part 136;
and amendments to the procedure for determination of the MDL primarily
to address laboratory contamination and to better account for intra-
laboratory variability. Collectively, EPA's current understanding
indicates that adoption of these proposed revisions would improve data
quality, update methods to keep current with technology advances,
provide additional
[[Page 8958]]
clarity for ATPs, and provide the regulated community with greater
flexibility.
The following paragraphs provide details on the proposed revisions.
A. Changes to 40 CFR 136.3 and Appendix A to Include New Versions of
Previously Approved EPA Methods
EPA proposes revisions to the approved EPA Methods 608, 624, and
625 which it adopted in 1984, and proposes to make a minor correction
to the parameter list in EPA Method 611. These four EPA methods are
listed in Table IC at 40 CFR part 136. Methods 608 and 625 also are
listed in Tables ID and IG, and Methods 624 and 625 are listed in Table
IF. EPA also proposes minor corrections to microbiological methods
1600, 1603, 1680, and 1682. These four EPA methods are listed in Table
IA at 40 CFR part 136, and Methods 1600 and 1603 are listed in Table
IH.
1. Methods 608, 624, and 625
The proposed revisions take advantage of improvements in analytical
technology and allow greater flexibility in order to accommodate future
improvements to the methods and generally obviate any need for
additional revisions. EPA revised these methods in collaboration with
other EPA offices, states, and environmental laboratory organizations.
The revisions conform to the following principles:
Updated Technology: EPA changed the GC columns from packed columns
to capillary (open tubular) columns. Capillary columns provide greater
resolution and decreased adsorption (loss) of the analytes and,
therefore, result in a significant improvement in the accuracy
(recovery) and precision of the results.
Method Flexibility: The revised methods allow greater method
flexibility so that the methods more closely align with 40 CFR 136.6.
This flexibility would make it easier for laboratories to make in-house
improvements and technology updates in the future that will not
compromise the original quality control acceptance criteria of the
methods. Consistent with 40 CFR 136.6, EPA built into the methods
procedures that will allow a laboratory to make limited changes to a
method without applying for an ATP; however, the laboratory must
document that the revisions produce results consistent with the QC
acceptance criteria in the method in order to take advantage of the
built-in flexibility. For example, the revised methods allow access to
a greater list of compounds than the list of compounds determined by
the original versions of these methods, provided that the laboratory
can demonstrate acceptable accuracy and precision with these analytes
in the specified matrices. The expanded list of compounds is an
amalgamation of lists from Methods 1624, 1625, 1699 and other EPA
methods that demonstrate the technology can be used to quantify these
additional analytes. The revisions also allow more flexibility to adopt
different extraction procedures, such as solid phase extraction. The
revised methods include requirements for a laboratory to develop its
own in-house QC acceptance criteria for tests of the laboratory control
sample and tests of matrix spike and matrix spike duplicate samples,
provided the LCS and MS/MSD meet minimum criteria specified in the
method. The revisions also clarify that hydrogen can be used as a
carrier gas for the methods. Some of the flexibility EPA proposes to
add to the methods is currently specified in 40 CFR 136.6(b)(4)(xvi).
Because EPA proposes to incorporate that flexibility directly into the
method, EPA proposes to delete the corresponding text from 40 CFR
136.6.
Method Harmonization: EPA updated these methods to make them more
consistent with the most recent updates of similar methods from the
Office of Ground Water and Drinking Water and the Office of Resource
Conservation and Recovery. EPA revised the required QC frequencies and
standards (internal standards and surrogates) to more closely match the
methods from other EPA analytical method programs. Laboratories that
run methods from multiple EPA programs will benefit from these
revisions.
2. Method 611
EPA proposes a minor correction to a parameter name in the
parameter list of of EPA Method 611 (``Haloethers''). As currently
listed, the compound with the CAS Registry Number 108-60-1 is bis(2-
chloroisopropyl)ether. EPA proposes to correct the analyte name to
2,2'-oxybis(1-chloropropane), which matches the CAS Number 108-60-1.
The original analyte name bis(2-chloroisopropyl)ether has a CAS number
of 39638-32-9. EPA is unaware that this chemical has ever been in
industrial production, and is therefore unlikely to be a compound of
monitoring concern. Furthermore, it is not possible to procure an
analytical standard reference material for the compound with CAS number
39638-32-9. The compound in the parameter list should be 2,2'-oxybis(1-
chloropropane), CAS number 108-60-1.
3. Methods 1600, 1603, 1680, and 1682
EPA proposes the following changes for EPA microbiological methods
1600, 1603, 1680, and 1682. These changes correct typographical or
other errors that EPA identified in the methods after publication. EPA
proposes to revise all of these methods with new EPA document numbers
and dates.
a. EPA Method 1600 for Enterococci using membrane filtration: In
Table 3 Verification controls, EPA changed the negative control for
brain heart infusion broth incubated at 45 [deg]C from E. coli to
Enterobacter aerogenes. E. coli is thermotolerant and E. aerogenes is
not, so E. coli is not an appropriate negative control when heated.
b. EPA Method 1603 for E. coli using membrane filtration: In
Section 11.5, EPA changed the number of colonies on a countable plate
from 20-60 to 20-80 colonies. Sixty colonies was a typographical error.
In addition the following sentence was inadvertently omitted and EPA
included it: Sample volumes of 1-100 mL are normally tested at half-log
intervals (e.g., 100, 30, 10, and 3 mL).
c. EPA Method 1680 for fecal coliforms using multiple tube
fermentation: in Section 3.1 Definitions, the sentence ``The
predominant fecal coliform is E. coli.'' should read ``The predominant
fecal coliform can be E. coli.''
d. EPA Method 1682 for Salmonella by MSRV medium: (1) In Section
9.3, Table 2, the lab-prepared spike acceptance criteria should read
``Detect--254%'' and ``Detect--287%'' and (2) in Section 14.5, Table 9,
the spiked Salmonella for Example 2, Liquid should read ``3.7x10 \8\
CFU/mL.''
B. Methods Incorporated 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 pollutant and regulated
entities often have a choice in the selected method. The proposed rule
contains revisions to methods that will be incorporated by reference
from two VCSBs: Standard Methods and ASTM. EPA proposed VCSB methods in
compliance with the National Technology Transfer Act (see Section V.I
below). The proposed VCSB methods are available on their respective
VCSB Web sites to everyone at a cost determined by the VCSB, generally
from $40 to $80. Both organizations also offer memberships or
subscriptions that allow unlimited access to their methods. The cost of
obtaining these methods is not a
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significant financial burden for a discharger or environmental
laboratory, making the methods reasonably available. The proposal also
includes USGS methods and vendor ATPs that are incorporated by
reference. The ATPs and USGS methods are available free of charge on
the Web site for that organization. Therefore, EPA concludes that the
proposed methods and ATPs incorporated by reference are reasonably
available. The individual standards are discussed in greater detail
below.
C. Changes to 40 CFR 136.3 to Include New Versions of Approved Standard
Methods
EPA proposes to approve new versions of currently approved Standard
Methods. The new versions of currently approved Standard Methods
clarify or improve the instructions in the method, improve the QC
instructions, or make editorial corrections. Consistent with the
previous method update rule (77 FR 29767-29768), EPA proposes to
generally approve and include in 40 CFR part 136 only the most recent
version of a method published by the Standard Methods Committee by
listing only one version of the method with the year of publication
designated by the last four digits in the method number (e.g., SM 3111
B-2011). The date indicates the latest revision date of the method.
This allows use of a specific method in any edition that includes a
method with the same method number and year of publication.
Most of the revisions that EPA proposes to Standard Methods
previously approved in 40 CFR part 136 do not contain any substantive
changes. The following describes the proposed non-substantive changes
related to Standard Methods in 40 CFR part 136. Each entry contains the
proposed Standard Methods number and date, the parameter, and a brief
description of the analytical technique. The methods listed below are
organized according to the table at 40 CFR part 136 in which they
appear.
The following changes would apply to Table IA at 40 CFR part 136:
1. SM 9221 (B,C,E,F)-2006, Coliform (fecal), Coliform (fecal) in
presence of chlorine, Coliform (total), Coliform (total) in presence of
chlorine, E. coli, most probable number (MPN), 5 tube 3 dilution.
2. SM 9223-2004, E. coli, multiple tube/multiple well.
3. SM 9230 (B,C)-2007, Fecal Streptococci, Enterococci, most
probable number (MPN), 5 tube 3 dilution or membrane filtration.
The following changes would apply to Table IB at 40 CFR part 136:
1. SM 2120 B-2011, color, platinum cobalt method.
2. SM 2130 B-2011, turbidity, nephelometric method.
3. SM 2310 B-2011, acidity, titration using electrometric endpoint
or phenolphthalein endpoint.
4. SM 2320 B-2011, alkalinity, electrometric or colorimetric
titration to pH 4.5.
5. SM 2340 B-2011 and SM 2340 C-2011, hardness, by the calculation
method or EDTA titration.
6. SM 2510 B-2011, conductivity, Wheatstone bridge method.
7. SM 2540 B-2011, SM 2540 C-2011, SM 2540 D-2011, SM 2540 E-2011,
and SM 2540 F-2011, total, filterable, non-filterable, volatile, and
settleable residue (solids, listed in the same order as the method
numbers), all by gravimetric methodologies.
8. SM 2550 B-2010, temperature, thermometric.
9. SM 3111 B-2011, SM 3111 C-2011, SM 3111 D-2011, and SM 3111 E-
2011, metals, direct aspiration AA methods with different gas mixtures.
Each method has a different list of metals; no changes are proposed to
these lists.
10. SM 3112 B-2011, metals, applicable to mercury, cold-vapor
atomic absorption spectrometric method.
11. SM 3114 B-2011 and SM 3114 C-2011, total arsenic and total
selenium, hydride generation/atomic absorption spectrometric methods.
Both analyze total arsenic and total selenium.
12. SM 3120 B-2011, metals, ICP method; no changes are proposed for
the approved list of metals.
13. SM 3125 B-2011, metals, ICP/MS method; no changes are proposed
for the approved list of metals.
14. SM 3500-Al B-2011, aluminum, colorimetric method.
15. SM 3500-As B-2011, arsenic, colorimetric method (SDDC).
16. SM 3500-Ca B-2011, calcium, titrimetric method (EDTA).
17. SM 3500-Cr B-2011 and SM 3500-Cr C-2011, chromium, the ``B''
method uses a colorimetric method (diphenyl-carbazide) and is approved
for total or dissolved chromium, the ``C'' method uses ion
chromatography and is only approved for dissolved chromium.
18. SM 3500-Cu B-2011 and SM 3500-Cu C-2011, copper, both method
sections use colorimetric methods, the ``B'' method uses a neocuproine
reagent and the ``C'' method uses a bathocuproine reagent.
19. SM 3500-Fe B-2011, iron, colorimetric method (phenanthroline).
20. SM 3500-K B-2011 and SM 3500-K C-2011, potassium, the ``B''
method is a flame photometric method and the ``C'' method is an
electrode method.
21. SM 3500-Mn B-2011, manganese, colorimetric method (persulfate).
22. SM 3500-Na B-2011, sodium, flame photometric method.
23. SM 3500-Pb B-2011, lead, colorimetric method (dithizone).
24. SM 3500-V B-2011, vanadium, colorimetric method (gallic acid).
25. SM 3500-Zn B-2011, zinc, colorimetric method (zincon).
26. SM 4110 (B-D)-2011, anions, ion chromatography; no changes are
proposed for the approved analyte list.
27. SM 4140 B-2011, inorganic anions, capillary ion electrophoresis
with indirect UV detection: No changes are proposed for the approved
analyte list.
28. SM 4500-B B-2011, boron, spectrophotometer or filter photometer
(curcumin).
29. SM 4500-Cl- (B-E)-2011, chloride, titrimetric:
(silver nitrate), (mercuric nitrate), automated (ferricyanide),
potentiometric titration
30. SM 4500-Cl (B-G)-2011, chlorine (residual), amperometric
direct, amperometric direct (low level), iodometric direct, back
titration ether end-point, titrimetric: N,N-diethyl-p-phenylenediamine
with ferrous ammonium sulfate (DPD-FAS), spectrophotometric (DPD).
31. SM 4500-CN- (B-G)-2011, cyanide, manual distillation
with MgCl2 followed by: Titrimetric, spectrophotometric,
manual, ion selective electrode, cyanide amenable to chlorination
(CATC); manual distillation with MgCl2, followed by:
Titrimetric or spectrophotometric.
32. SM 4500-F- (B-E)-2011, fluoride, manual
distillation, followed by any of the following: Electrode, manual,
colorimetric, fluoride dye reagent (SPADNS is the common name for the
fluoride dye reagent which is a mixture of chemicals), automated
complexone.
33. SM 4500-H\+\ B-2011, hydrogen ion (pH), electrometric
measurement.
34. SM 4500-NH3 (B-H)-2011, ammonia (as nitrogen),
manual distillation or gas diffusion (pH > 11), followed by any of the
following: Titration, electrode, manual phenate, salicylate, or other
substituted phenols in Berthelot reaction based methods; automated
phenate, salicylate, or other substituted phenols in Berthelot reaction
based methods.
35. SM 4500-NO2- B-2011, nitrite (as
nitrogen), spectrophotometric: Manual.
36. SM 4500-NO3- D-2011, nitrate (as
nitrogen), ion selective electrode.
37. SM 4500-NO3- (E,F, H)-2011, nitrate-
nitrite (as nitrogen), colorimetric: Cadmium reduction-manual and
automated, and colorimetric: Automated hydrazine.
[[Page 8960]]
38. SM 4500-NO3- (E,F)-2011, nitrite (as
nitrogen), colorimetric: Cadmium reduction-manual and automated.
39. SM 4500-Norg (B-D)-2011, total Kjeldahl nitrogen (as
nitrogen, organic), semi-automated block digester colorimetric
(distillation not required).
40. SM 4500-O (B-G), oxygen (dissolved), Winkler (azide
modification), electrode.
41. SM 4500-P (B (5), E-H)-2011, phosphorus and ortho-phosphate,
persulfate digestion, digestion, followed by any of the following:
Manual or automated ascorbic acid reduction. The ``B Part 5'' method is
the persulfate digestion procedure and is required prior to measurement
of total phosphorus using SM 4500 P (E-H). The ``E'' through ``G''
methods are approved for both total phosphorus and ortho-phosphate. The
``H'' method is only approved for total phosphorous.
42. SM 4500-S2- (B-D, F,G)-2011, sulfide, sample
pretreatment, titrimetric (iodine) analysis, colorimetric (methylene
blue), ion selective electrode.
43. SM 4500-SiO2 (C,E,F)-2011, silica, 0.45-micron
filtration followed by any of the following: Colorimetric, manual or
automated (Molybdosilicate).
44. SM 4500-SO32- B-2011, sulfite,
titrimetric (iodine-iodate).
45. SM 4500-SO42- (C-G)-2011, sulfate,
automated colorimetric, gravimetric, and turbidimetric.
46. SM 5210 B-2011, biochemical oxygen demand (BOD5), dissolved
oxygen depletion.
47. SM 5220 (B-D)-2011, chemical oxygen demand (COD), titrimetric;
spectrophotometric, manual or automatic.
48. SM 5310 (B-D)-2011, total organic carbon (TOC), combustion,
heated persulfate or UV persulfate oxidation.
49. SM 5520 (B,F)-2011, oil and grease, hexane extractable material
(HEM): n-hexane extraction and gravimetry, silica gel treated HEM (SGT-
HEM): Silica gel treatment and gravimetry.
50. SM 5530 (B,D)-2010, phenols, manual distillation, followed by
colorimetric (4AAP) manual.
51. SM 5540 C-2011, surfactants, colorimetric (methylene blue).
The following changes would apply to Table IC at 40 CFR part 136:
1. SM 6200 (B,C)-2011, volatile organic compounds, purge and trap
capillary-column gas chromatographic/mass spectrometric (GC/MS), purge
and trap capillary-column gas chromatographic (GC).
2. SM 6440 B-2005, polynuclear aromatic hydrocarbons (PAHs), high
performance liquid chromatography (HPLC).
The following changes would apply to Table ID at 40 CFR part 136:
1. SM 6630 (B, C)-2007, organochlorine pesticides, gas
chromatography (GC).
2. SM 6640 B-2006, acidic herbicide compounds, gas chromatography
(GC).
EPA also proposes revisions to certain Standard Methods approved in
Part 136 for which Standard Methods adopted updates that contain
substantive changes. The following summarizes these changes for each
method, organized by the table at 40 CFR part 136 in which they appear.
The following changes would apply to Table IA and/or Table IH at 40
CFR part 136:
1. EPA proposes that the membrane filtration method SM 9222 B-1997
be replaced with SM 9222 B-2006. This method analyzes Coliform (total)
in the presence of chlorine. The newer method includes a number of
technology updates that do not significantly change the procedure. In
addition, the method:
a. Modified the procedure to allow for the use of a humidified
incubator if loose-lidded plates are used during incubation.
b. Added a note that five typical and five atypical colonies per
membrane need to be identified during coliform verification.
c. Moved the definition of ``Coliform'' that was Section 4 of SM
9222, and renumbered the rest of the document, such that the
``Procedure'' is now Section 4, instead of Section 5. This is not a
substantive change except that in Table IA, Parameter 4 ``Coliform
(total), in presence of chlorine, number per 100 mL'' the citation for
``MF with enrichment'' would be changed from ``9222 (B+B.5c)-1997'' to
``9222 (B+B.4c)-2006.''
2. EPA proposes that the membrane filtration method SM 9222 D-1997
be replaced with SM 9222 D-2006. This method analyzes Coliform (fecal)
and Coliform (fecal) in the presence of chlorine. The new method allows
use of a dry recirculating incubator as specified in the culture dishes
section. In addition, EPA proposes to add the following footnote to
Tables IA and IH regarding SM9222D-2006 for fecal coliform verification
frequency: ``The verification frequency is at least five typical and
five atypical colonies per sampling site on the day of sample
collection & analysis.'' SM 9222 D-2006 specifies that the fecal
coliform colonies should be verified ``at a frequency established by
the laboratory,'' which can be as low as zero. Colonies need be
verified to prevent misidentification of results as false positive or
false negative.
3. EPA proposes that the membrane filtration method SM 9222 G-1997
be replaced with SM 9222 G-2006 in Table IH. These methods analyze for
E. coli and Fecal Coliforms. The newer method includes a number of
technology updates that do not significantly change the procedure. In
addition, the method now has a modified composition of EC broth to
include different quantities of KH2PO4 and 4-
methylumbelliferyl-[beta]-D-glucuronide.
The following changes would apply to Table IB at 40 CFR part 136:
EPA proposes SM 2120 F-2011 be added to Table IB for Color. EPA
previously approved it as SM 2120 E-1993. It is also similar to the
currently approved National Council for Air and Stream Improvement,
Inc. method that uses American Dye Manufacturers Institute weighted-
ordinate spectrophotometric parameters.
1. EPA proposes that SM 3113 B-2004, a metals atomic absorption
furnace method, be replaced with the revised version SM 3113 B-2010.
The only substantive change would be a reduction in the required
replicate analyses of each calibration standard from three to two.
Similar EPA methods do not require replicates of each calibration
standard.
Finally, Standard Methods requested that EPA propose SM 6810 for
the analysis of pharmaceutical and personal care products in water. EPA
does not propose to add this method because no supporting data were
received by the deadline to demonstrate that the method had undergone
full inter-laboratory validation.
D. Changes to 40 CFR 136.3 to Include New Versions of Approved ASTM
Methods
EPA proposes to approve new versions of currently approved ASTM
methods, for the same reasons outlined in the first paragraph of
Section IV.B above. Many of the changes EPA proposes to ASTM Methods
approved in 40 CFR part 136 do not contain any substantive changes. The
following describes the proposed changes related to ASTM Methods in 40
CFR part 136. Each entry contains (in the following order): proposed
ASTM method number and date, the parameter, a brief description of the
analytical technique, and a brief description of any substantive
changes in this revision from the last approved version of the method.
The methods listed below are organized according to the table at 40 CFR
part 136 in which they appear.
The following changes would apply to Table IB at 40 CFR part 136:
[[Page 8961]]
1. ASTM D 511-09 (A, B), calcium and magnesium, titrimetric (EDTA),
AA direct aspiration; the modified method includes less specific
calibration requirements for the part A titrimetric method than the
previous version. However, the revised requirements are still more
comprehensive than other approved methods. Therefore, EPA considers
this revised method has adequate calibration criteria.
2. ASTM D 516-11, sulfate ion, turbidimetric, no substantive
changes.
3. ASTM D 858-12 (A-C), manganese, atomic absorption (AA) direct
aspiration, AA furnace; the modified method allows for pH adjustments
in the laboratory, if the sample is returned within 14 days following
sampling. The modified method also allows the use of block digestion
systems for trace metal analysis, and quality control procedures now
require the lab to analyze a continuing calibration blank and
continuing calibration verification at a frequency of 10%.
4. ASTM D 859-10, silica, colorimetric, manual; the modified method
allows the use of direct reading spectrophotometer or filter
photometer, which is common for most approved colorimetric methods.
5. ASTM D 1067-11, acidity or alkalinity, electrometric endpoint or
phenolphthalein endpoint; electrometric or colorimetric titration to pH
4.5, manual; no substantive changes
6. ASTM D 1068-10 (A-C), iron, AA direct aspiration; AA furnace;
Colorimetric (Phenanthroline); EPA originally approved Parts A-D, but
ASTM discontinued Part B. EPA proposes that Parts C and D in the
existing 40 CFR part 136 Table 1B, be shifted to Parts B and C to
account for the discontinued Part B. Additionally, ASTM increased the
frequency of quality control parameters for Test Method A--Atomic
Absorption. The method now includes a method blank, a matrix spike
sample and a control sample with every ten samples.
7. ASTM D 1126-12, hardness, titrimetric (EDTA); no substantive
changes.
8. ASTM D 1179-10, fluoride ion, electrode, manual; colorimetric,
(SPADNS); The revision removed calculation, precision and bias, and
quality control procedures (method blank, matrix spike, LCS) previously
included for Test Method B-Ion Selective Electrode. The method replaces
those requirements with a lab duplicate and a reference sample
analysis. This is similar to EPA approved SM 4500-F- (C, D)
currently in 40 CFR part 136. The revision also removed the silver
sulfate reagent used to remove chloride from the sample, as it is no
longer considered a major interference.
9. ASTM D 1246-10, bromide ion, electrode; no substantive changes.
10. ASTM D 1687-12 (A-C), chromium (total) and dissolved hexavalent
chromium, colorimetric (diphenyl-carbazide); AA direct aspiration; AA
furnace; ASTM modified the method to allow the use of block digestion
systems for trace metal analysis, and now allows for pH adjustments in
the laboratory if the sample is returned within 14 days following
sampling.
11. ASTM D 1688-12 (A-C), copper, AA direct aspiration, AA furnace;
ASTM modified the method to allow the use of block digestion systems
for trace metal analysis, and now allows for pH adjustments in the
laboratory if the sample is returned within 14 days following sampling.
ASTM also requires analysis of a continuing calibration blank and
continuing calibration verification at a 10% frequency.
12. ASTM D 1691-12 (A, B), zinc, AA direct aspiration; ASTM
modified the method to allow the use of block digestion systems for
trace metal analysis, and now allows for pH adjustments in the
laboratory if the sample is returned within 14 days following sampling.
13. ASTM D 1976-12, dissolved, total-recoverable, or total
elements, inductively coupled plasma/atomic emission spectroscopy (ICP/
AES); ASTM modified the method to allow block digestion systems for
trace metal analysis.
14. ASTM D 3223-12, total mercury, cold vapor, manual; ASTM
modified the method to allow the use of block digestion systems for
trace metal analysis, and requires analysis of a continuing calibration
blank and continuing calibration verification at a 10% frequency.
15. ASTM D 3373-12, vanadium, AA furnace; ASTM modified the method
to allow the use of block digestion systems for trace metal analysis,
and requires analysis of a continuing calibration blank and continuing
calibration verification at a 10% frequency. ASTM now allows for pH
adjustments in the laboratory if the sample is returned within 14 days
following sampling.
16. ASTM D 3557-12 (A-D), cadmium, AA direct aspiration, AA
furnace, Voltammetry; ASTM modified the method to allow the use of
block digestion systems for trace metal analysis, and requires analysis
of a continuing calibration blank and continuing calibration
verification at a 10% frequency. ASTM now allows for pH adjustments in
the laboratory if the sample is returned within 14 days following
sampling.
17. ASTM D 3590-11 (A, B), total Kjeldahl nitrogen, manual
digestion and distillation or gas diffusion; semi-automated block
digester colorimetric (distillation not required); ASTM revised the
preservation method to allow storing samples at 2-6 [deg]C, instead of
the previous 4 [deg]C. The method includes OI Analytical Flow Injection
Analysis (FIA) performance data using an alternative copper sulfate
catalyst in place of mercury (note: ``OI Analytical'' is a company
name, not an acronym).
18. ASTM D 4382-12, barium, AA furnace; ASTM modified the method to
allow the use of block digestion systems for trace metal analysis, and
requires analysis of a continuing calibration blank and continuing
calibration verification at a 10% frequency.
19. ASTM D 4658-09, sulfide ion, ion selective electrode; no
substantive changes.
20. ASTM D 5257-11, dissolved hexavalent chromium, ion
chromatography; ASTM recommends buffering samples containing very high
levels of anionic species to a pH of 9-9.5, then filtering the sample
and storing it at <6 [deg]C for a holding time of 28 days to prevent
reduction of Cr(VI) to Cr(III). ASTM added an allowance for alternate
holding times in Sections 1.3 and 9.2 if the user ``demonstrates that
holding time does not affect sample integrity per US EPA 40 CFR 136 . .
.''
21. ASTM D 5673-10, dissolved elements and total-recoverable
elements, ICP/MS; no substantive changes.
22. ASTM D 5907-13, filterable matter (total dissolved solids) and
nonfilterable matter (total suspended solids), gravimetric, 180[deg]
gravimetric, 103-105[deg] post washing of residue; no substantive
changes.
23. ASTM D 6508-10, inorganic anions (fluoride, bromide, chloride,
nitrite, nitrate, orthophosphate, and sulfate), capillary ion
electrophoresis with indirect UV detection; no substantive changes.
24. ASTM D 7284-13, total cyanide, manual distillation with
MgCl2 followed by flow injection, gas diffusion amperometry;
ASTM modified the method to include the use of a collector tube of the
micro distillation apparatus with 1.5 ml of 1.0 M NaOH, and included
information regarding the use of this collector tube in the procedure.
ASTM also added information regarding the precision and bias associated
with this method based on an interlaboratory study.
[[Page 8962]]
25. ASTM D 7511-12, total cyanide, segmented flow injection, in-
line ultraviolet digestion, followed by gas diffusion amperometry; no
substantive changes.
The following changes would apply to Table IC at 40 CFR part 136:
1. ASTM D 7065-11, nonylphenol, bisphenol A, p-tert-octylphenol,
nonylphenol monoethoxylate, nonylphenol diethoxylate, gas
chromatography/mass spectrometry (GC/MS); no substantive changes.
E. Changes to 40 CFR 136.3 To Include New United States Geological
Survey (USGS) Methods
1. EPA proposes to add the USGS Methods I-2547-11 and I-2548-11
titled ``Colorimetric Determination of Nitrate Plus Nitrite in Water by
Enzymatic Reduction, Automated Discrete Analyzer Methods,'' to Table IB
for the analytes nitrate, nitrite, and combined nitrate-nitrite. Method
I-2548-11 is a low level (analytical range) version of Method I-2547-
11. They are both included in the same method title. The method can be
found in USGS Survey Techniques and Methods, Book 5, Chapter B8. The
method is available for free from the USGS Web site. This method
follows the same procedure as in ATP Case No. N07-0003--Nitrate
Elimination Company Inc.'s (NECi) Method N07-0003, Revision 9.0, March
2014, ``Method for Nitrate Reductase Nitrate-Nitrogen Analysis,'' which
EPA also proposes to approve. Additional details on the ATP study and
multi-laboratory validation can be found in Section E.1 below.
F. Changes to 40 CFR 136.3 to Include ATPs
To promote method innovation, EPA maintains a program that allows
method developers to apply for EPA review of an alternative method to
an existing approved method and potentially for EPA approval of that
ATP. This ATP program is described for CWA applications at 40 CFR 136.4
and 136.5. EPA proposes for nationwide use six alternate test
procedures. Based on EPA's review, the performance of these ATPs is
equally effective as other methods already approved for measurement.
These proposed new methods include: NECi Method N07-0003, ``Method for
Nitrate Reductase Nitrate-Nitrogen Analysis;'' Timberline Instruments,
LLC Method Ammonia-001, ``Determination of Inorganic Ammonia by
Continuous Flow Gas Diffusion and Conductivity Cell Analysis;'' IDEXX
Laboratories, Inc. Colilert[supreg]-18, ``Coliform/E. coli Enzyme
Substrate Test for fecal coliforms in Wastewater;'' NCASI Method TNTP-
W10900, ``Total (Kjeldahl) Nitrogen and Total Phosphorus in Pulp and
Paper Biologically Treated Effluent by Alkaline Persulfate Digestion;''
Hach Company Method 10242, ``Simplified Spectrophotometric Measurement
of Total Kjeldahl Nitrogen in Water and Wastewater;'' and Hach Company
Method 10206, ``Spectrophotometric Measurement of Nitrate in Water and
Wastewater.'' Descriptions of these new methods included for approval
are as follows:
1. The Nitrate Elimination Company Inc. (NECi) Method N07-0003,
``Nitrate Reductase Nitrate-Nitrogen Analysis,'' Revision 9.0, dated
March 2014 (The Nitrate Elimination Company, Inc 2014a). The analysis
measures nitrate, nitrite, and combined nitrate-nitrite. NECi Method
N07-0003 is a ``green'' alternative to the other approved methods which
use cadmium, a known carcinogen for the reduction of nitrate to nitrite
prior to analyses. NECi Method N07-003 uses automated discreet analysis
and spectrophotometry to determine concentrations of nitrate and
nitrite, combined or separately in wastewater. The method involves the
following steps:
Enzymatic reduction of nitrate in a sample to nitrite
using eukaryotic nitrate reductase;
Diazotizing the nitrite originally in the sample plus the
reduced nitrate with sulfanilamide followed by coupling with N-(1-
napthyl)ethylenediamine dihydrochloride under acidic conditions to form
a highly colored azo dye;
Colorimetric determination in which the absorbance of
color at 546 nm is directly proportional to the concentration of the
nitrite plus the reduced nitrate in the sample;
Measurement of nitrite separately, if needed, by analysis
of the sample while eliminating the reduction step;
Subtraction of the nitrite value from that of the combined
nitrate-nitrite value to measure nitrate separately if needed.
NECi Method N07-0003 can be obtained from The Nitrate Elimination
Company, 334 Hecla Street, Lake Linden, Michigan, 49945. Telephone:
906-370-1130.
2. Timberline Instruments, LLC Method Ammonia-001, ``Determination
of Inorganic Ammonia by Continuous Flow Gas Diffusion and Conductivity
Cell Analysis,'' dated June 24, 2011 (Timberline Instruments, LLC
2011a). Timberline Ammonia-001 is an automated method that uses a gas
permeation cell and a conductivity detector to determine concentrations
of ammonia in wastewater. The method involves the following steps:
An aqueous sample is combined with sodium hydroxide to a
pH above 11 producing ammonia in a non-ionized form in solution.
This solution is conveyed to a membrane assembly and the
gaseous ammonia in the aqueous sample migrates through the hydrophobic
membrane into a borate buffer absorption solution, which is then
transported to a conductivity cell.
The measured changes in conductivity are used to
quantitate ammonia in the sample using an external calibration.
Timberline Instruments, LLC Method Ammonia-001 can be obtained from
Timberline Instruments, LLC, 1880 South Flatiron Court, Boulder,
Colorado 80301. Telephone: 303-440-8779.
3. IDEXX Laboratories, Inc., Colilert[supreg]-18, ``Coliform/E.
coli Enzyme Substrate Test for fecal coliforms in Wastewater'' (ATP
Case No. N09-0004). The method is identical to the already approved E.
coli Colilert[supreg]-18 method, with one exception. The current method
was designed for total coliforms and E. coli, at an incubation
temperature of 35 0.5[deg]C for these organisms. The
addendum to the IDEXX Colilert[supreg]-18 method allows for incubation
at 44.5 0.2[deg]C for fecal coliforms.
The Colilert[supreg]-18 Coliform/E. coli Enzyme Substrate Test can
be obtained from IDEXX Laboratories Inc., One IDEXX Drive, Westbrook,
ME 04092, Telephone: 1-800-321-0707.
4. National Council for Air and Stream Improvement, Inc. (NCASI)
Method TNTP-W10900, ``Total (Kjeldahl) Nitrogen (TKN) and Total
Phosphorus in Pulp and Paper Biologically Treated Effluent by Alkaline
Persulfate Digestion,'' dated June 2011 (National Council for Air and
Stream Improvement, Inc. 2011a). Unlike the other ATPs in the proposed
rule, this method is for measurements in pulp, paper and paperboard
mill biologically treated effluent only. NCASI Method TNTP-W10900 uses
an alkaline persulfate digestion procedure to convert inorganic and
organic nitrogen containing compounds to nitrate and inorganic and
organic phosphorus containing compounds to orthophosphate which are
then measured using a spectrophotometer to determine the concentration
of total Kjeldahl nitrogen and total phosphorus in a sample.
The method involves the following steps:
Oxidation of the inorganic and organic nitrogen containing
compounds to nitrate and the inorganic and organic
[[Page 8963]]
forms of phosphorus to orthophosphate by heating acidified, unfiltered
samples in the presence of persulfate (a strong oxidizer) at 120[deg]C
and 15 psi positive pressure for 30 minutes.
Analysis of the digestate for measurement of nitrate and
orthophosphate using the approved colorimetric procedures.
NCASI Method TNTP-W10900 can be obtained from The National Council
for Air and Stream Improvement, Inc., Publications Coordinator, P.O.
Box 13318, Research Triangle Park, NC 27709-3318, Telephone: 919-941-
6400.
5. Hach Company Method 10242, ``Simplified Spectrophotometric
Measurement of Total Kjeldahl Nitrogen in Water and Wastewater,''
Revision 1.1, dated January 10, 2013 (Hach Company 2013a). Hach Company
Method 10242 is a simplified green chemistry alternative to the other
approved methods for measuring TKN. The method uses less toxic reagents
(e.g., eliminating the use of mercuric sulfate). Hach Company Method
10242 uses a spectrophotometer to measure the concentration of total
Kjeldahl nitrogen in a sample.
The method involves the following steps:
Oxidation of the inorganic and organic nitrogen containing
compounds to nitrate by digestion with peroxodisulfate;
Reaction of nitrate with 2,6-dimethylphenol in a solution
of sulfuric and phosphoric acid to form nitrodimethylphenol;
Spectrophotometric measurement of the nitrodimethylphenol
in which the absorbance of color at 345 nm is directly proportional to
the concentration of total nitrogen in the sample;
Measurement of oxidized forms of nitrogen (nitrite +
nitrate) in the original sample in a second test vial;
Subtraction of the concentration of the oxidized forms of
nitrogen from the total nitrogen concentration resulting in the
concentration of total Kjeldahl nitrogen in the sample.
Hach Company Method 10242 can be obtained from Hach Company, 5600
Lindbergh Drive, Loveland, CO 80539. Telephone: 970-669-3050.
6. Hach Company Method 10206, ``Spectrophotometric Measurement of
Nitrate in Water and Wastewater,'' Revision 2.1, dated January 10, 2013
(Hach Company 2013b). Hach Company Method 1206 is a ``green''
alternative to the other approved methods which use cadmium, a known
carcinogen for the reduction of nitrate to nitrite prior to analyses.
Hach Company Method 10206 uses a spectrophotometer to measure the
concentration of nitrate or combined nitrate-nitrite in a sample.
The method involves the following steps:
Reaction of nitrate with 2,6-dimethylphenol in a solution
of sulfuric and phosphoric acid to form nitrodimethylphenol;
Spectrophotometric measurement of the nitrodimethylphenol
in which the absorbance of color at 345 nm is directly proportional to
the concentration of nitrate or, if the sample has been preserved with
sulfuric acid, combined nitrate-nitrite in the sample.
Hach Company Method 10206 can be obtained from Hach Company, 5600
Lindbergh Drive, Loveland, CO 80539. Telephone: 970-669-3050.
G. Changes to 40 CFR part 136 to Align With 40 CFR part 122
The procedures approved in 40 CFR part 136 are often required as
part of an application for a NPDES Permit NPDES, for reports required
to be submitted under NPDES permits and/or for other requests for
quantitative or qualitative effluent data under 40 CFR parts 122 and
125. EPA is clarifying the language in 40 CFR 136.1, 136.2, and 136.3
so that the term ``Director'' as used in 40 CFR part 136 parallels that
in 40 CFR part 122. These sections use the terms ``Administrator'' and
``State having an authorized program'' and define these terms in 136.3.
EPA proposes to revise these provisions to substitute the single term
``Director'' and define ``Director'' in section 40 CFR 136.3(d) by
cross-reference to the definition of ``Director'' in the NPDES
regulations at section 40 CFR 122.2.
EPA recently revised 40 CFR part 122 to include a definition of
``sufficiently sensitive.'' The term is used to describe what approved
methods are adequate for NPDES permits. 40 CFR part 136.6(a)(2) uses
the same term ``sufficiently sensitive'' in a different context to
describe how sensitive a modified method should be compared to the
original method. 40 CFR 136.6(a)(2) currently states that the modified
method must be sufficiently sensitive and meet or exceed performance of
the approved method(s) for the analyte(s) of interest, as documented by
meeting the initial and ongoing quality control requirements in the
method.
EPA proposes to delete the words ``be sufficiently sensitive and''
from 40 CFR 136.6(a)(2) to eliminate unnecessary confusion. It will not
change the requirements of 40 CFR 136.6(a)(2). If a method modification
meets or exceeds the performance of the approved method, this includes
sensitivity.
H. Corrections to 40 CFR Part 136
These changes consist of typographical errors, updates that went
unnoticed during the last update to 40 CFR part 136 to methods from
VCSBs, and technology updates to toxicity methods.
1. EPA proposes to make a number of clarifications and corrections
to its Whole Effluent Toxicity acute and chronic methods manuals
(Methods for Measuring the Acute Toxicity of Effluents and Receiving
Waters to Freshwater and Marine Organisms, EPA-821-R-02-012, October
2002; Short-term Methods for Estimating the Chronic Toxicity of
Effluents and Receiving Waters to Freshwater Organisms, EPA/821/R-02/
013, October 2002; and Methods for Measuring the Chronic Toxicity of
Effluents and Receiving Waters to Marine and Estuarine Organisms, EPA/
821/R-02/014, October 2002) listed in Table IA. Clarifications include
testing all concentrations rather than only high and low
concentrations, definition of terms (e.g., the acronym YCT--yeast,
cereal leaves, and trout chow, is not defined), consistency corrections
among the three manuals, notation that Cusum figure axes should be log
scale, pH and temperature measurements should be done at the beginning
of the test (rather than only at the end of the test), etc. Corrections
also include deletion of unavailable products, typographical errors,
etc.
2. EPA proposes to change the Standard Method listed for E. coli
most probable number (MPN) in Tables IA and IH. During a previous
revision, Standard Methods added sampling as section 9221B.1. As a
result, section 9221B.1 in previously approved versions has become
section 9221B.2. EPA proposes to change SM 9221B.1 to 9221B.2 in Tables
IA and IH for E. coli MPN. The related footnotes in Tables IA and IH
(12, 14 and 11, 13, respectively) are accurate and EPA does not propose
to change them.
3. EPA proposes to change Table IA for Enterococci. EPA proposes to
reinstate a line for Enterococci that was erroneously deleted in the
2012 Methods Update Rule. The line ``MPN, multiple tube'' with Standard
Method 9230B-2007 should be added.
4. EPA proposes to change one of the Table IB hardness entries that
currently states ``Ca plus Mg as their carbonates, by inductively
coupled plasma or AA direct aspiration. (See Parameters 13 and 33).''
EPA proposes to revise the entry to ``Ca plus Mg as their carbonates,
by any approved method for Ca and Mg (See Parameters 13 and 33),
provided
[[Page 8964]]
that the sum of the lowest point of quantitation for Ca and Mg is below
the NPDES permit requirement for Hardness.'' The rationale behind this
change is that if one calcium and magnesium method approved by EPA can
be used to calculate hardness, then other approved EPA methods should
also be permitted to do so.
5. EPA proposes to edit Table IB, footnote 24. EPA proposes to
delete ``p 14'' from the footnote because the method is not on that
page.
6. EPA proposes to delete Method 200.5, in Table IB from the
cobalt, molybdenum and thallium entries. These analytes have not
undergone formal testing by this method, and this method should not
have been approved for these analytes.
7. EPA proposes to remove the reference to costs in 40 CFR 136.3
because costs are not included in the referenced documents.
8. EPA proposes to remove the first instance of ``are'' in 40 CFR
136.3(e) because it is an error.
I. Changes to Table II at 40 CFR 136.3(e) to Required Containers,
Preservation Techniques, and Holding Times
EPA proposes revisions to Table II at 40 CFR 136.3(e) to amend some
of the current requirements.
1. EPA proposes to add rows to Table II that specify holding times
for total/fecal coliforms, and fecal streptococci in Table IH.
Currently these bacterial tests are unspecified. EPA proposes the same
holding time requirements as the other bacterial tests.
2. EPA proposes to change the sodium thiosulfate concentrations in
Table II for bacterial tests from 0.0008% sodium thiosulfate to 0.008%.
EPA proposed this change in its last update to 40 CFR part 136 (75 FR
58066-58067), but inadvertently omitted it in the publication of the
final rule.
3. EPA proposes to re-insert language that was accidentally deleted
from footnote 5 of Table II during the last update to 40 CFR part 136.
Footnote 5 currently reads ``ASTM D7365-09a specifies treatment options
for samples containing oxidants (e.g., chlorine). Also, Section 9060A
of Standard Methods for the Examination of Water and Wastewater (20th
and 21st editions) addresses dechlorination procedures.'' EPA proposes
to revise the footnote to read ``ASTM D7365-09a specifies treatment
options for samples containing oxidants (e.g., chlorine) for cyanide
analysis. Also, Section 9060A of Standard Methods for the Examination
of Water and Wastewater (20th and 21st editions) addresses
dechlorination procedures for microbiological analyses.'' The footnote
needs to specify that treatment options for samples containing oxidants
is specifically for cyanide analysis, and that the dechlorination
procedures are specifically for microbiological analyses.
4. EPA seeks comment on how to approve variances to sample
preservation, containers or holding times listed in Table II for
specific dischargers. Before the 2012 Final Method Update Rule (FR 77:
29758), the regulation required parties requesting a variance from
Table II for specific dischargers to send the request to the
appropriate EPA regional office for review, and then for the regional
office to send the request to the National ATP Coordinator at EPA
Headquarters for review and recommendation. Following receipt of such
recommendation, the regional office could approve a variance. In the
2012 Final Method Update Rule, EPA changed the requirement so that
either the Regional ATP Coordinator or the permitting authority could
approve an exception to Table II for specific dischargers. The primary
rationale for this change, as stated in the preamble of the 2010
Proposed Method Update Rule (FR 76: 77742) was: ``EPA is revising the
text at 136.3(e) to allow a party to explain, without a cumbersome
waiver process, to their permitting or other authority their basis for
an alternative approach.'' Giving this authority to either the Regional
ATP Coordinator or the permitting authority speeds up the approval
process. Also, the permitting authority is more likely to know about
special circumstances surrounding the local dischargers (e.g., unusual
discharge matrices, remote locations, etc.).
This change in the approval process resulted in the following
potential complications and EPA is interested in public comment on
them. First, it created a parallel authority to approve variances to
Table II for specific dischargers. A discharger could make a request to
both the Regional ATP Coordinator and the permitting authority, receive
contradictory answers, and then choose the answer that the discharger
prefers. Second, when there are different authorities approving a Table
II variance for specific dischargers, there is potential for the data
and documentation required by one authority to differ significantly
from that required by the other authority.
EPA seeks comment on potential paths forward that would eliminate
these concerns, while streamlining the process so that approval can be
granted within the EPA region or by the state permitting authority. One
possibility is for the permitting authority and the Regional ATP
Coordinator to approve Table II variances for specific dischargers
collaboratively. The permitting authority could provide the initial
review and approval, and then approved requests could be sent to the
Regional ATP Coordinator for final review and approval. Both
organizations would need to agree for specific dischargers to be
allowed Table II variances. Another option is to give the Regional ATP
Coordinator exclusive rights to approve Table II variances for specific
dischargers. Another option is to give the permitting authority
exclusive rights to approve Table II variances. Other options are also
possible, such as leaving 40 CFR 136.3(e) unchanged.
EPA also seeks comment on what data should be submitted to support
a request for a Table II variance for a specific discharger. 40 CFR
136.3(e) requires that data be included with any request to modify
Table II requirements for a specific discharger. The data would need to
prove that the variance does not compromise the analytical results.
J. Clarifications/Corrections to ATP Procedures in 40 CFR 136.4, 136.5
and Allowed Modifications in 136.6
40 CFR 136.4 and 136.5 describe EPA procedures for obtaining
approval to use an alternate test procedures either on a national
basis, or for limited use by dischargers or facilities specified in the
approval. In the 2012 Method Update Rule, EPA made several clarifying
changes to the language of these sections. At the same time, however,
in many places in 40 CFR 136.4 and 136.5 where the phrase ``Regional
Alternate Test Procedures Coordinator'' or ``Regional ATP Coordinator''
appears, EPA inadvertently also inserted the phrase ``or permitting
authority'' following the phrase. This error resulted from the use of
the ``search and replace'' function on the computer. The effect of the
change was to inadvertently authorize State permitting authorities to
approve ATPs for limited use within the State. EPA never intended this
result as is demonstrated by two facts. First, in its proposal for the
2012 Update, EPA did not propose to authorize State NPDES permitting
authorities to approve limited use ATPs. Second, the rule states that
the approval may be restricted to specific dischargers or facilities,
or to all dischargers or facilities ``specified in the approval for the
Region.'' (emphasis added). This language evidences EPA's intent that
the Region--not the state--would be
[[Page 8965]]
authorized to issue any such limited use ATP approval. Finally, as
further evidence of EPA's intent, in several places, the text of the
rule makes more sense if read to authorize only the Regional ATP
Coordinator, and not the State permitting authority, to approve limited
use ATPs. For example, 40 CFR 136.5(d)(1) provides that after a review
of the application by the Alternate Test Procedure Regional ATP
Coordinator or permitting authority, the Regional ATP Coordinator or
permitting authority notifies the applicant and the appropriate State
agency of approval or rejection of the use of the alternate test
procedure.
As currently written, if the State is acting on a request for
approval, the regulation would require the State to inform itself of
its own action in approving or rejecting the ATP, a somewhat
superfluous requirement.
Consequently, EPA proposes to delete all instances of ``or
permitting authority'' from 40 CFR 136.4 and 136.5 to correct this
error and revise the rule text to its original intent. Based on this
revision, EPA and EPA alone would have the authority to approve limited
use ATPs.
EPA also proposes changes to 40 CFR 136.4 and 136.5 to clarify the
process for nationwide approval and the Regional ATP Coordinator's role
in limited use ATP approvals. These changes do not significantly change
the process, the intent is to make wording simpler and clearer.
Finally, EPA proposes to add language to 40 CFR 136.6(b)(1) to
clarify that if a method user is uncertain whether or not a
modification is allowed under 40 CFR 136.6, the user should contact
either its Director or EPA Regional ATP Coordinator.
K. Changes to Appendix B to 40 CFR part 136--Definition and Procedure
for the Determination of the MDL
EPA proposes revisions to the procedure for determination of the
MDL primarily to address laboratory blank contamination and to better
account for intra-laboratory variability. EPA's consideration of
revisions to the MDL procedure for this rulemaking is specific to these
revisions, and other changes to the procedure are outside the scope of
this action. The proposed changes originated from The National
Environmental Laboratory Accreditation Conference Institute and also
reflect review by EPA, states, and commercial laboratories. The
proposed revisions address the following issues and would add new
requirements.
Background contamination: laboratories would be required to
evaluate the MDL to account for background levels of contamination. As
laboratory methods become more and more sensitive, background levels of
contamination are more likely to contribute to the result. This
modification would reduce false positive detects.
MDLs that represent multiple instruments: if a laboratory uses MDL
values that represent multiple instruments, then the laboratory would
be required to calculate the MDL using spiked samples and blank samples
from all of these instruments. Currently, laboratories can run all of
their MDL samples on the most sensitive instrument, and then use that
MDL for other instruments. This modification will make the MDL more
representative of the laboratory's actual capability.
Ongoing MDL quarterly verification: laboratories would be required
to check their MDL values once a quarter. Currently, laboratories can
run MDL samples once a year under the most ideal circumstances (e.g.,
immediately after the instrument has been serviced or after an annual
maintenance routine). Quarterly evaluation will determine if the
detection limit has significantly drifted during the year. Laboratories
would be exempt from running these samples for a method during quarters
when no samples are run using that method.
EPA requests comment on whether it should adopt these proposed
changes, in part, or in whole.
V. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review and Review and
Executive Order 13563: Improving Regulation and Regulatory Review
This rule is not a significant regulatory action and was therefore
not submitted to the Office of Management and Budget for review.
B. Paperwork Reduction Act
This action does not impose an information collection burden under
the PRA. This rule does not impose any information collection,
reporting, or recordkeeping requirements. This proposal would merely
add or revise CWA test procedures.
C. Regulatory Flexibility Act
I certify that this action would 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 and revised versions of CWA testing procedures.
Generally, these changes would have a positive impact on small entities
by increasing method flexibility, thereby allowing entities to reduce
costs by choosing more cost-effective methods. In general, EPA expects
the proposed revisions would lead to few, if any, increased costs. As
explained previously, most of the proposed changes clarify procedures
for EPA approval of ATPs, clarify or improve the instructions in the
method, update the technology used in the method, improve the QC
instructions, make editorial corrections, or reflect the most recent
approval year of an already approved method. In some cases, the
proposal would add alternatives to currently approved methods for a
particular analyte (e.g. Method N07-0003 for Nitrate Reductase Nitrate-
Nitrogen Analysis). Because these methods would be alternatives rather
than requirements, there are no direct costs associated with their
proposal. EPA proposes methods that would be incorporated by reference.
If a permittee elected to use these methods, they could incur a small
cost associated with obtaining these methods. See Section IV.B.
Finally, the proposed changes to the MDL procedure would lead to
limited increased costs. In the vast majority of cases, laboratories
already collect samples that could be used in the revised procedure
and/or would simply adjust the time period of collection. The total
number of MDL samples run annually would only increase to any
appreciable extent for laboratories that own many instruments. EPA has
not estimated costs for these cases, because such costs, if incurred,
would be negligible in comparison to overall laboratory expenditures.
D. Unfunded Mandates Reform Act
This action does not contain any unfunded mandate as described in
UMRA, 2 U.S.C. 1531-1538, and does not significantly or uniquely affect
small governments. The action imposes no enforceable duty on any state,
local or tribal governments or the private sector.
E. Executive Order 13132: Federalism
This proposed rule does not have federalism implications. It 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.
[[Page 8966]]
F. Executive Order 13175: Consultation and Coordination with Indian
Tribal Governments
This proposed rule does not have tribal implications as specified
in Executive Order 13175. This rule would merely approve new and
revised versions of test procedures. EPA does not expect the proposal
would lead to any costs to any tribal governments, and if incurred,
projects they would be minimal. Thus, Executive Order 13175 does not
apply to this action.
G. Executive Order 13045: Protection of Children from Environmental
Health Risks and Safety Risks
EPA interprets EO 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. This action is not subject to Executive Order 13045
because it does not concern an environmental health risk or safety
risk.
H. Executive Order 13211: Actions that Significantly Affect Energy
Supply, Distribution, or Use
This action is not subject to Executive Order 13211 because it is
not a significant regulatory action under Executive Order 12866.
I. National Technology Transfer and Advancement Act of 1995
This action involved technical standards. The EPA proposes to
approve the use of technical standards developed and recommended by the
Standard Methods Committee and ASTM International for use in compliance
monitoring where EPA determined that those standards meet the needs of
CWA programs. As explained in Section IV.C, EPA does not propose to add
one SM method because it did not receive data to demonstrate that the
method had undergone full inter-laboratory validation. EPA proposes all
other methods recommended by VCSBs in advance of the proposed rule.
J. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations
The EPA believes the human health or environmental risk addressed
by this action will not have potential disproportionately high and
adverse human health or environmental effects on minority, low-income
or indigenous populations.
List of Subjects in 40 CFR Part 136
Environmental protection, Incorporation by reference, Reporting and
recordkeeping requirements, Test procedures, Water pollution control.
Dated: February 5, 2015.
Gina McCarthy,
Administrator.
For the reasons set out in the preamble, title 40, chapter I of the
Code of Federal Regulations is proposed to be amended as follows:
PART 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. Section 136.1 is amended by revising paragraph (a) to read as
follows:
Sec. 136.1 Applicability.
(a) The procedures prescribed herein shall, except as noted in
Sec. Sec. 136.4, 136.5, and 136.6, be used to perform the measurements
indicated whenever the waste constituent specified is required to be
measured for:
(1) An application submitted to the Director and/or reports
required to be submitted under NPDES permits or other requests for
quantitative or qualitative effluent data under parts 122 to 125 of
this chapter; and
(2) Reports required to be submitted by dischargers under the NPDES
established by parts 124 and 125 of this chapter; and
(3) Certifications issued by States pursuant to section 401 of the
Clean Water Act (CWA), as amended.
* * * * *
0
3. Section 136.2 is amended by revising paragraph (d) to read as
follows:
Sec. 136.2 Definitions.
* * * * *
(d) Director means the director as defined in 40 CFR 122.2.
* * * * *
0
4. In Sec. 136.3:
0
a. Revise paragraph (a) introductory text and tables IA, IB, IC, ID,
IF, IG, and IH.
0
b. Revise paragraphs (b) introductory text, (b)(8)(iv), (b)(8)(v),
(b)(8)(xiii), (b)(8)(xv), (b)(10)(viii), (b)(10)(x) through (lviii),
(b)(10)(lxi) through (lxiii), (b)(10)(lxviii), (b)(15)(v),
(b)(15)(viii) through (x), (b)(15)(xii), (b)(15)(xiii), (b)(15)(xv)
through (xvii), (b)(15)(xxii) through (xxiv), (b)(15)(xxx),
(b)(15)(xxxv), (b)(15)(xxxvii), (b)(15)(xxxix), (b)(15)(xlii),
(b)(15)(l), (b)(15)(lii), (b)(15)(lv), (b)(15)(lviii), (b)(15)(lxi),
(b)(15)(lxvi), and (b)(15)(lxviii).
0
c. Redesignate paragraphs (b)(19)(vii) and (viii) as paragraphs
(b)(19)(ix) and (x), respectively.
0
d. Add paragraphs (b)(19)(vii) and (viii).
0
e. Revise paragraphs (b)(20)(i) through (iv).
0
f. Remove paragraph (b)(20)(v).
0
g. Revise paragraph (b)(25).
0
h. Redesignate paragraphs (b)(33) and (34) as paragraphs (b)(35) and
(36), respectively, and redesignate paragraphs (b)(26) through (32) as
paragraphs (b)(27) through (33), respectively.
0
i. Add paragraph (b)(26).
0
j. Add paragraph (b)(34).
0
k. Revise newly redesignated paragraph (b)(35).
0
l. Revise paragraph (c) and the table in paragraph (e).
The revisions and additions read as follows:
Sec. 136.3 Identification of test procedures.
(a) Parameters or pollutants, for which methods are approved, are
listed together with test procedure descriptions and references in
Tables IA, IB, IC, ID, IE, IF, IG, and IH of this section. The methods
listed in Tables IA, IB, IC, ID, IE, IF, IG, and IH are incorporated by
reference, see paragraph (b) of this section, with the exception of EPA
Methods 200.7, 601-613, 624.1, 625.1, 1613, 1624, and 1625. The full
texts of Methods 601-613, 624.1, 625.1, 1613, 1624, and 1625 are
printed in appendix A of this part, and the full text of Method 200.7
is printed in appendix C of this part. The full text for determining
the method detection limit when using the test procedures is given in
appendix B of this part. In the event of a conflict between the
reporting requirements of 40 CFR parts 122 and 125 and any reporting
requirements associated with the methods listed in these tables, the
provisions of 40 CFR parts 122 and 125 are controlling and will
determine a permittee's reporting requirements. The full text of the
referenced test procedures are incorporated by reference into Tables
IA, IB, IC, ID, IE, IF, IG, and IH. The date after the method number
indicates the latest editorial change of the method. The discharge
parameter values for which reports are required must be determined by
one of the standard analytical test procedures incorporated by
reference and described in Tables IA,
[[Page 8967]]
IB, IC, ID, IE, IF, IG, and IH or by any alternate test procedure which
has been approved by the Administrator under the provisions of
paragraph (d) of this section and Sec. Sec. 136.4 and 136.5. Under
certain circumstances paragraph (c) of this section, Sec. 136.5(a)
through (d) or 40 CFR 401.13, other additional or alternate test
procedures may be used.
Table IA--List of Approved Biological Methods for Wastewater and Sewage Sludge
----------------------------------------------------------------------------------------------------------------
Standard AOAC, ASTM,
Parameter and units Method \1\ EPA methods USGS Other
----------------------------------------------------------------------------------------------------------------
Bacteria:
1. Coliform (fecal), number Most Probable p. 132 \3\1680 9221 C E-
per 100 mL or number per gram Number (MPN), 5 11 15 1681 11 2006
dry weight. tube, 3 20.
dilution, or.
Multiple tube/ ................ ......... .............. Colilert-18
multiple well, [supreg] 13 18
or. 29
Membrane filter p. 124 \3\...... 9222 D- B-0050-85 \4\.
(MF) \2\, single 2006
step. \30\
2. Coliform (fecal) in MPN, 5 tube, 3 p. 132 \3\...... 9221 C E-
presence of chlorine, dilution, or. 2006
number per 100 mL.
MF \2\, single p. 124 \3\...... 9222 D-
step \5\. 2006
\30\
3. Coliform (total), MPN, 5 tube, 3 p. 114 \3\...... 9221 B-
number per 100 mL. dilution, or. 2006
MF \2\, single p. 108 \3\...... 9222 B- B-0025-85 \4\.
step or two step. 2006
4. Coliform (total), in MPN, 5 tube, 3 p. 114 \3\...... 9221 B-
presence of chlorine, dilution, or. 2006
number per 100 mL.
MF \2\ with p. 111 \3\...... 9222 B-
enrichment \5\. 2006
5. E. coli, number per 100 MPN 6 8 16 ................ 9221B.2-2
mL \21\. multiple tube, 006/
or. 9221F-20
06 12 14
multiple tube/ ................ 9223 B- 991.15 \10\... Colilert[supreg]
multiple well, 2004 13 18 Colilert-
or. \13\ 18[supreg] 13
17 18
MF 2 6 7 8 single 1603 \22\....... ......... .............. mColiBlue-24
step. [supreg] \19\
6. Fecal streptococci, MPN, 5 tube, 3 p. 139 \3\...... 9230 B-
number per 100 mL. dilution, or. 2007
MF \2\, or....... p. 136 \3\...... 9230 C- B-0055-85 \4\.
2007
Plate count...... p. 143 \3\......
7. Enterococci, number per MPN, 5 tube, 3 p. 139 \3\...... 9230 B-
100 mL \21\. dilution, or. 2007
MPN 6 8, multiple ................ 9230 D- D6503-99 \9\.. Enterolert
tube/multiple 2007 [supreg] 13 24
well, or.
MF 2 6 7 8 single 1600 \25\....... 9230 C-
step or. 2007
Plate count...... p. 143 \3\......
8. Salmonella, number per MPN multiple tube 1682 \23\.......
gram dry weight \11\.
Aquatic Toxicity:
9. Toxicity, acute, fresh Ceriodaphnia 2002.0 \26\.....
water organisms, LC50, dubia acute.
percent effluent.
Daphnia puplex 2021.0 \26\.....
and Daphnia
magna acute.
Fathead Minnow, 2000.0 \26\.....
Pimephales
promelas, and
Bannerfin
shiner,
Cyprinella
leedsi, acute.
Rainbow Trout, 2019.0 \26\.....
Oncorhynchus
mykiss, and
brook trout,
Salvelinus
fontinalis,
acute.
10. Toxicity, acute, Mysid, Mysidopsis 2007.0 \26\.....
estuarine and marine bahia, acute.
organisms of the Atlantic
Ocean and Gulf of Mexico,
LC50, percent effluent.
Sheepshead 2004.0 \26\.....
Minnow,
Cyprinodon
variegatus,
acute.
[[Page 8968]]
Silverside, 2006.0 \26\.....
Menidia
beryllina,
Menidia menidia,
and Menidia
peninsulae,
acute.
11. Toxicity, chronic, Fathead minnow, 1000.0 \27\.....
fresh water organisms, Pimephales
NOEC or IC25, percent promelas, larval
effluent. survival and
growth.
Fathead minnow, 1001.0 \27\.....
Pimephales
promelas, embryo-
larval survival
and
teratogenicity.
Daphnia, 1002.0 \27\.....
Ceriodaphnia
dubia, survival
and reproduction.
Green alga, 1003.0 \27\.....
Selenastrum
capricornutum,
growth.
12. Toxicity, chronic, Sheepshead 1004.0 \28\.....
estuarine and marine minnow,
organisms of the Atlantic Cyprinodon
Ocean and Gulf of Mexico, variegatus,
NOEC or IC25, percent larval survival
effluent. and growth.
Sheepshead 1005.0 \28\.....
minnow,
Cyprinodon
variegatus,
embryo-larval
survival and
teratogenicity.
Inland 1006.0 \28\.....
silverside,
Menidia
beryllina,
larval survival
and growth.
Mysid, Mysidopsis 1007.0 \28\.....
bahia, survival,
growth, and
fecundity.
Sea urchin, 1008.0 \28\.....
Arbacia
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.
\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.2-2006. Lactose broth may be used in lieu of lauryl
tryptose broth (LTB), if at least 25 parallel tests are conducted between this broth and LTB using the water
samples normally tested, and this comparison demonstrates that the false-positive rate and false-negative rate
for total coliform using lactose broth is less than 10 percent. No requirement exists to run the completed
phase on 10 percent of all total coliform-positive tubes on a seasonal basis.
\13\ These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is
used to detect the enzyme [beta]-glucuronidase produced by E. coli.
\14\ After prior enrichment in a presumptive medium for total coliform using 9221B.2-2006, 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-2006. 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] 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], and Quanti-Tray[supreg] 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\ Recommended for enumeration of target organism in wastewater effluent.
[[Page 8969]]
\22\ Method 1603: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-
Thermotolerant Escherichia coli Agar (modified mTEC), EPA-821-R-14-010. September 2014. U.S. EPA.
\23\ Method 1682: Salmonella in Sewage Sludge (Biosolids) by Modified Semisolid Rappaport-Vassiliadis (MSRV)
Medium, EPA-821-R-14-012. July 2014. U.S. EPA.
\24\ A description of the Enterolert[supreg] test may be obtained from IDEXX Laboratories Inc.
\25\ Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-[beta]-D-
Glucoside Agar (mEI), EPA-821-R-14-011. September 2014. U.S. EPA.
\26\ 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.
\27\ 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.
\28\ 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.
\29\ Colilert-18[supreg] is an optimized formulation of the Colilert[supreg] for the determination of total
coliforms and E. coli that has been adapted to detect fecal coliforms. To use Colilert-18[supreg] to assay for
fecal coliforms, the incubation temperature is 44.5 + 0.2[deg]C. This test is recommended for wastewater
samples.
\30\ The verification frequency is at least five typical and five atypical colonies per sampling site on the day
of sample collection and analysis.
Table IB--List of Approved Inorganic Test Procedures
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter Methodology \58\ EPA \52\ Standard methods ASTM USGS/AOAC/Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acidity, as CaCO3, mg/L......... Electrometric endpoint ...................... 2310 B-2011.......... D1067-11............. I-1020-85. \2\
or phenolphthalein
endpoint.
2. Alkalinity, as CaCO3, mg/L...... Electrometric or ...................... 2320 B-1997.......... D1067-11............. 973.43 \3\, I-1030-
Colorimetric 85. \2\
titration to pH 4.5,
Manual.
Automatic............. 310.2 (Rev. 1974) \1\. ..................... ..................... I-2030-85. \2\
3. Aluminum--Total, \4\ mg/L....... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 D-2011 or 3111 E- ..................... I-3051-85. \2\
aspiration \36\. 2011.
AA furnace......... ...................... 3113 B-2010..........
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14\3,\ I-4471-97.
\50\
Direct Current Plasma ...................... ..................... D4190-08............. See footnote. \34\
(DCP) \36\.
Colorimetric ...................... 3500-Al B-2011.......
(Eriochrome cyanine
R).
4. Ammonia (as N), mg/L............ Manual distillation 350.1, Rev. 2.0 (1993) 4500-NH3 B-2011...... ..................... 973.49. \3\
\6\ or gas diffusion
(pH > 11), followed
by any of the
following:
Nesslerization........ ...................... ..................... D1426-08 (A)......... 973.49 \3\, I-3520-
85. \2\
Titration............. ...................... 4500-NH3 C-2011......
Electrode............. ...................... 4500-NH3 D-2011 or E- D1426-08 (B).........
2011.
Manual phenate, ...................... 4500-NH3 F-2011...... ..................... See footnote. \60\
salicylate, or other
substituted phenols
in Berthelot reaction
based methods.
Automated phenate, 350.1 \30\, Rev. 2.0 4500-NH3 G-2011...... ..................... I-4523-85. \2\
salicylate, or other (1993). 4500-NH3 H-2011......
substituted phenols
in Berthelot reaction
based methods.
Automated electrode... ...................... ..................... ..................... See footnote. \7\
Ion Chromatography.... ...................... ..................... D6919-09.............
Automated gas ...................... ..................... ..................... Timberline Ammonia-
diffusion, followed 001 \74\
by conductivity cell
analysis.
5. Antimony--Total, \4\ mg/L....... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration \36\.
AA furnace......... ...................... 3113 B-2010..........
STGFAA............. 200.9, Rev. 2.2 (1994)
[[Page 8970]]
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
6. Arsenic-Total, \4\ mg/L......... Digestion \4\, 206.5 (Issued 1978)
followed by any of \1\.
the following:
AA gaseous hydride. ...................... 3114 B-2011 or....... D2972-08 (B)......... I-3062-85. \2\
3114 C-2011..........
AA furnace......... ...................... 3113 B-2010.......... D2972-08 (C)......... I-4063-98. \49\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12.............
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-
05. \70\
Colorimetric (SDDC) ...................... 3500-As B-2011....... D2972-08 (A)......... I-3060-85. \2\
7. Barium-Total, \4\ mg/L.......... Digestion\4\, followed
by any of the
following:
AA direct ...................... 3111 D-2011.......... ..................... I-3084-85. \2\
aspiration \36\.
AA furnace......... ...................... 3113 B-2010.......... D4382-12.............
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... ..................... I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14\3\, I-4471-97.
\50\
DCP \36\........... ...................... ..................... ..................... See footnote. \34\
8. Beryllium--Total, \4\ mg/L...... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 D-2011 or 3111 E- D3645-08 (A)......... I-3095-85. \2\
aspiration. 2011.
AA furnace......... ...................... 3113 B-2010.......... D3645-08 (B).........
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES............ 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
DCP................ ...................... ..................... D4190-08............. See footnote. \34\
Colorimetric ...................... See footnote. \61\
(aluminon).
9. Biochemical oxygen demand Dissolved Oxygen ...................... 5210 B-2011.......... ..................... 973.44 \3\, p. 17
(BOD5), mg/L. Depletion. \9\, I-1578-78 \8\,
See footnote. \10,
63\
10. Boron--Total, \37\ mg/L........ Colorimetric ...................... 4500-B B-2011........ ..................... I-3112-85. \2\
(curcumin).
ICP/AES............... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS................ 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
DCP................... ...................... ..................... D4190-08............. See footnote. \34\
11. Bromide, mg/L.................. Electrode............. ...................... ..................... D1246-10............. I-1125-85. \2\
Ion Chromatography.... 300.0, Rev 2.1 (1993) 4110 B-2011, C-2011, D4327-03............. 993.30. \3\
and 300.1-1, Rev 1.0 D-2011.
(1997).
CIE/UV................ ...................... 4140 B-2011.......... D6508-10, D6508, Rev.
2 \54\.
12. Cadmium--Total, \4\ mg/L....... Digestion \4\,
followed by any of
the following:
[[Page 8971]]
AA direct ...................... 3111 B-2011.......... D3557-12 (A or B).... 974.27 \3\, p. 37
aspiration \36\. or 3111 C-2011....... \9\, I-3135-85 \2\
or I-3136-85. \2\
AA furnace......... ...................... 3113 B-2010.......... D3557-12 (D)......... I-4138-89. \51\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12............. I-1472-85 \2\ or I-
\68\; 200.7, Rev. 4.4 4471-97. \50\
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
Voltametry \11\.... ...................... ..................... D3557-12 (C).........
Colorimetric ...................... 3500-Cd-D-1990.......
(Dithizone).
13. Calcium--Total, \4\ mg/L....... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011.......... D511-09(B)........... I-3152-85. \2\
aspiration.
ICP/AES............ 200.5, Rev 4.2 (2003) 3120 B-2011.......... ..................... I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14. \3\
DCP................ ...................... ..................... ..................... See footnote. \34\
Titrimetric (EDTA). ...................... 3500-Ca B-2011....... D511-09 (A)..........
Ion Chromatography. ...................... ..................... D6919-09.............
14. Carbonaceous biochemical oxygen Dissolved Oxygen ...................... 5210 B-2011.......... ..................... See footnote. \35,
demand (CBOD5), mg/L \12\. Depletion with 63\
nitrification
inhibitor.
15. Chemical oxygen demand (COD), Titrimetric........... 410.3 (Rev. 1978) \1\. 5220 B-2011.......... D1252-06 (A)......... 973.46 \3\, p. 17
mg/L. or C-2011............ \9\, I-3560-85. \2\
Spectrophotometric, 410.4, Rev. 2.0 (1993) 5220 D-2011.......... D1252-06 (B)......... See footnotes. \13,
manual or automatic. 14\, I-3561-85. \2\
16. Chloride, mg/L................. Titrimetric: (silver ...................... 4500-Cl - B-2011..... D512-04 (B).......... I-1183-85. \2\
nitrate).
(Mercuric nitrate). ...................... 4500-Cl - C-2011..... D512-04 (A).......... 973.51 \3\, I-1184-
85. \2\
Colorimetric: ...................... ..................... ..................... I-1187-85. \2\
manual.
Automated ...................... 4500-Cl - E-2011..... ..................... I-2187-85. \2\
(ferricyanide).
Potentiometric ...................... 4500-Cl - D-2011.....
Titration.
Ion Selective ...................... ..................... D512-04 (C)..........
Electrode.
Ion Chromatography. 300.0, Rev 2.1 (1993) 4110 B-2011 or 4110 C- D4327-03............. 993.30 \3\, I-2057-
and 300.1-1, Rev 1.0 2011. 90. \51\
(1997).
CIE/UV............. ...................... 4140 B-2011.......... D6508-10, D6508, Rev.
2 \54\.
17. Chlorine--Total residual, mg/L. Amperometric direct... ...................... 4500-Cl D-2011....... D1253-08.............
Amperometric direct ...................... 4500-Cl E-2011.......
(low level).
Iodometric direct.. ...................... 4500-Cl B-2011.......
Back titration ...................... 4500-Cl C-2011.......
ether end-point
\15\.
DPD-FAS............ ...................... 4500-Cl F-2011.......
Spectrophotometric, ...................... 4500-Cl G-2011.......
DPD.
Electrode.......... ...................... ..................... ..................... See footnote. \16\
17A. Chlorine-Free Available, mg/L. Amperometric direct... ...................... 4500-Cl D-2011....... D1253-08.............
Amperometric direct ...................... 4500-Cl E-2011.......
(low level).
DPD-FAS............ ...................... 4500-Cl F-2011.......
Spectrophotometric, ...................... 4500-Cl G-2011.......
DPD.
[[Page 8972]]
18. Chromium VI dissolved, mg/L.... 0.45-micron filtration
followed by any of
the following:
AA chelation- ...................... 3111 C-2011.......... ..................... I-1232-85. \2\
extraction.
Ion Chromatography. 218.6, Rev. 3.3 (1994) 3500-Cr C-2011....... D5257-11............. 993.23.
Colorimetric ...................... 3500-Cr B-2011....... D1687-12 (A)......... I-1230-85. \2\
(diphenyl-
carbazide).
19. Chromium--Total, \4\ mg/L...... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011.......... D1687-12 (B)......... 974.27 \3\, I-3236-
aspiration \36\. 85. \2\
AA chelation- ...................... 3111 C-2011..........
extraction.
AA furnace......... ...................... 3113 B-2010.......... D1687-12 (C)......... I-3233-93. \46\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\, 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-
05. \70\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
Colorimetric ...................... 3500-Cr B-2011.......
(diphenyl-
carbazide).
20. Cobalt--Total, \4\ mg/L........ Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011 or 3111 C- D3558-08 (A or B).... p. 37 \9\, I-3239-85.
aspiration. 2011. \2\
AA furnace......... ...................... 3113 B-2010.......... D3558-08 (C)......... I-4243-89. \51\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.7, Rev. 4.4 (1994) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-
05. \70\
DCP................ ...................... ..................... D4190-08............. See footnote. \34\
21. Color, platinum cobalt units or Colorimetric (ADMI)... ...................... 2120 F-2011.......... ..................... See footnote. \18\
dominant wavelength, hue,
luminance purity.
(Platinum cobalt) ...................... 2120 B-2011.......... ..................... I-1250-85. \2\
Spectrophotometric.
22. Copper--Total, \4\ mg/L........ Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011 or....... D1688-12 (A or B).... 974.27 \3\, p. 37
aspiration \36\. 3111 C-2011.......... \9\, I-3270-85 \2\
or I-3271-85. \2\
AA furnace......... ...................... 3113 B-2010.......... D1688-12 (C)......... I-4274-89. \51\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-
05. \70\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
Colorimetric ...................... 3500-Cu B-2011.......
(Neocuproine).
Colorimetric ...................... 3500-Cu C-2011....... ..................... See footnote. \19\
(Bathocuproine).
23. Cyanide--Total, mg/L........... Automated UV digestion/ ...................... ..................... ..................... Kelada-01. \55\
distillation and
Colorimetry.
[[Page 8973]]
Segmented Flow ...................... ..................... D7511-12.............
Injection, In-Line
Ultraviolet
Digestion,
followed by gas
diffusion
amperometry.
Manual distillation 335.4, Rev. 1.0 (1993) 4500-CN - B-2011 and D2036-09(A), D7284-13 10-204-00-1-X. \56\
with MgCl2, followed \57\. C-2011.
by any of the
following:
Flow Injection, gas ...................... ..................... D2036-09(A) D7284-13.
diffusion
amperometry.
Titrimetric........ ...................... 4500-CN - D-2011..... D2036-09(A).......... p. 22. \9\
Spectrophotometric, ...................... 4500-CN - E-2011..... D2036-09(A).......... I-3300-85. \2\
manual.
Semi-Automated \20\ 335.4, Rev. 1.0 (1993) ..................... ..................... 10-204-00-1-X \56\, I-
\57\. 4302-85. \2\
Ion Chromatography. ...................... ..................... D2036-09(A)..........
Ion Selective ...................... 4500-CN - F-2011..... D2036-09(A)..........
Electrode.
24. Cyanide-Available, mg/L........ Cyanide Amenable to ...................... 4500-CN - G-2011..... D2036-09(B)..........
Chlorination (CATC);
Manual distillation
with MgCl2, followed
by Titrimetric or
Spectrophotometric.
Flow injection and ...................... ..................... D6888-09............. OIA-1677-09. \44\
ligand exchange,
followed by gas
diffusion
amperometry \59\.
Automated ...................... ..................... ..................... Kelada-01. \55\
Distillation and
Colorimetry (no UV
digestion).
24.A Cyanide-Free, mg/L............ Flow Injection, ...................... ..................... D7237-10............. OIA-1677-09. \44\
followed by gas
diffusion amperometry.
Manual micro- ...................... ..................... D4282-02.............
diffusion and
colorimetry.
25. Fluoride--Total, mg/L.......... Manual distillation ...................... 4500-F - B-2011......
\6\, followed by any
of the following:
Electrode, manual.. ...................... 4500-F - C-2011...... D1179-10 (B).........
Electrode, ...................... ..................... ..................... I-4327-85. \2\
automated.
Colorimetric, ...................... 4500-F - D-2011...... D1179-10 (A).........
(SPADNS).
Automated ...................... 4500-F - E-2011......
complexone.
Ion Chromatography. 300.0, Rev 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30. \3\
and 300.1-1, Rev 1.0
(1997).
CIE/UV............. ...................... 4140 B-2011.......... D6508-10, D6508, Rev.
2 \54\.
26. Gold--Total, \4\ mg/L.......... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration.
AA furnace......... 231.2 (Issued 1978) 3113 B-2010..........
\1\.
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14. \3\
DCP................ ...................... ..................... ..................... See footnote. \34\
27. Hardness--Total, as CaCO3, mg/L Automated colorimetric 130.1 (Issued 1971)
\1\.
Titrimetric (EDTA). ...................... 2340 C-2011.......... D1126-12............. 973.52B \3\, I-1338-
85. \2\
[[Page 8974]]
Ca plus Mg as their ...................... 2340 B-2011..........
carbonates, by any
approved method
for Ca and Mg (See
Parameters 13 and
33), provided that
the sum of the
lowest point of
quantitation for
Ca and Mg is below
the NPDES permit
requirement for
Hardness.
28. Hydrogen ion (pH), pH units.... Electrometric ...................... 4500-H \+\ B-2011.... D1293-99 (A or B).... 973.41 \3\, I-1586-
measurement. 85. \2\
Automated electrode 150.2 (Dec. 1982) \1\. ..................... ..................... See footnote \21\, I-
2587-85. \2\
29. Iridium--Total, \4\ mg/L....... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration.
AA furnace......... 235.2 (Issued 1978)
\1\.
ICP/MS............. ...................... 3125 B-2011..........
30. Iron--Total, \4\ mg/L.......... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011 or....... D1068-10 (A)......... 974.27 \3\, I-3381-
aspiration \36\. 3111 C-2011.......... 85. \2\
AA furnace......... ...................... 3113 B-2010.......... D1068-10 (B).........
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14. \3\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
Colorimetric ...................... 3500-Fe-2011......... D1068-10 (C)......... See footnote. \22\
(Phenanthroline).
31. Kjeldahl Nitrogen \5\--Total, Manual digestion \20\ ...................... 4500-Norg B-2011 or C- D3590-11 (A)......... I-4515-91. \45\
(as N), mg/L. and distillation or 2011 and 4500-NH3 B-
gas diffusion, 2011.
followed by any of
the following:
Titration.......... ...................... 4500-NH3 C-2011...... ..................... 973.48. \3\
Nesslerization..... ...................... ..................... D1426-08 (A).........
Electrode.......... ...................... 4500-NH3 D-2011 or E- D1426-08 (B).........
2011.
Semi-automated 350.1, Rev. 2.0 (1993) 4500-NH3 G-2011......
phenate. 4500-NH3 H-2011......
Manual phenate, ...................... 4500-NH3 F-2011...... ..................... See footnote. \60\
salicylate, or
other substituted
phenols in
Berthelot reaction
based methods.
--------------------------------------------------------------------------------------------------------------------
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).
[[Page 8975]]
Semi-automated 351.2, Rev. 2.0 (1993) 4500-Norg D-2011..... D3590-11 (B)......... I-4515-91 \45\
block digestor
colorimetric
(distillation not
required).
Block digester, ...................... ..................... ..................... See footnote. \39\
followed by Auto
distillation and
Titration.
Block digester, ...................... ..................... ..................... See footnote. \40\
followed by Auto
distillation and
Nesslerization.
Block Digester, ...................... ..................... ..................... See footnote. \41\
followed by Flow
injection gas
diffusion
(distillation not
required).
Digestion with ...................... ..................... ..................... Hach 10242. \75\
peroxdisulfate,
followed by
Spectrophotometric
(2,6-dimethyl
phenol).
Digestion with ...................... ..................... ..................... NCASI TNTP W10900.
persulfate, \77\
followed by
Colorimetric.
32. Lead--Total, \4\ mg/L.......... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011 or 3111 C- D3559-08 (A or B).... 974.27 \3\, I-3399-
aspiration \36\. 2011.. 85. \2\
AA furnace......... ...................... 3113 B-2010.......... D3559-08 (D)......... I-4403-89. \51\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
Voltametry \11\.... ...................... ..................... D3559-08 (C).........
Colorimetric ...................... 3500-Pb B-2011.......
(Dithizone).
33. Magnesium--Total, \4\ mg/L..... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011.......... D511-09 (B).......... 974.27 \3\, I-3447-
aspiration. 85. \2\
ICP/AES............ 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14. \3\
DCP................ ...................... ..................... ..................... See footnote. \34\
Ion Chromatography. ...................... ..................... D6919-09.............
34. Manganese--Total, \4\ mg/L..... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011.......... D858-12 (A or B)..... 974.27 \3\, I-3454-
aspiration \36\. 85. \2\
AA furnace......... ...................... 3113 B-2010.......... D858-12 (C)..........
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
[[Page 8976]]
Colorimetric ...................... 3500-Mn B-2011....... ..................... 920.203. \3\
(Persulfate).
Colorimetric ...................... ..................... ..................... See footnote. \23\
(Periodate).
35. Mercury--Total, \4\ mg/L....... Cold vapor, Manual.... 245.1, Rev. 3.0 (1994) 3112 B-2011.......... D3223-12............. 977.22 \3\, I-3462-
85. \2\
Cold vapor, 245.2 (Issued 1974)
Automated. \1\.
Cold vapor atomic 245.7 Rev. 2.0 (2005) ..................... ..................... I-4464-01. \71\
fluorescence \17\.
spectrometry
(CVAFS).
Purge and Trap 1631E \43\............
CVAFS.
36. Molybdenum--Total, \4\ mg/L.... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 D-2011.......... ..................... I-3490-85. \2\
aspiration.
AA furnace......... ...................... 3113 B-2010.......... ..................... I-3492-96. \47\
ICP/AES \36\....... 200.7, Rev. 4.4 (1994) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
DCP................ ...................... ..................... ..................... See footnote. \34\
37. Nickel--Total, \4\ mg/L........ Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011 or....... D1886-08 (A or B).... I-3499-85. \2\
aspiration \36\. 3111 C-2011..........
AA furnace......... ...................... 3113 B-2010.......... D1886-08 (C)......... I-4503-89. \51\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-
05. \70\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
38. Nitrate (as N), mg/L........... Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30. \3\
and 300.1-1, Rev. 1.0
(1997).
CIE/UV............. ...................... 4140 B-2011.......... D6508-10, D6508, Rev.
2 \54\.
Ion Selective ...................... 4500-NO3 - D-2011....
Electrode.
Colorimetric 352.1 (Issued 1971) ..................... ..................... 973.50 \3\, 419D
(Brucine sulfate). \1\. \1,7\, p. 28. \9\
Spectrophotometric ...................... ..................... ..................... Hach 10206. \75\
(2,6-dimethylpheno
l).
Nitrate-nitrite N ...................... ..................... ..................... See footnote. \62\
minus Nitrite N
(See parameters 39
and 40).
Enzymatic ...................... ..................... ..................... I-2547-11. \72\
reduction, I-2548-11. \72\
followed by N07-0003. \73\
automated
colorimetric
determination.
39. Nitrate-nitrite (as N), mg/L... Cadmium reduction, ...................... 4500-NO3 - E-2011.... D3867-04 (B).........
Manual.
Cadmium reduction, 353.2, Rev. 2.0 (1993) 4500-NO3 - F-2011.... D3867-04 (A)......... I-2545-90. \51\
Automated.
Automated hydrazine ...................... 4500-NO3 - H-2011....
Reduction/ ...................... ..................... ..................... See footnote. \62\
Colorimetric.
Ion Chromatography. 300.0, Rev. 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30. \3\
and 300.1-1, Rev. 1.0
(1997).
[[Page 8977]]
CIE/UV............. ...................... 4140 B-2011.......... D6508-10............. D6508, Rev. 2. \54\
Enzymatic ...................... ..................... ..................... I-2547-11. \72\
reduction, I-2548-11. \72\
followed by N07-0003. \73\
automated
colorimetric
determination.
Spectrophotometric ...................... ..................... ..................... Hach 10206. \75\
(2,6-
dimethylphenol).
40. Nitrite (as N), mg/L........... Spectrophotometric: ...................... 4500-NO2 - B-2011.... ..................... See footnote. \25\
Manual.
Automated ...................... ..................... ..................... I-4540-85 \2\, See
(Diazotization). footnote. \62\
Automated (*bypass 353.2, Rev. 2.0 (1993) 4500-NO3 - F-2011.... D3867-04 (A)......... I-4545-85. \2\
cadmium reduction).
Manual (*bypass ...................... 4500-NO3 - E-2011.... D3867-04 (B).........
cadmium reduction).
Ion Chromatography. 300.0, Rev. 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30. \3\
and 300.1-1, Rev. 1.0
(1997).
CIE/UV............. ...................... 4140 B-2011.......... D6508-10, D6508, Rev.
2 \54\.
Enzymatic ...................... ..................... ..................... I-2547-11. \72\
reduction, I-2548-11. \72\
followed by N07-0003. \73\
automated
colorimetric
determination.
41. Oil and grease--Total Hexane extractable 1664 Rev. A; 1664 Rev. 5520 B-2011 \38\.....
recoverable, mg/L. material (HEM): n- B \42\.
Hexane extraction and
gravimetry.
Silica gel treated 1664 Rev. A; 1664 Rev. 5520 B-2011 \38\ and
HEM (SGT-HEM): B \42\. 5520 F-2011 \38\.
Silica gel
treatment and
gravimetry.
42. Organic carbon--Total (TOC), mg/ Combustion............ ...................... 5310 B-2011.......... D7573-09............. 973.47 \3\, p. 14.
L. \24\
Heated persulfate ...................... 5310 C-2011.......... D4839-03............. 973.47 \3,\, p. 14.
or UV persulfate 5310 D-2011.......... \24\
oxidation.
43. Organic nitrogen (as N), mg/L.. Total Kjeldahl N
(Parameter 31) minus
ammonia N (Parameter
4).
44. Ortho-phosphate (as P), mg/L... Ascorbic acid method:
Automated.......... 365.1, Rev. 2.0 (1993) 4500-P F-2011 or G- ..................... 973.56 \3\, I-4601-
2011. 85. \2\
Manual single ...................... 4500-P E-2011........ D515-88 (A).......... 973.55. \3\
reagent.
Manual two reagent. 365.3 (Issued 1978)\1\
Ion Chromatography. 300.0, Rev. 2.1 (1993) 4110 B-2011 or C-2000 D4327-03............. 993.30. \3\
and 300.1-1, Rev. 1.0
(1997).
CIE/UV............. ...................... 4140 B-2011.......... D6508-10, D6508, Rev.
2 \54\.
45. Osmium--Total \4\, mg/L........ Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 D-2011..........
aspiration.
AA furnace......... 252.2 (Issued 1978)
\1\.
46. Oxygen, dissolved, mg/L........ Winkler (Azide ...................... 4500-O (B-F)-2011.... D888-09 (A).......... 973.45B \3\, I-1575-
modification). 78. \8\
Electrode.......... ...................... 4500-O G-2011........ D888-09 (B).......... I-1576-78. \8\
[[Page 8978]]
Luminescence Based ...................... ..................... D888-09 (C).......... See footnote. \63\
Sensor. See footnote. \64\
47. Palladium--Total, \4\ mg/L..... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration.
AA furnace......... 253.2 (Issued 1978)
\1\.
ICP/MS............. ...................... 3125 B-2011..........
DCP................ ...................... ..................... ..................... See footnote. \34\
48. Phenols, mg/L.................. Manual distillation 420.1 (Rev. 1978) \1\. 5530 B-2010.......... D1783-01.............
\26\, followed by any
of the following:
Colorimetric (4AAP) 420.1 (Rev. 1978) \1\. 5530 D-2010 \27\..... D1783-01 (A or B)....
manual.
Automated 420.4 Rev. 1.0 (1993).
colorimetric
(4AAP).
49. Phosphorus (elemental), mg/L... Gas-liquid ...................... ..................... ..................... See footnote. \28\
chromatography.
50. Phosphorus--Total, mg/L........ Digestion \20\, ...................... 4500-P B(5)-2011..... ..................... 973.55. \3\
followed by any of
the following:
Manual............. 365.3 (Issued 1978) 4500-P E-2011........ D515-88 (A)..........
\1\.
Automated ascorbic 365.1 Rev. 2.0 (1993). 4500-P (F-H)-2011.... ..................... 973.56 \3\, I-4600-
acid reduction. 85. \2\
ICP/AES \4, 36\.... 200.7, Rev. 4.4 (1994) 3120 B-2011.......... ..................... I-4471-97. \50\
Semi-automated 365.4 (Issued 1974) ..................... D515-88 (B).......... I-4610-91. \48\
block digestor \1\.
(TKP digestion).
Digestion with ...................... ..................... ..................... NCASI TNTP W10900.
persulfate, \77\
followed by
Colorimetric.
51. Platinum--Total, \4\ mg/L...... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration.
AA furnace......... 255.2 (Issued 1978)
\1\.
ICP/MS............. ...................... 3125 B-2011..........
DCP................ ...................... ..................... ..................... See footnote. \34\
52. Potassium--Total, \4\ mg/L..... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011.......... ..................... 973.53 \3\, I-3630-
aspiration. 85. \2\
ICP/AES............ 200.7, Rev. 4.4 (1994) 3120 B-2011..........
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14. \3\
Flame photometric.. ...................... 3500-K B-2011........
Electrode.......... ...................... 3500-K C-2011........
Ion Chromatography. ...................... ..................... D6919-09.............
53. Residue--Total, mg/L........... Gravimetric, 103- ...................... 2540 B-2011.......... ..................... I-3750-85. \2\
105[deg].
54. Residue--filterable, mg/L...... Gravimetric, 180[deg]. ...................... 2540 C-2011.......... D5907-13............. I-1750-85. \2\
55. Residue--non-filterable (TSS), Gravimetric, 103- ...................... 2540 D-2011.......... D5907-13............. I-3765-85. \2\
mg/L. 105[deg] post washing
of residue.
56. Residue--settleable, mg/L...... Volumetric, (Imhoff ...................... 2540 F-2011..........
cone), or gravimetric.
57. Residue--Volatile, mg/L........ Gravimetric, 550[deg]. 160.4 (Issued 1971) 2540-E-2011.......... ..................... I-3753-85. \2\
\1\.
58. Rhodium--Total, \4\ mg/L....... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration, or.
AA furnace......... 265.2 (Issued 1978)
\1\.
ICP/MS............. ...................... 3125 B-2011..........
59. Ruthenium--Total, \4\ mg/L..... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration, or.
[[Page 8979]]
AA furnace......... 267.2 \1\.............
ICP/MS............. ...................... 3125 B-2011..........
60. Selenium--Total, \4\ mg/L...... Digestion \4\,
followed by any of
the following:
AA furnace......... ...................... 3113 B-2010.......... D3859-08 (B)......... I-4668-98. \49\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES \36\....... 200.5, Rev 4.2 (2003) 3120 B-2011.......... D1976-12.............
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-
05. \70\
AA gaseous hydride. ...................... 3114 B-2011, or 3114 D3859-08 (A)......... I-3667-85. \2\
C-2011.
61. Silica--Dissolved, \37\ mg/L... 0.45-micron filtration
followed by any of
the following:
Colorimetric, ...................... 4500-SiO 2 C-2011.... D859-10.............. I-1700-85. \2\
Manual.
Automated ...................... 4500-SiO 2 E-2011 or ..................... I-2700-85. \2\
(Molybdosilicate). F-2011.
ICP/AES............ 200.5, Rev. 4.2 (2003) 3120 B-2011.......... ..................... I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14. \3\
62. Silver--Total, \4\ \31\ mg/L... Digestion\4, 29\,
followed by any of
the following:
AA direct ...................... 3111 B-2011 or....... ..................... 974.27 \3\, p. 37
aspiration. 3111 C-2011.......... \9\, I-3720-85. \2\
AA furnace......... ...................... 3113 B-2010.......... ..................... I-4724-89. \51\
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES............ 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
DCP................ ...................... ..................... ..................... See footnote. \34\
63. Sodium--Total, \4\ mg/L........ Digestion \4,\,
followed by any of
the following:
AA direct ...................... 3111 B-2011.......... ..................... 973.54 \3\, I-3735-
aspiration. 85. \2\
ICP/AES............ 200.5, Rev. 4.2 (2003) 3120 B-2011.......... ..................... I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14. \3\
DCP................ ...................... ..................... ..................... See footnote. \34\
Flame photometric.. ...................... 3500-Na B-2011.......
Ion Chromatography. ...................... ..................... D6919-09.............
64. Specific conductance, micromhos/ Wheatstone bridge..... 120.1 (Rev. 1982) \1\. 2510 B-2011.......... D1125-95(99) (A)..... 973.40 \3\, I-2781-
cm at 25 [deg]C. 85. \2\
65. Sulfate (as SO4), mg/L......... Automated colorimetric 375.2, Rev. 2.0 (1993) 4500-SO 4 \2\- F-2011
or G-2011.
Gravimetric........ ...................... 4500-SO4 2- C-2011 or ..................... 925.54. \3\
D-2011.
Turbidimetric...... ...................... 4500-SO4 2- E-2011... D516-11..............
Ion Chromatography. 300.0, Rev. 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30 \3\, I-4020-
and 300.1-1, Rev. 1.0 05. \70\
(1997).
CIE/UV............. ...................... 4140 B-2011.......... D6508-1010........... D6508, Rev. 2. \54\
66. Sulfide (as S), mg/L........... Sample Pretreatment... ...................... 4500-S 2-> B, C-2011.
Titrimetric ...................... 4500-S 2- F-2011..... ..................... I-3840-85. \2\
(iodine).
Colorimetric ...................... 4500-S 2- D-2011.....
(methylene blue).
[[Page 8980]]
Ion Selective ...................... 4500-S 2- G-2011..... D4658-09.............
Electrode.
67. Sulfite (as SO3), mg/L......... Titrimetric (iodine- ...................... 4500-SO3 2- B-2011...
iodate).
68. Surfactants, mg/L.............. Colorimetric ...................... 5540 C-2011.......... D2330-02.............
(methylene blue).
69. Temperature, [deg]C............ Thermometric.......... ...................... 2550 B-2010.......... ..................... See footnote. \32\
70. Thallium--Total, \4\ mg/L...... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011..........
aspiration.
AA furnace......... 279.2 (Issued 1978) \ 3113 B-2010..........
1\.
STGFAA............. 200.9, Rev. 2.2 (1994)
ICP/AES............ 200.7, Rev. 4.4 (1994) 3120 B-2011.......... D1976-12.............
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4471-
97. \50\
71. Tin--Total, \4\ mg/L........... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011.......... ..................... I-3850-78. \8\
aspiration.
AA furnace......... ...................... 3113 B-2010..........
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-2011.......... D5673-10............. 993.14. \3\
72. Titanium--Total, \4\ mg/L...... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 D-2011..........
aspiration.
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-2011.......... D5673-10............. 993.14. \3\
DCP................ ...................... ..................... ..................... See footnote. \34\
73. Turbidity, NTU \53\............ Nephelometric......... 180.1, Rev. 2.0 (1993) 2130 B-2011.......... D1889-00............. I-3860-85. \2\
See footnote. \65\
See footnote. \66\
See footnote. \67\
74. Vanadium--Total, \4\ mg/L...... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 D-2011..........
aspiration.
AA furnace......... ...................... 3113 B-2010.......... D3373-12.............
ICP/AES............ 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-
05. \70\
DCP................ ...................... ..................... D4190-08............. See footnote. \34\
Colorimetric ...................... 3500-V B-2011........
(Gallic Acid).
75. Zinc--Total \4\, mg/L.......... Digestion \4\,
followed by any of
the following:
AA direct ...................... 3111 B-2011 or 3111 C- D1691-12 (A or B).... 974.27 \3\, p. 37
aspiration \36\. 2011. \9\, I-3900-85. \2\
AA furnace......... 289.2 (Issued 1978)
\1\.
ICP/AES \36\....... 200.5, Rev. 4.2 (2003) 3120 B-2011.......... D1976-12............. I-4471-97. \50\
\68\; 200.7, Rev. 4.4
(1994).
ICP/MS............. 200.8, Rev. 5.4 (1994) 3125 B-2011.......... D5673-10............. 993.14 \3\, I-4020-05
\70\
DCP \36\........... ...................... ..................... D4190-08............. See footnote. \34\
Colorimetric ...................... 3500 Zn B-2011....... ..................... See footnote. \33\
(Zincon).
[[Page 8981]]
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 the 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 determinations (FLAA) a
combination acid (nitric and hydrochloric acids) digestion is preferred prior to analysis. The approved total recoverable digestion is described as
Method 200.2 in Supplement I of ``Methods for the Determination of Metals in Environmental Samples'' EPA/600R-94/111, May, 1994, and is reproduced in
EPA Methods 200.7, 200.8, and 200.9 from the same Supplement. However, when using the gaseous hydride technique or for the determination of certain
elements such as antimony, arsenic, selenium, silver, and tin by non-EPA graphite furnace atomic absorption methods, mercury by cold vapor atomic
absorption, the noble metals and titanium by FLAA, a specific or modified sample digestion procedure may be required and in all cases the referenced
method write-up should be consulted for specific instruction and/or cautions. For analyses using inductively coupled plasma-atomic emission
spectrometry (ICP-AES), the direct current plasma (DCP) technique or EPA spectrochemical techniques (platform furnace AA, ICP-AES, and ICP-MS) use EPA
Method 200.2 or an approved alternate procedure (e.g., CEM microwave digestion, which may be used with certain analytes as indicated in Table IB); 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. (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 BOD.'' The
addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit
requires reporting the traditional BOD5 may not use a nitrification inhibitor in the procedure for reporting the results. Only when a discharger's
permit specifically states CBOD5 is required can the permittee report data using a nitrification inhibitor.
\13\ OIC Chemical Oxygen Demand Method. 1978. Oceanography International Corporation.
\14\ Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company.
\15\ The back titration method will be used to resolve controversy.
\16\ Orion Research Instruction Manual, Residual Chlorine Electrode Model 97-70. 1977. Orion Research Incorporated. The calibration graph for the Orion
residual chlorine method must be derived using a reagent blank and three standard solutions, containing 0.2, 1.0, and 5.0 mL 0.00281 N potassium
iodate/100 mL solution, respectively.
\17\ Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-05-001. Revision 2.0, February 2005. US EPA.
\18\ National Council of the Paper Industry for Air and Stream Improvement (NCASI) Technical Bulletin 803, May 2000.
\19\ Method 8506, Biocinchoninate 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.
[[Page 8982]]
\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 300.1-1, 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 US EPA. Revision 1.0, 1997, including errata cover sheet April 27, 1999. Determination of
Inorganic Ions in Drinking Water by Ion Chromatography.
\53\ Styrene divinyl benzene beads (e.g., AMCO-AEPA-1 or equivalent) and stabilized formazin (e.g., Hach StablCal\TM\ or equivalent) are acceptable
substitutes for formazin.
\54\ Method D6508-10, Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and Chromate
Electrolyte. 2010. ASTM.
\55\ Kelada-01, Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, and Thiocyanate, EPA 821-B-01-009, Revision 1.2, August 2001.
US EPA. Note: A 450-W UV lamp may be used in this method instead of the 550-W lamp specified if it provides performance within the quality control
(QC) acceptance criteria of the method in a given instrument. Similarly, modified flow cell configurations and flow conditions may be used in the
method, provided that the QC acceptance criteria are met.
\56\ QuikChem Method 10-204-00-1-X, Digestion and Distillation of Total Cyanide in Drinking and Wastewaters using MICRO DIST and Determination of
Cyanide by Flow Injection Analysis. Revision 2.2, March 2005. Lachat Instruments.
\57\ When using sulfide removal test procedures described in EPA Method 335.4-1, 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 D6888-09 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 may
be used. This method has poorer precision and bias than the methods of choice.
\62\ Easy (1-Reagent) Nitrate Method, Revision November 12, 2011. Craig Chinchilla.
\63\ Hach Method 10360, Luminescence Measurement of Dissolved Oxygen in Water and Wastewater and for Use in the Determination of BOD5 and cBOD5.
Revision 1.2, October 2011. Hach Company. This method may be used to measure dissolved oxygen when performing the methods approved in Table IB for
measurement of biochemical oxygen demand (BOD) and carbonaceous biochemical oxygen demand (CBOD).
\64\ In-Situ Method 1002-8-2009, Dissolved Oxygen (DO) Measurement by Optical Probe. 2009. In-Situ Incorporated.
\65\ Mitchell Method M5331, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.
\66\ Mitchell Method M5271, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.
\67\ Orion Method AQ4500, Determination of Turbidity by Nephelometry. Revision 5, March 12, 2009. Thermo Scientific.
\68\ EPA Method 200.5, Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry, EPA/
600/R-06/115. Revision 4.2, October 2003. US EPA.
\69\ Method 1627, Kinetic Test Method for the Prediction of Mine Drainage Quality, EPA-821-R-09-002. December 2011. US EPA.
[[Page 8983]]
\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, Revision 9.0, March 2014, Method for Nitrate Reductase Nitrate-Nitrogen Analysis, The Nitrate Elimination Co., Inc.
\74\ Timberline Instruments, LLC Method Ammonia-001, Timberline Instruments, LLC.
\75\ Hach Company Method 10206, Hach Company.
\76\ Hach Company Method 10242, 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.
Table IC--List of Approved Test Procedures for Non-Pesticide Organic Compounds
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter \1\ Method EPA \2\ \7\ Standard methods ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acenaphthene................. GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
2. Acenaphthylene............... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
3. Acrolein..................... GC................. 603
GC/MS.............. 624.1 \4\,1624B
4. Acrylonitrile................ GC................. 603
GC/MS.............. 624.1 \4\,1624B
5. Anthracene................... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440B-2005 D4657-92 (98)
6. Benzene...................... GC................. 602 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
7. Benzidine.................... Spectro-photometric ........................ ........................ ........................ See footnote \3\,
p.1.
GC/MS.............. 625.1 \5\, 1625B 6410 B-2000
HPLC............... 605
8. Benzo(a)anthracene........... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
9. Benzo(a)pyrene............... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
10. Benzo(b)fluoranthene........ GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
11. Benzo(g,h,i)perylene........ GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
12. Benzo(k)fluoranthene........ GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 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-2000 ........................ See footnote \9\,
p. 27.
15. bis(2-Chloroethoxy) methane. GC................. 611
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
16. bis(2-Chloroethyl) ether.... GC................. 611
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
17. bis(2-Ethylhexyl) phthalate. GC................. 606
[[Page 8984]]
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
18. Bromodichloromethane........ GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
19. Bromoform................... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
20. Bromomethane................ GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
21. 4-Bromophenyl phenyl ether.. GC................. 611
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
22. Carbon tetrachloride........ GC................. 601 6200 C-2011 ........................ See footnote \3\,
p. 130.
GC/MS.............. 624.1, 1624B 6200 B-2011
23. 4-Chloro-3-methyl phenol.... GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
24. Chlorobenzene............... GC................. 601, 602 6200 C-2011 ........................ See footnote \3\,
p. 130.
GC/MS.............. 624.1, 1624B 6200 B-2011
25. Chloroethane................ GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
26. 2-Chloroethylvinyl ether.... GC................. 601
GC/MS.............. 624.1, 1624B
27. Chloroform.................. GC................. 601 6200 C-2011 ........................ See footnote \3\,
p. 130.
GC/MS.............. 624.1, 1624B 6200 B-2011
28. Chloromethane............... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
29. 2-Chloronaphthalene......... GC................. 612
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
30. 2-Chlorophenol.............. GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
31. 4-Chlorophenyl phenyl ether. GC................. 611
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
32. Chrysene.................... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
33. Dibenzo(a,h)anthracene...... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
34. Dibromochloromethane........ GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
35. 1,2-Dichlorobenzene......... GC................. 601, 602 6200 C-2011
GC/MS.............. 625.1, 1625B 6200 B-2011 ........................ See footnote \9\,
p. 27.
36. 1,3-Dichlorobenzene......... GC................. 601, 602 6200 C-2011
GC/MS.............. 624.1, 1625B 6200 B-2011 ........................ See footnote \9\,
p. 27.
37. 1,4-Dichlorobenzene......... GC................. 601, 602 6200 C-2011
GC/MS.............. 624.1, 1625B 6200 B-2011 ........................ See footnote \9\,
p. 27.
38. 3,3'-Dichlorobenzidine...... GC/MS.............. 625.1, 1625B 6410 B-2000
HPLC............... 605
39. Dichlorodifluoromethane..... GC................. 601
GC/MS.............. ........................ 6200 C-2011
40. 1,1-Dichloroethane.......... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
41. 1,2-Dichloroethane.......... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
42. 1,1-Dichloroethene.......... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
43. trans-1,2-Dichloroethene.... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
44. 2,4-Dichlorophenol.......... GC................. 604 6420 B-2000
[[Page 8985]]
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
45. 1,2-Dichloropropane......... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
46. cis-1,3-Dichloropropene..... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
47. trans-1,3-Dichloropropene... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
48. Diethyl phthalate........... GC................. 606
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
49. 2,4-Dimethylphenol.......... GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
50. Dimethyl phthalate.......... GC................. 606
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
51. Di-n-butyl phthalate........ GC................. 606
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
52. Di-n-octyl phthalate........ GC................. 606
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
53. 2, 4-Dinitrophenol.......... GC................. 604 6420 B-2000 ........................ See footnote \9\,
p. 27.
GC/MS.............. 625.1, 1625B 6410 B-2000
54. 2,4-Dinitrotoluene.......... GC................. 609
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
55. 2,6-Dinitrotoluene.......... GC................. 609
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
56. Epichlorohydrin............. GC................. ........................ ........................ ........................ See footnote \3\,
p. 130.
GC/MS.............. ........................ ........................ ........................ See footnote \6\,
p. S102.
57. Ethylbenzene................ GC................. 602 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
58. Fluoranthene................ GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
59. Fluorene.................... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
60. 1,2,3,4,6,7,8-Heptachloro- GC/MS.............. 1613B
dibenzofuran.
61. 1,2,3,4,7,8,9-Heptachloro- GC/MS.............. 1613B
dibenzofuran.
62. 1,2,3,4,6,7,8- Heptachloro- GC/MS.............. 1613B
dibenzo-p-dioxin.
63. Hexachlorobenzene........... GC................. 612
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
64. Hexachlorobutadiene......... GC................. 612
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
65. Hexachlorocyclopentadiene... GC................. 612
GC/MS.............. 625.1\ 5\, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
66. 1,2,3,4,7,8-Hexachloro- GC/MS.............. 1613B
dibenzofuran.
67. 1,2,3,6,7,8-Hexachloro- GC/MS.............. 1613B
dibenzofuran.
68. 1,2,3,7,8,9-Hexachloro- GC/MS.............. 1613B
dibenzofuran.
69. 2,3,4,6,7,8-Hexachloro- GC/MS.............. 1613B
dibenzofuran.
70. 1,2,3,4,7,8-Hexachloro- GC/MS.............. 1613B
dibenzo-p-dioxin.
71. 1,2,3,6,7,8-Hexachloro- GC/MS.............. 1613B
dibenzo-p-dioxin.
72. 1,2,3,7,8,9-Hexachloro- GC/MS.............. 1613B
dibenzo-p-dioxin.
73. Hexachloroethane............ GC................. 612
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
74. Indeno(1,2,3-c,d) pyrene.... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
[[Page 8986]]
HPLC............... 610 6440 B-2005 D4657-92 (98)
75. Isophorone.................. GC................. 609
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
76. Methylene chloride.......... GC................. 601 6200 C-2011 ........................ See footnote \3\,
p. 130.
GC/MS.............. 624.1, 1624B 6200 B-2011
77. 2-Methyl-4,6-dinitrophenol.. GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
78. Naphthalene................. GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005
79. Nitrobenzene................ GC................. 609
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... ........................ ........................ D4657-92 (98)
80. 2-Nitrophenol............... GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
81. 4-Nitrophenol............... GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
82. N-Nitrosodimethylamine...... GC................. 607
GC/MS.............. 625.1 \ 5\, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
83. N-Nitrosodi-n-propylamine... GC................. 607
GC/MS.............. 625.1 \ 5\, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
84. N-Nitrosodiphenylamine...... GC................. 607
GC/MS.............. 625.1 \5\, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
85. Octachlorodibenzofuran...... GC/MS.............. 1613B \10\
86. Octachlorodibenzo-p-dioxin.. GC/MS.............. 1613B \10\
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-2000 ........................ 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-2000
89. PCB-1221.................... GC................. 608.3 ........................ ........................ See footnote \3\,
p. 43; See
footnote. \8\
GC/MS.............. 625.1 6410 B-2000
90. PCB-1232.................... GC................. 608.3 ........................ ........................ See footnote \3\,
p. 43; See
footnote. \8\
GC/MS.............. 625.1 6410 B-2000
91. PCB-1242.................... GC................. 608.3 ........................ ........................ See footnote \3\,
p. 43; See
footnote. \8\
GC/MS.............. 625.1 6410 B-2000
92. PCB-1248.................... GC................. 608.3 ........................ ........................ See footnote \3\,
p. 43; See
footnote. \8\
GC/MS.............. 625.1 6410 B-2000
93. PCB-1254.................... GC................. 608.3 ........................ ........................ See footnote \3\,
p. 43; See
footnote. \8\
GC/MS.............. 625.1 6410 B-2000
94. PCB-1260.................... GC................. 608.3 ........................ ........................ See footnote \3\,
p. 43; See
footnote. \8\
GC/MS.............. 625.1 6410 B-2000
95. 1,2,3,7,8-Pentachloro- GC/MS.............. 1613B
dibenzofuran.
96. 2,3,4,7,8-Pentachloro- GC/MS.............. 1613B
dibenzofuran.
97. 1,2,3,7,8,-Pentachloro- GC/MS.............. 1613B
dibenzo-p-dioxin.
[[Page 8987]]
98. Pentachlorophenol........... GC................. 604 6420 B-2000 ........................ See footnote \3\,
p. 140.
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
99. Phenanthrene................ GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98)
100. Phenol..................... GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
101. Pyrene..................... GC................. 610
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
HPLC............... 610 6440 B-2005 D4657-92 (98).
102. 2,3,7,8-Tetrachloro- GC/MS.............. 1613B \10\
dibenzofuran.
103. 2,3,7,8-Tetrachloro-dibenzo- GC/MS.............. 613, 625.1 \5a\, 1613B
p-dioxin.
104. 1,1,2,2-Tetrachloroethane.. GC................. 601 6200 C-2011 ........................ See footnote \3\,
p. 130.
GC/MS.............. 624.1, 1624B 6200 B-2011
105. Tetrachloroethene.......... GC................. 601 6200 C-2011 ........................ See footnote \3\,
p. 130.
GC/MS.............. 624.1, 1624B 6200 B-2011
106. Toluene.................... GC................. 602 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
107. 1,2,4-Trichlorobenzene..... GC................. 612 ........................ ........................ See footnote \3\,
p. 130.
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
108. 1,1,1-Trichloroethane...... GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
109. 1,1,2-Trichloroethane...... GC................. 601 6200 C-2011 ........................ See footnote \3\,
p. 130.
GC/MS.............. 624.1, 1624B 6200 B-2011
110. Trichloroethene............ GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
111. Trichlorofluoromethane..... GC................. 601 6200 C-2011
GC/MS.............. 624.1 6200 B-2011
112. 2,4,6-Trichlorophenol...... GC................. 604 6420 B-2000
GC/MS.............. 625.1, 1625B 6410 B-2000 ........................ See footnote \9\,
p. 27.
113. Vinyl chloride............. GC................. 601 6200 C-2011
GC/MS.............. 624.1, 1624B 6200 B-2011
114. Nonylphenol................ GC/MS.............. ........................ ........................ D7065-11
115. Bisphenol A (BPA).......... GC/MS.............. ........................ ........................ D7065-11
116. p-tert-Octylphenol (OP).... GC/MS.............. ........................ ........................ D7065-11
117. Nonylphenol Monoethoxylate GC/MS.............. ........................ ........................ D7065-11
(NP1EO).
118. Nonylphenol Diethoxylate GC/MS.............. ........................ ........................ D7065-11
(NP2EO).
119. Adsorbable Organic Halides Adsorption and 1650 \11\
(AOX). Coulometric
Titration.
120. Chlorinated Phenolics...... In Situ Acetylation 1653 \11\
and GC/MS.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IC notes:
\1\ All parameters are expressed in micrograms per liter ([micro]g/L) except for Method 1613B, in which the parameters are expressed in picograms per
liter (pg/L).
\2\ The full text of Methods 601-613, 1613B, 1624B, and 1625B are provided at Appendix A, Test Procedures for Analysis of Organic Pollutants, of this
Part 136. The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at Appendix B,
Definition and Procedure for the Determination of the Method Detection Limit, of this Part 136. Methods 608.3, 624.1, and 625.1 are available at:
water.epa.gov/scitech/methods/cwa/methods_index.cfm.
\3\ Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA.
\4\ Method 624.1 may be used for quantitative determination of acrolein and acrylonitrile, provided that the laboratory has documentation to
substantiate the ability to detect and quantify these analytes at levels necessary to comply with any associated regulations. In addition, the use of
sample introduction techniques other than simple purge-and-trap may be required. QC acceptance criteria from Method 603 should be used when analyzing
samples for acrolein and acrylonitrile in the absence of such criteria in Method 624.1.
\5\ Method 625.1 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, N-nitrosodi-n-propylamine, and N-
nitrosodiphenylamine. However, when they are known to be present, Methods 605, 607, and 612, or Method 1625B, are preferred methods for these
compounds.
\5a\ Method 625.1 screening only.
[[Page 8988]]
\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 each in Section 8.2 of each of these Methods. Additionally, each laboratory, on an on-going basis must
spike and analyze 10% (5% for Methods 624.1 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 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-3116-87 is in Open File Report 93-125, Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory--Determination of
Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. USGS.
\10\ Analysts may use Fluid Management Systems, Inc. Power-Prep system in place of manual cleanup provided the analyst meets the requirements of Method
1613B (as specified in Section 9 of the method) and permitting authorities. Method 1613, Revision B, Tetra- through Octa-Chlorinated Dioxins and
Furans by Isotope Dilution HRGC/HRMS. Revision B, 1994. U.S. EPA. The full text of this method is provided in Appendix A to 40 CFR part 136 and at
http://water.epa.gov/scitech/methods/cwa/index.cfm.
\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,
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.
Table ID--List of Approved Test Procedures for Pesticides \1\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter Method EPA 2 7 10 Standard methods ASTM Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Aldrin.......................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812-96 See footnote,\3\ p.
(02). 7; See footnote,\4\
O-3104-83; See
footnote, \8\
3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
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-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\8\
3M0222.
GC/MS................. 625.1 \5\............. 6410 B-2000.......... ..................... See footnote,\11\ O-
1126-95.
9. [beta]-BHC...................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\8\
96(02). 3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
10. [delta]-BHC.................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\8\
96(02). 3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
11. [gamma]-BHC (Lindane).......... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1 \5\............. 6410 B-2000.......... ..................... See footnote,\11\ O-
1126-95.
12. Captan......................... GC.................... 617, 608.3............ 6630 B-2007.......... D3086-90, D5812- See footnote,\3\ p.
96(02). 7.
13. Carbaryl....................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94, See footnote,\6\
p. S60.
[[Page 8989]]
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-2007.......... ..................... See footnote,\4\ page
27; See footnote,\6\
p. S73.
GC/MS................. 625.1.................
15. Chlordane...................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
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-2006.......... ..................... 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-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3105-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
19. 4,4'-DDE....................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2000.......... ..................... See footnote,\11\ O-
1126-95.
20. 4,4'-DDT....................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
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-2007.......... ..................... 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-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1................. 6410 B-2000.......... ..................... See footnote,\11\ O-
1126-95.
29. Dioxathion..................... GC.................... 614.1, 1657........... ..................... ..................... See footnote,\4\ page
27; See footnote,\6\
p. S73.
30. Disulfoton..................... GC.................... 507, 614, 622, 1657... ..................... ..................... See footnote,\3\ p.
25; See footnote,\6\
p. S51.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\11\ O-
1126-95.
31. Diuron......................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
[[Page 8990]]
HPLC.................. 632...................
HPLC/MS............... 553................... ..................... ..................... See footnote,\12\ O-
2060-01.
32. Endosulfan I................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 625.1 \5\............. 6410 B-2000.......... ..................... See footnote,\13\ O-
2002-01.
33. Endosulfan II.................. GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\8\
3M0222.
GC/MS................. 625.1 \5\............. 6410 B-2000.......... ..................... See footnote,\13\ O-
2002-01.
34. Endosulfan Sulfate............. GC.................... 617, 608.3............ 6630 C-2007.......... ..................... See footnote,\8\
3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
35. Endrin......................... GC.................... 505, 508, 617, 1656, 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
608.3. 96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 525.1, 525.2, 625.1 6410 B-2000..........
\5\.
36. Endrin aldehyde................ GC.................... 617, 608.3............ 6630 C-2007.......... ..................... See footnote,\8\
3M0222.
GC/MS................. 625.1.................
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-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
608.3. 96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
GC/MS................. 525.1, 525.2, 625.1... 6410 B-2000..........
41. Heptachlor epoxide............. GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\6\ p. S73;
See footnote,\8\
3M0222.
GC/MS................. 625.1................. 6410 B-2000..........
42. Isodrin........................ GC.................... 617, 608.3............ 6630 B-2007 & C-2007. ..................... 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................. ...................... ..................... ..................... Seeootnote,\11\ O-
1126-95.
44. Malathion...................... GC.................... 614, 1657............. 6630 B-2007.......... ..................... 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-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
1656, 608.3. 96(02). 7; See footnote,\4\
O-3104-83; See
footnote,\8\ 3M0222.
[[Page 8991]]
GC/MS................. 525.1, 525.2, 625.1... ..................... ..................... See footnote,\11\ O-
1126-95.
47. Mexacarbate.................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94; See footnote,\6\
p. S60.
HPLC.................. 632...................
GC/MS................. 625.1.................
48. Mirex.......................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7; See footnote,\4\
O-3104-83.
GC/MS................. 625.1.................
49. Monuron........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
50. Monuron-TCA.................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
51. Neburon........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
52. Parathion methyl............... GC.................... 614, 622, 1657........ 6630 B-2007.......... ..................... 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-2007.......... ..................... 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-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
96(02). 7.
55. Perthane....................... GC.................... 617, 608.3............ ..................... D3086-90, D5812- See footnote,\4\ O-
96(02). 3104-83.
56. Prometon....................... GC.................... 507, 619.............. ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\11\ O-
1126-95.
57. Prometryn...................... GC.................... 507, 619.............. ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.1, 525.2, 625.1... ..................... ..................... See footnote,\13\ O-
2002-01.
58. Propazine...................... GC.................... 507, 619, 1656, 608.3. ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.1, 525.2, 625.1...
59. Propham........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
60. Propoxur....................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
94; See footnote,\6\
p. S60.
HPLC.................. 632...................
61. Secbumeton..................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
83; See footnote,\6\
p. S68.
GC.................... 619...................
62. Siduron........................ TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
HPLC.................. 632...................
HPLC/MS............... ...................... ..................... ..................... See footnote,\12\ O-
2060-01.
63. Simazine....................... GC.................... 505, 507, 619, 1656, ..................... ..................... See footnote,\3\ p.
608.3. 83; See footnote,\6\
p. S68; See
footnote,\9\ O-3106-
93.
GC/MS................. 525.1, 525.2, 625.1... ..................... ..................... See footnote,\11\ O-
1126-95.
64. Strobane....................... GC.................... 617, 608.3............ 6630 B-2007 & C-2007. ..................... See footnote,\3\ p.
7.
65. Swep........................... TLC................... ...................... ..................... ..................... See footnote,\3\ p.
104; See
footnote,\6\ p. S64.
[[Page 8992]]
HPLC.................. 632...................
66. 2,4,5-T........................ GC.................... 615................... 6640 B-2006.......... ..................... See footnote,\3\ p.
115; See
footnote,\4\ O-3105-
83.
67. 2,4,5-TP (Silvex).............. GC.................... 615................... 6640 B-2006.......... ..................... 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-2007 & C-2007. D3086-90, D5812- See footnote,\3\ p.
608.3. 96(02). 7; See footnote,\8\;
See footnote,\4\ O-
3105-83.
GC/MS................. 525.1, 525.2, 625.1... 6410 B-2000..........
70. Trifluralin.................... GC.................... 508, 617, 627, 1656, 6630 B-2007.......... ..................... See footnote,\3\ p.
608.3. 7; See footnote,\9\
O-3106-93.
GC/MS................. 525.2, 625.1.......... ..................... ..................... See footnote,\11\ O-
1126-95.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table ID notes:
\1\ Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides may be found under Table IC, where
entries are listed by chemical name.
\2\ The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at Appendix B,
Definition and Procedure for the Determination of the Method Detection Limit, of this Part 136.
\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 608.3 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 5% 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: http://water.epa.gov/scitech/methods/cwa/methods_index.cfm (this is a placeholder for now).
\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.
* * * * *
Table 1F--List of Approved Methods for Pharmaceutical Pollutants
------------------------------------------------------------------------
Analytical
Pharmaceuticals pollutants CAS Registry No. method number
------------------------------------------------------------------------
Acetonitrile................. 75-05-8 1666/1671/D3371/
D3695/624.1.
n-Amyl acetate............... 628-63-7 1666/D3695.
n-Amyl alcohol............... 71-41-0 1666/D3695.
Benzene...................... 71-43-2 D4763/D3695/
502.2/524.2/
624.1.
[[Page 8993]]
n-Butyl-acetate.............. 123-86-4 1666/D3695.
tert-Butyl alcohol........... 75-65-0 1666/624.1.
Chlorobenzene................ 108-90-7 502.2/524.2/
624.1.
Chloroform................... 67-66-3 502.2/524.2/551/
624.1.
o-Dichlorobenzene............ 95-50-1 1625C/502.2/
524.2/624.1.
1,2-Dichloroethane........... 107-06-2 D3695/502.2/
524.2/624.1.
Diethylamine................. 109-89-7 1666/1671.
Dimethyl sulfoxide........... 67-68-5 1666/1671.
Ethanol...................... 64-17-5 1666/1671/D3695/
624.1.
Ethyl acetate................ 141-78-6 1666/D3695/
624.1.
n-Heptane.................... 142-82-5 1666/D3695.
n-Hexane..................... 110-54-3 1666/D3695.
Isobutyraldehyde............. 78-84-2 1666/1667.
Isopropanol.................. 67-63-0 1666/D3695.
Isopropyl acetate............ 108-21-4 1666/D3695.
Isopropyl ether.............. 108-20-3 1666/D3695.
Methanol..................... 67-56-1 1666/1671/D3695/
624.1.
Methyl Cellosolve [supreg] (2- 109-86-4 1666/1671.
Methoxy ethanol).
Methylene chloride........... 75-09-2 502.2/524.2/
624.1.
Methyl formate............... 107-31-3 1666.
4-Methyl-2-pentanone (MIBK).. 108-10-1 1624C/1666/D3695/
D4763/524.2/
624.1.
Phenol....................... 108-95-2 D4763.
n-Propanol................... 71-23-8 1666/1671/D3695/
624.1.
2-Propanone (Acetone)........ 67-64-1 D3695/D4763/
524.2/624.1.
Tetrahydrofuran.............. 109-99-9 1666/524.2/
624.1.
Toluene...................... 108-88-3 D3695/D4763/
502.2/524.2/
624.1.
Triethlyamine................ 121-44-8 1666/1671.
Xylenes...................... (Note 1) 1624C/1666/
624.1.
------------------------------------------------------------------------
Table 1F note:
\1\ 1624C: m-xylene 108-38-3, o,p-xylene, E-14095 (Not a CAS number;
this is the number provided in the Environmental Monitoring Methods
Index [EMMI] database.); 1666: m,p-xylene 136777-61-2, o-xylene 95-47-
6.
Table 1G--Test Methods for Pesticide Active Ingredients (40 CFR part 455)
----------------------------------------------------------------------------------------------------------------
EPA analytical method
EPA survey code Pesticide name CAS No. No.(s) \3\
----------------------------------------------------------------------------------------------------------------
8.................................. Triadimefon........... 43121-43-3 507/633/525.1/525.2/
1656/625.1.
12................................. Dichlorvos............ 62-73-7 1657/507/622/525.1/
525.2/625.1.
16................................. 2,4-D; 2,4-D Salts and 94-75-7 1658/515.1/615/515.2/
Esters [2,4-Dichloro- 555.
phenoxyacetic acid].
17................................. 2,4-DB; 2,4-DB Salts 94-82-6 1658/515.1/615/515.2/
and Esters [2,4- 555.
Dichlorophenoxybutyri
c acid].
22................................. Mevinphos............. 7786-34-7 1657/507/622/525.1/
525.2/625.1.
25................................. Cyanazine............. 21725-46-2 629/507/608.3/625.1.
26................................. Propachlor............ 1918-16-7 1656/508/608.1/525.1/
525.2/608.3/625.1.
27................................. MCPA; MCPA Salts and 94-74-6 1658/615/555.
Esters [2-Methyl-4-
chlorophenoxyacetic
acid].
30................................. Dichlorprop; 120-36-5 1658/515.1/615/515.2/
Dichlorprop Salts and 555.
Esters [2-(2,4-
Dichlorophenoxy)
propionic acid].
31................................. MCPP; MCPP Salts and 93-65-2 1658/615/555.
Esters [2-(2-Methyl-4-
chlorophenoxy)
propionic acid].
35................................. TCMTB [2- 21564-17-0 637.
(Thiocyanomethylthio)
benzo-thiazole].
39................................. Pronamide............. 23950-58-5 525.1/525.2/507/633.1/
625.1.
41................................. Propanil.............. 709-98-8 632.1/1656/608.3.
45................................. Metribuzin............ 21087-64-9 507/633/525.1/525.2/
1656/608.3/ 625.1.
52................................. Acephate.............. 30560-19-1 1656/1657/608.3.
53................................. Acifluorfen........... 50594-66-6 515.1/515.2/555.
54................................. Alachlor.............. 15972-60-8 505/507/645/525.1/
525.2/1656/608.3/
625.1.
55................................. Aldicarb.............. 116-06-3 531.1.
58................................. Ametryn............... 834-12-8 507/619/525.2/625.1.
60................................. Atrazine.............. 1912-24-9 505/507/619/525.1/
525.2/1656/ 608.3/
625.1.
62................................. Benomyl............... 17804-35-2 631.
68................................. Bromacil; Bromacil 314-40-9 507/633/525.1/525.2/
Salts and Esters. 1656/608.3/ 625.1.
69................................. Bromoxynil............ 1689-84-5 1625/1661/625.1.
69................................. Bromoxynil octanoate.. 1689-99-2 1656/608.3.
70................................. Butachlor............. 23184-66-9 507/645/525.1/525.2/
1656/608.3/625.1.
73................................. Captafol.............. 2425-06-1 1656/608.3/625.1.
75................................. Carbaryl [Sevin]...... 63-25-2 531.1/632/553/625.1.
76................................. Carbofuran............ 1563-66-2 531.1/632/625.1.
[[Page 8994]]
80................................. Chloroneb............. 2675-77-6 1656/508/608.1/525.1/
525.2/608.3/625.1.
82................................. Chlorothalonil........ 1897-45-6 508/608.2/525.1/525.2/
1656/608.3/625.1.
84................................. Stirofos.............. 961-11-5 1657/507/622/525.1/
525.2/625.1.
86................................. Chlorpyrifos.......... 2921-88-2 1657/508/622/625.1.
90................................. Fenvalerate........... 51630-58-1 1660.
103................................ Diazinon.............. 333-41-5 1657/507/614/622/
525.2/625.1.
107................................ Parathion methyl...... 298-00-0 1657/614/622/625.1.
110................................ DCPA [Dimethyl 2,3,5,6- 1861-32-1 508/608.2/525.1/525.2/
tetrachloro- 515.1 \2\/515.2 \2\/
terephthalate]. 1656/608.3/625.1.
112................................ Dinoseb............... 88-85-7 1658/515.1/615/515.2/
555/625.1.
113................................ Dioxathion............ 78-34-2 1657/614.1.
118................................ Nabonate [Disodium 138-93-2 630.1.
cyanodithio-
imidocarbonate].
119................................ Diuron................ 330-54-1 632/553.
123................................ Endothall............. 145-73-3 548/548.1.
124................................ Endrin................ 72-20-8 1656/505/508/617/
525.1/525.2/608.3/
625.1.
125................................ Ethalfluralin......... 55283-68-6 1656/627/608.3 See
footnote 1.
126................................ Ethion................ 563-12-2 1657/614/614.1/625.1.
127................................ Ethoprop.............. 13194-48-4 1657/507/622/525.1/
525.2/625.1.
132................................ Fenarimol............. 60168-88-9 507/633.1/525.1/525.2/
1656/608.3/625.1.
133................................ Fenthion.............. 55-38-9 1657/622/625.1.
138................................ Glyphosate [N- 1071-83-6 547.
(Phosphonomethyl)
glycine].
140................................ Heptachlor............ 76-44-8 1656/505/508/617/
525.1/525.2/608.3/
625.1.
144................................ Isopropalin........... 33820-53-0 1656/627/608.3.
148................................ Linuron............... 330-55-2 553/632.
150................................ Malathion............. 121-75-5 1657/614/625.1.
154................................ Methamidophos......... 10265-92-6 1657.
156................................ Methomyl.............. 16752-77-5 531.1/632.
158................................ Methoxychlor.......... 72-43-5 1656/505/508/608.2/
617/525.1/525.2/
608.3/625.1.
172................................ Nabam................. 142-59-6 630/630.1.
173................................ Naled................. 300-76-5 1657/622/625.1.
175................................ Norflurazon........... 27314-13-2 507/645/525.1/525.2/
1656/608.3/625.1.
178................................ Benfluralin........... 1861-40-1 1656/627/608.3 See
footnote 1.
182................................ Fensulfothion......... 115-90-2 1657/622/625.1.
183................................ Disulfoton............ 298-04-4 1657/507/614/622/
525.2/625.1.
185................................ Phosmet............... 732-11-6 1657/622.1/625.1.
186................................ Azinphos Methyl....... 86-50-0 1657/614/622/625.1.
192................................ Organo-tin pesticides. 12379-54-3 Ind-01/200.7/200.9.
197................................ Bolstar............... 35400-43-2 1657/622.
203................................ Parathion............. 56-38-2 1657/614/625.1.
204................................ Pendimethalin......... 40487-42-1 1656.
205................................ Pentachloronitrobenzen 82-68-8 1656/608.1/617/608.3/
e. 625.1.
206................................ Pentachlorophenol..... 87-86-5 1625/515.2/555/515.1/
525.1/525.2/625.1.
208................................ Permethrin............ 52645-53-1 608.2/508/525.1/525.2/
1656/1660/608.3 \4\/
625.1 \4\.
212................................ Phorate............... 298-02-2 1657/622/625.1.
218................................ Busan 85 [Potassium 128-03-0 630/630.1.
dimethyldithiocarbama
te].
219................................ Busan 40 [Potassium N- 51026-28-9 630/630.1.
hydroxymethyl-N-
methyldithiocarbamate
].
220................................ KN Methyl [Potassium N- 137-41-7 630/630.1.
methyl-
dithiocarbamate].
223................................ Prometon.............. 1610-18-0 507/619/525.2/625.1.
224................................ Prometryn............. 7287-19-6 507/619/525.1/525.2/
625.1.
226................................ Propazine............. 139-40-2 507/619/525.1/525.2/
1656/608.3/625.1.
230................................ Pyrethrin I........... 121-21-1 1660.
232................................ Pyrethrin II.......... 121-29-9 1660.
236................................ DEF [S,S,S-Tributyl 78-48-8 1657.
phosphorotrithioate].
239................................ Simazine.............. 122-34-9 505/507/619/525.1/
525.2/1656/608.3/
625.1.
241................................ Carbam-S [Sodium 128-04-1 630/630.1.
dimethyldithio-
carbamate].
243................................ Vapam [Sodium 137-42-8 630/630.1.
methyldithiocarbamate
].
252................................ Tebuthiuron........... 34014-18-1 507/525.1/525.2/
625.1.
254................................ Terbacil.............. 5902-51-2 507/633/525.1/525.2/
1656/608.3/625.1.
255................................ Terbufos.............. 13071-79-9 1657/507/614.1/525.1/
525.2/625.1.
256................................ Terbuthylazine........ 5915-41-3 619/1656/608.3.
257................................ Terbutryn............. 886-50-0 507/619/525.1/525.2/
625.1.
259................................ Dazomet............... 533-74-4 630/630.1/1659.
262................................ Toxaphene............. 8001-35-2 1656/505/508/617/
525.1/525.2/608.3/
625.1.
263................................ Merphos [Tributyl 150-50-5 1657/507/525.1/525.2/
phosphorotrithioate]. 622/625.1.
264................................ Trifluralin \1\....... 1582-09-8 1656/508/617/627/
525.2/608.3/625.1.
[[Page 8995]]
268................................ Ziram [Zinc 137-30-4 630/630.1.
dimethyldithiocarbama
te].
----------------------------------------------------------------------------------------------------------------
Table 1G notes:
\1\ Monitor and report as total Trifluralin.
\2\ Applicable to the analysis of DCPA degradates.
\3\ EPA Methods 608.1 through 645, 1645 through 1661, and Ind-01 are available in Methods for the Determination
of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume I, EPA 821-R-93-010A, Revision I,
August 1993, U.S. EPA. EPA Methods 200.9 and 505 through 555 are available in Methods for the Determination of
Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume II, EPA 821-R-93-010B, August 1993,
U.S. EPA. The full text of Methods 608.3, 625.1, and 1625 are provided at Appendix A of this part 136. The
full text of Method 200.7 is provided at Appendix C of this part 136. Methods 608.3 and 625.1 are available
at: http://water.epa.gov/scitech/methods/cwa/methods_index.cfm (this is a placeholder for now).
\4\ Permethrin is not listed within methods 608.3 and 625.1; however, cis-permethrin and trans-permethrin are
listed. Permethrin can be calculated by adding the results of cis and trans-permethrin.
Table 1H--List of Approved Microbiological Methods for Ambient Water
----------------------------------------------------------------------------------------------------------------
AOAC,
Parameter and units Method \1\ EPA Standard ASTM, Other
methods USGS
----------------------------------------------------------------------------------------------------------------
Bacteria:
----------------------------------------------------------------------------------------------------------------
1. Coliform (fecal), number per Most Probable p. 132 \3\........ 9221 C E-
100 mL or number per gram dry Number (MPN), 5 2006
weight. tube, 3 dilution,
or.
Membrane filter p. 124 \3\........ 9222 D- B-0050-8
(MF),\2\ single 2006 \27\ 5 \4\
step.
2. Coliform (fecal) in presence MPN, 5 tube, 3 p. 132 \3\........ 9221 C E-
of chlorine, number per 100 mL. dilution, or. 2006
MF \2\, single p. 124 \3\........ 9222 D-
step \5\. 2006 \27\
3. Coliform (total), number per MPN, 5 tube, 3 p. 114 \3\........ 9221 B-
100 mL. dilution, or. 2006
MF \2\, single p. 108 \3\........ 9222 B- B-0025-8
step or two step. 2006 5 \4\
4. Coliform (total), in MPN, 5 tube, 3 p. 114 \3\........ 9221 B-
presence of chlorine, number dilution, or. 2006
per 100 mL.
MF \2\ with p. 111 \3\........ 9222 B-
enrichment. 2006
5.E. coli, number per 100 mL... MPN,6 8 14 .................. 9221 B.2-
multiple tube, or. 2006/9221
F-2006 11
13
Multiple tube/ .................. 9223 B- 991.15 Colilert[supreg]
multiple well, or. 2004 \12\ \10\ 12 16, Colilert-
[supreg] 12 15
16
MF 2 5 6 7 8, two 1103.1 \19\....... 9222 B- D5392-93
step, or. 2006/9222 \9\
G-2006,\1
8\ 9213 D-
2007
Single step....... 1603 \20\, 1604 .......... ........ mColiBlue-24[supr
\21\. eg] \17\
6. Fecal streptococci, number MPN, 5 tube, 3 p. 139 \3\........ 9230 B-
per 100 mL. dilution, or. 2007
MF \2\, or........ p. 136 \3\........ 9230 C- B-0055-8
2007 5 \4\
Plate count....... p. 143 \3\........
7. Enterococci, number per 100 MPN,6 8 multiple .................. 9230 D- D6503-99 Ente-
mL. tube/multiple 2007 \9\ rolert[supreg]
well, or. 12 22
MF 2 5 6 7 8 two 1106.1 \23\....... 9230 C- D5259-92
step, or. 2007 \9\
Single step, or... 1600 \24\......... 9230 C-
2007
Plate count....... p. 143 \3\........
Protozoa:......................
8.Cryptosporidium.............. Filtration/IMS/FA. 1622 \25\, 1623
\26\.
9.Giardia...................... Filtration/IMS/FA. 1623 \26\.........
----------------------------------------------------------------------------------------------------------------
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\ 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.
[[Page 8996]]
\7\ 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.
\8\ To assess the comparability of results obtained with individual methods, it is suggested that side-by-side
tests be conducted across seasons of the year with the water samples routinely tested in accordance with the
most current Standard Methods for the Examination of Water and Wastewater or EPA alternate test procedure
(ATP) guidelines.
\9\ Annual Book of ASTM Standards--Water and Environmental Technology. Section 11.02. 2000, 1999, 1996. ASTM
International.
\10\ Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. 1995. AOAC
International.
\11\ The multiple-tube fermentation test is used in 9221B.2-2006. 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.
\12\ These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is
used to detect the enzyme [beta]-glucuronidase produced by E. coli.
\13\ After prior enrichment in a presumptive medium for total coliform using 9221B.2-2006, 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-2006. Commercially available EC-MUG media or EC media supplemented in the laboratory with
50 [micro]g/mL of MUG may be used.
\14\ 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.
\15\ 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.
\16\ Descriptions of the Colilert[supreg], Colilert-18[supreg], Quanti-Tray[supreg], and Quanti-Tray[supreg]/
2000 may be obtained from IDEXX Laboratories Inc.
\17\ A description of the mColiBlue24[supreg] test may be obtained from Hach Company.
\18\ Subject total coliform positive samples determined by 9222B-1997 or other membrane filter procedure to
9222G-1997 using NA-MUG media.
\19\ Method 1103.1: Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane-Thermotolerant
Escherichia coli Agar (mTEC), EPA-821-R-10-002. March 2010. US EPA.
\20\ Method 1603: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-
Thermotolerant Escherichia coli Agar (Modified mTEC), EPA-821-R-14-010. September 2014. US EPA.
\21\ Preparation and use of MI agar with a standard membrane filter procedure is set forth in the article,
Brenner et al. 1993. New Medium for the Simultaneous Detection of Total Coliform and Escherichia coli in
Water. Appl. Environ. Microbiol. 59:3534-3544 and in 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.
\22\ A description of the Enterolert[supreg] test may be obtained from IDEXX Laboratories Inc.
\23\ Method 1106.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar
(mE-EIA), EPA-821-R-09-015. December 2009. US EPA.
\24\ Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-[beta]-D-
Glucoside Agar (mEI), EPA-821-R-14-011. September 2014. US EPA.
\25\ 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.
\26\ Method 1623 uses 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.
\27\ The verification frequency is at least five typical and five atypical colonies per sampling site on the day
of sample collection and analysis.
(b) The documents required in this section are incorporated by
reference into this section in accordance with 5 U.S.C. 552(a) and 1
CFR part 51. Copies of the documents may be obtained from the sources
listed in paragraph (b) of this section. Documents may be inspected at
EPA's Water Docket, EPA West, 1301 Constitution Avenue NW., Room 3334,
Washington, DC 20004, (Telephone: 202-566-2426); or at the National
Archives and Records Administration (NARA). For information on the
availability of this material at NARA, call 202-741-6030, or go to:
http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html. These test procedures are incorporated as they
exist on the day of approval and a notice of any change in these test
procedures will be published in the Federal Register. The full texts of
the methods from the following references which are cited in Tables IA,
IB, IC, ID, IE, IF, IG and IH of this section are incorporated by
reference into this regulation and may be obtained from the source
identified.
* * * * *
(8) * * *
* * * * *
(iv) Method 1600: Enterococci in Water by Membrane Filtration Using
membrane-Enterococcus Indoxyl-[beta]-D-Glucoside Agar (mEI). September
2014. EPA-821-R-14-011. Table IA, Note 25; Table IH, Note 24.
(v) Method 1603: Escherichia coli (E. coli) in Water by Membrane
Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar
(Modified mTEC). September 2014. EPA-821-R-14-010. Table IA, Note 22;
Table IH, Note 20.
* * * * *
(xiii) 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 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) * * *
* * * * *
(viii) 2120, Color. 2011. Table IB.
* * * * *
(x) 2310, Acidity. 2011. Table IB.
(xi) 2320, Alkalinity. 2011. Table IB.
(xii) 2340, Hardness. 2011. Table IB.
(xiii) 2510, Conductivity. 2011. Table IB.
(xiv) 2540, Solids. 2011. Table IB.
(xv) 2550, Temperature. 2011. Table IB.
(xvi) 3111, Metals by Flame Atomic Absorption Spectrometry. 2011.
Table IB.
(xvii) 3112, Metals by Cold-Vapor Atomic Absorption Spectrometry.
2011. Table IB.
(xviii) 3113, Metals by Electrothermal Atomic Absorption
Spectrometry. 2010. Table IB.
(xix) 3114, Arsenic and Selenium by Hydride Generation/Atomic
Absorption Spectrometry. 2011. Table IB.
[[Page 8997]]
(xx) 3120, Metals by Plasma Emission Spectroscopy. 2011. Table IB.
(xxi) 3125, Metals by Inductively Coupled Plasma-Mass Spectrometry.
2011. Table IB.
(xxii) 3500-Al, Aluminum. 2011. Table IB.
(xxiii) 3500-As, Arsenic. 2011. Table IB.
(xxiv) 3500-Ca, Calcium. 2011. Table IB.
(xxv) 3500-Cr, Chromium. 2011. Table IB.
(xxvi) 3500-Cu, Copper. 2011. Table IB.
(xxvii) 3500-Fe, Iron. 2011. Table IB.
(xxviii) 3500-Pb, Lead. 2011. Table IB.
(xxix) 3500-Mn, Manganese. 2011. Table IB.
(xxx) 3500-K, Potassium. 2011. Table IB.
(xxxi) 3500-Na, Sodium. 2011. Table IB.
(xxxii) 3500-V, Vanadium. 2011. Table IB.
(xxxiii) 3500-Zn, Zinc. 2011. Table IB.
(xxxiv) 4110, Determination of Anions by Ion Chromatography. 2011.
Table IB.
(xxxv) 4140, Inorganic Anions by Capillary Ion Electrophoresis.
2011. Table IB.
(xxxvi) 4500-B, Boron. 2011. Table IB.
(xxxvii) 4500-Cl-, Chloride. 2011. Table IB.
(xxxviii) 4500-Cl, Chlorine (Residual). 2011. Table IB.
(xxxix) 4500-CN -, Cyanide. 2011. Table IB.
(xl) 4500-F-, Fluoride. 2011. Table IB.
(xli) 4500-H\+\, pH Value. 2011. Table IB.
(xlii) 4500-NH3, Nitrogen (Ammonia). 2011. Table IB.
(xliii) 4500-NO2-, Nitrogen (Nitrite). 2011.
Table IB.
(xliv) 4500-NO3-, Nitrogen (Nitrate). 2011.
Table IB.
(xlv) 4500-Norg, Nitrogen (Organic). 2011. Table IB.
(xlvi) 4500-O, Oxygen (Dissolved). 2011. Table IB.
(xlvii) 4500-P, Phosphorus. 2011. Table IB.
(xlviii) 4500-SiO2, Silica. 2011. Table IB.
(xlix) 4500-S\2\-, Sulfide. 2011. Table IB.
(l) 4500-SO3\2\-, Sulfite. 2011. Table IB.
(li) 4500-SO4\2\-, Sulfate. 2011. Table IB.
(lii) 5210, Biochemical Oxygen Demand (BOD). 2011. Table IB.
(liii) 5220, Chemical Oxygen Demand (COD). 2011. Table IB.
(liv) 5310, Total Organic Carbon (TOC). 2011. Table IB.
(lv) 5520, Oil and Grease. 2011. Table IB.
(lvi) 5530, Phenols. 2010. Table IB.
(lvii) 5540, Surfactants. 2011. Table IB.
(lviii) 6200, Volatile Organic Compounds. 2011. Table IC.
* * * * *
(lxi) 6440, Polynuclear Aromatic Hydrocarbons. 2005. Table IC.
(lxii) 6630, Organochlorine Pesticides. 2007. Table ID.
(lxiii) 6640, Acidic Herbicide Compounds. 2006. Table ID.
* * * * *
(lxviii) 9222, Membrane Filter Technique for Members of the
Coliform Group. 2006. Table IA; Table IH, Note 18.
* * * * *
(15) * * *
* * * * *
(v) ASTM D511-09, Standard Test Methods for Calcium and Magnesium
in Water. May 2009. Table IB.
* * * * *
(viii) ASTM D516-11, Standard Test Method for Sulfate Ion in Water,
September 2011. Table IB.
(ix) ASTM D858-12, Standard Test Methods for Manganese in Water.
September 2012. Table IB.
(x) ASTM D859-10, Standard Test Method for Silica in Water. July
2010. Table IB.
* * * * *
(xii) ASTM D1067-11, Standard Test Methods for Acidity or
Alkalinity of Water. April 2011. Table IB.
(xiii) ASTM D1068-10, Standard Test Methods for Iron in Water.
October 2010. Table IB.
* * * * *
(xv) ASTM D1126-12, Standard Test Method for Hardness in Water.
March 2012. Table IB.
(xvi) ASTM D1179-10, Standard Test Methods for Fluoride Ion in
Water. July 2010. Table IB.
(xvii) ASTM D1246-10, Standard Test Method for Bromide Ion in
Water. July 2010. Table IB.
* * * * *
(xxii) ASTM D1687-12 (Approved September 1, 2012), Standard Test
Methods for Chromium in Water. August 2007. Table IB.
(xxiii) ASTM D1688-12, Standard Test Methods for Copper in Water.
September 2012. Table IB.
(xxiv) ASTM D1691-12, Standard Test Methods for Zinc in Water.
September 2012. Table IB.
* * * * *
(xxx) ASTM D1976-12, Standard Test Method for Elements in Water by
Inductively-Coupled Argon Plasma Atomic Emission Spectroscopy. March
2012. Table IB.
* * * * *
(xxxv) ASTM D3223-12, Standard Test Method for Total Mercury in
Water. September 2012. Table IB.
* * * * *
(xxxvii) ASTM D3373-12, Standard Test Method for Vanadium in Water.
September 2012. Table IB.
* * * * *
(xxxix) ASTM D3557-12, Standard Test Method for Cadmium in Water.
September 2012. Table IB.
* * * * *
(xlii) ASTM D3590-11, Standard Test Methods for Total Kjeldahl
Nitrogen in Water. April 2011. Table IB.
* * * * *
(l) ASTM D4382-12, Standard Test Method for Barium in Water, Atomic
Absorption Spectrophotometry, Graphite Furnace. September 2012. Table
IB.
* * * * *
(lii) ASTM D4658-09, Standard Test Method for Sulfide Ion in Water.
May 2009. Table IB.
* * * * *
(lv) ASTM D5257-11, Standard Test Method for Dissolved Hexavalent
Chromium in Water by Ion Chromatography. April 2011. Table IB.
* * * * *
(lviii) ASTM D5673-10, Standard Test Method for Elements in Water
by Inductively Coupled Plasma--Mass Spectrometry. September 2010. Table
IB.
(lix) ASTM D5907-13, Standard Test Method for Filterable and
Nonfilterable Matter in Water. July 2013. Table IB.
* * * * *
(lxi) ASTM. D6508-10, Standard Test Method for Determination of
Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion
Electrophoresis and Chromate Electrolyte. October 2010. Table IB, Note
54.
* * * * *
(lxvi) ASTM. D7284-13, Standard Test Method for Total Cyanide in
Water by Micro Distillation followed by Flow Injection Analysis with
Gas Diffusion Separation and Amperometric Detection. July 2013. Table
IB.
* * * * *
(lxviii) ASTM. D7511-12, Standard Test Method for Total Cyanide by
Segmented Flow Injection Analysis, In-Line Ultraviolet Digestion and
Amperometric Detection. January 2012. Table IB.
* * * * *
(19) * * *
* * * * *
(vii) Method 10206, TNTplus 835-836 Nitrate Method,
Spectrophotometric Measurement of Nitrate in Water and
[[Page 8998]]
Wastewater. Revision 2.1, January 10, 2013. Table IB, Note 75.
(viii) Method 10242, TNTplus 880 Total Kjeldahl Nitrogen Method,
Simplified Spectrophotometric Measurement of Total Kjeldahl Nitrogen in
Water and Wastewater. Revision 1.1, January 10, 2013. Table IB, Note
75.
* * * * *
(20) * * *
(i) Colilert[supreg]. 2013. Table IA, Notes 17 and 18; Table IH,
Notes 14, 15 and 16.
(ii) Colilert-18[supreg]. 2013. Table IA, Notes 17 and 18; Table
IH, Notes 14, 15 and 16.
(iii) Enterolert[supreg]. 2013. Table IA, Note 24; Table IH, Note
12.
(iv) Quanti-Tray[supreg]. 2013. Table IA, Note 18; Table IH, Notes
14 and 16.
* * * * *
(25) National Council of the Paper Industry for Air and Stream
Improvements, Inc. (NCASI), 260 Madison Avenue, New York NY 10016.
(i) NCASI Methods TNTP-W10900 as an Alternative Testing Procedure
to EPA Method 351.2 and EPA Method 365.4. June 2011. Table IB, Note 77.
(ii) NCASI Technical Bulletin No. 253, An Investigation of Improved
Procedures for Measurement of Mill Effluent and Receiving Water Color.
December 1971. Table IB, Note 18.
(iii) NCASI Technical Bulletin No. 803, An Update of Procedures for
the Measurement of Color in Pulp Mill Wastewaters. May 2000. Table IB,
Note 18.
(26) The Nitrate Elimination Co., Inc. (NECi), 334 Hecla St., Lake
Linden NI 49945.
(i) NECi Method N07-0003, Method for Nitrate Reductase Nitrate-
Nitrogen Analysis. Revision 9.0. March 2014. Table IB, Note 73.
(ii) [Reserved]
* * * * *
(34) Timberline Instruments, LLC, 1880 South Flatiron Ct., Unit I,
Boulder CO 80301.
(i) Determination of Inorganic Ammonia by Continuous Flow Gas
Diffusion and Conductivity Cell Analysis. June 24, 2011. Table IB, Note
74.
(ii) [Reserved]
(35) 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.
(i) Colorimetric determination of nitrate plus nitrite in water by
enzymatic reduction, automated discrete analyzer methods. U.S.
Geological Survey Techniques and Methods, Book 5, Chapter B8. 2011.
Table IB, Note 72.
(ii) Methods for Determination of Inorganic Substances in Water and
Fluvial Sediments, editors, Techniques of Water-Resources
Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1979.
Table IB, Note 8.
(iii) 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. 1989. Table IB, Note 2.
(iv) 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. Table IB, Note
24; Table ID, Note 4.
(v) OFR 76-177, Selected Methods of the U.S. Geological Survey of
Analysis of Wastewaters. 1976. Table IE, Note 2.
(vi) OFR 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.
Table ID, Note 14.
(vii) OFR 92-146, Methods of Analysis by the U.S. Geological Survey
National Water Quality Laboratory--Determination of Total Phosphorus by
a Kjeldahl Digestion Method and an Automated Colorimetric Finish That
Includes Dialysis. 1992. Table IB, Note 48.
(viii) 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, Note 51; Table IC, Note 9.
(ix) OFR 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. Table
IB, Note 46.
(x) OFR 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. Table ID, Note 9.
(xi) OFR 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. Table ID, Note
11.
(xii) OFR 97-198, Methods of Analysis by the U.S. Geological Survey
National Water Quality Laboratory--Determination of Molybdenum in Water
by Graphite Furnace Atomic Absorption Spectrophotometry. 1997. Table
IB, Note 47.
(xiii) OFR 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.
Table IB, Note 50.
(xiv) OFR 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. Table IB, Note 49.
(xv) OFR 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.
Table IB, Note 45.
(xvi) 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. Table IB, Note 70.
(xvii) U.S. Geological Survey Techniques of Water-Resources
Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for
Collection and Analysis of Aquatic Biological and Microbiological
Samples. 1989. Table IA, Note 4; Table IH, Note 4.
(xviii) Water-Resources Investigation Report 01-4098, Methods of
Analysis by the U.S. Geological Survey National Water Quality
Laboratory--Determination of Moderate-Use Pesticides and Selected
Degradates in Water by C-18 Solid-Phase Extraction and Gas
Chromatography/Mass Spectrometry. 2001. Table ID, Note 13.
(xix) 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. Table IB, Note 71.
(xx) Water-Resources Investigation Report 01-4134, Methods of
Analysis by
[[Page 8999]]
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. Table ID, Note 12.
(xxi) 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. Table IB, Note 32.
* * * * *
(c) Under certain circumstances, the Director may establish
limitations on the discharge of a parameter for which there is no test
procedure in this part or in 40 CFR parts 405 through 499. In these
instances the test procedure shall be specified by the Director.
* * * * *
(e) * * *
Table II--Required Containers, Preservation Techniques, and Holding Times
----------------------------------------------------------------------------------------------------------------
Maximum holding time
Parameter number/name Container \1\ Preservation 2 3 \4\
----------------------------------------------------------------------------------------------------------------
Table IA--Bacterial Tests:
----------------------------------------------------------------------------------------------------------------
1-5. Coliform, total, fecal, and E. PA, G.................. Cool, <10 [deg]C, 8 hours 22 23.
coli. 0.008% Na2S2O3\5\.
6. Fecal streptococci................ PA, G.................. Cool, <10 [deg]C, 8 hours \22\.
0.008% Na2S2O3\5\.
7. Enterococci....................... PA, G.................. Cool, <10 [deg]C, 8 hours \22\.
0.008% Na2S2O3\5\.
8. Salmonella........................ PA, G.................. Cool, <10 [deg]C, 8 hours \22\.
0.008% Na2S2O3\5\.
----------------------------------------------------------------------------------------------------------------
Table IA--Aquatic Toxicity Tests:
----------------------------------------------------------------------------------------------------------------
9-12. Toxicity, acute and chronic.... P, FP, G............... Cool, <=6 [deg]C \16\.. 36 hours.
----------------------------------------------------------------------------------------------------------------
Table IB--Inorganic Tests:
----------------------------------------------------------------------------------------------------------------
1. Acidity........................... P, FP, G............... Cool, <=6 [deg]C \18\.. 14 days.
2. Alkalinity........................ P, FP, G............... Cool, <=6 [deg]C \18\.. 14 days.
4. Ammonia........................... P, FP, G............... Cool, <=6 [deg]C \18\, 28 days.
H2SO4 to pH <2.
9. Biochemical oxygen demand......... P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
10. Boron............................ P, FP, or Quartz....... HNO3 to pH <2.......... 6 months.
11. Bromide.......................... P, FP, G............... None required.......... 28 days.
14. Biochemical oxygen demand, P, FP G................ Cool, <=6 [deg]C \18\.. 48 hours.
carbonaceous.
15. Chemical oxygen demand........... P, FP, G............... Cool, <=6 [deg]C \18\, 28 days.
H2SO4 to pH <2.
16. Chloride......................... P, FP, G............... None required.......... 28 days.
17. Chlorine, total residual......... P, G................... None required.......... Analyze within 15
minutes.
21. Color............................ P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
23-24. Cyanide, total or available P, FP, G............... Cool, <=6 [deg]C \18\, 14 days.
(or CATC) and free. NaOH to pH >10 [shel5]
[shel6], reducing
agent if oxidizer
present.
25. Fluoride......................... P...................... None required.......... 28 days.
27. Hardness......................... P, FP, G............... HNO3 or H2SO4 to pH <2. 6 months.
28. Hydrogen ion (pH)................ P, FP, G............... None required.......... Analyze within 15
minutes.
31, 43. Kjeldahl and organic N....... P, FP, G............... Cool, <=6 [deg]C \18\, 28 days.
H2SO4 to pH <2.
----------------------------------------------------------------------------------------------------------------
Table IB--Metals: \7\
----------------------------------------------------------------------------------------------------------------
18. Chromium VI...................... P, FP, G............... Cool, <=6 [deg]C \18\, 28 days.
pH = 9.3-9.7 \20\.
35. Mercury (CVAA)................... P, FP, G............... HNO3 to pH <2.......... 28 days.
35. Mercury (CVAFS).................. FP, G; and FP-lined cap 5 mL/L 12N HCl or 5 mL/ 90 days \17\.
\17\. L BrCl \17\.
3, 5-8, 12, 13, 19, 20, 22, 26, 29, P, FP, G............... HNO3 to pH <2, or at 6 months.
30, 32-34, 36, 37, 45, 47, 51, 52, least 24 hours prior
58-60, 62, 63, 70-72, 74, 75. to analysis \19\.
Metals, except boron, chromium VI,
and mercury.
38. Nitrate.......................... P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
39. Nitrate-nitrite.................. P, FP, G............... Cool, <=6 [deg]C \18\, 28 days.
H2SO4 to pH <2.
40. Nitrite.......................... P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
41. Oil and grease................... G...................... Cool to <=6 [deg]C 28 days.
\18\, HCl or H2SO4 to
pH <2.
42. Organic Carbon................... P, FP, G............... Cool to <=6 [deg]C 28 days.
\18\, HCl, H2SO4, or
H3PO4 to pH <2.
44. Orthophosphate................... P, FP, G............... Cool, to <=6 [deg]C Filter within 15
\18\ \24\. minutes; Analyze
within 48 hours.
[[Page 9000]]
46. Oxygen, Dissolved Probe.......... G, Bottle and top...... None required.......... Analyze within 15
minutes.
47. Winkler.......................... G, Bottle and top...... Fix on site and store 8 hours.
in dark.
48. Phenols.......................... G...................... Cool, <=6 [deg]C \18\, 28 days.
H2SO4 to pH <2.
49. Phosphorous (elemental).......... G...................... Cool, <=6 [deg]C \18\.. 48 hours.
50. Phosphorous, total............... P, FP, G............... Cool, <=6 [deg]C \18\, 28 days.
H2SO4 to pH <2.
53. Residue, total................... P, FP, G............... Cool, <=6 [deg]C \18\.. 7 days.
54. Residue, Filterable.............. P, FP, G............... Cool, <=6 [deg]C \18\.. 7 days.
55. Residue, Nonfilterable (TSS)..... P, FP, G............... Cool, <=6 [deg]C \18\.. 7 days.
56. Residue, Settleable.............. P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
57. Residue, Volatile................ P, FP, G............... Cool, <=6 [deg]C \18\.. 7 days.
61. Silica........................... P or Quartz............ Cool, <=6 [deg]C \18\.. 28 days.
64. Specific conductance............. P, FP, G............... Cool, <=6 [deg]C \18\.. 28 days.
65. Sulfate.......................... P, FP, G............... Cool, <=6 [deg]C \18\.. 28 days.
66. Sulfide.......................... P, FP, G............... Cool, <=6 [deg]C \18\, 7 days.
add zinc acetate plus
sodium hydroxide to pH
>9.
67. Sulfite.......................... P, FP, G............... None required.......... Analyze within 15
minutes.
68. Surfactants...................... P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
69. Temperature...................... P, FP, G............... None required.......... Analyze.
73. Turbidity........................ P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
----------------------------------------------------------------------------------------------------------------
Table IC--Organic Tests: \8\
----------------------------------------------------------------------------------------------------------------
13, 18-20, 22, 24-28, 34-37, 39-43, G, FP-lined septum..... Cool, <=6 [deg]C \18\, 14 days.
45-47, 56, 76, 104, 105, 108-111, 0.008% Na2S2O3\5\.
113. Purgeable Halocarbons.
6, 57, 106. Purgeable aromatic G, FP-lined septum..... Cool, <=6 [deg]C \18\, 14 days \9\.
hydrocarbons. 0.008% Na2S2O3\5\, HCl
to pH 2 \9\.
3, 4. Acrolein and acrylonitrile..... G, FP-lined septum..... Cool, <=6 [deg]C \18\, 14 days \10\.
0.008% Na2S2O3, pH to
4-5 \10\.
23, 30, 44, 49, 53, 77, 80, 81, 98, G, FP-lined cap........ Cool, <=6 [deg]C \18\, 7 days until
100, 112. Phenols \11\. 0.008% Na2S2O3. extraction, 40 days
after extraction.
7, 38. Benzidines \11\ \12\.......... G, FP-lined cap........ Cool, <=6 [deg]C \18\, 7 days until extraction
0.008% Na2S2O3\5\. \13\.
14, 17, 48, 50-52. Phthalate esters G, FP-lined cap........ Cool, <=6 [deg]C \18\.. 7 days until
\11\. extraction, 40 days
after extraction.
82-84. Nitrosamines \11\ \14\........ G, FP-lined cap........ Cool, <=6 [deg]C \18\, 7 days until
store in dark, 0.008% extraction, 40 days
Na2S2O3\5\. after extraction.
88-94. PCBs \11\..................... G, FP-lined cap........ Cool, <=6 [deg]C \18\.. 1 year until
extraction, 1 year
after extraction.
54, 55, 75, 79. Nitroaromatics and G, FP-lined cap........ Cool, <=6 [deg]C \18\, 7 days until
isophorone \11\. store in dark, 0.008% extraction, 40 days
Na2S2O3 \5\. after extraction.
1, 2, 5, 8-12, 32, 33, 58, 59, 74, G, FP-lined cap........ Cool, <=6 [deg]C \18\, 7 days until
78, 99, 101. Polynuclear aromatic store in dark, 0.008% extraction, 40 days
hydrocarbons \11\. Na2S2O3\5\. after extraction.
15, 16, 21, 31, 87. Haloethers \11\.. G, FP-lined cap........ Cool, <=6 [deg]C \18\, 7 days until
0.008% Na2S2O3\5\. extraction, 40 days
after extraction.
29, 35-37, 63-65, 107. Chlorinated G, FP-lined cap........ Cool, <=6 [deg]C \18\.. 7 days until
hydrocarbons \11\. extraction, 40 days
after extraction.
60-62, 66-72, 85, 86, 95-97, 102, G...................... See footnote 11........ See footnote 11.
103. CDDs/CDFs \11\.
Aqueous Samples: Field and Lab G...................... Cool, <=6 [deg]C \18\, 1 year.
Preservation. 0.008% Na2S2O3\5\, pH
<9.
Solids and Mixed-Phase Samples: G...................... Cool, <=6 [deg]C \18\.. 7 days.
Field Preservation.
Tissue Samples: Field G...................... Cool, <=6 [deg]C \18\.. 24 hours.
Preservation.
Solids, Mixed-Phase, and Tissue G...................... Freeze, <= -10 [deg]C.. 1 year.
Samples: Lab Preservation.
114-118. Alkylated phenols........... G...................... Cool, <6 [deg]C, H2SO4 28 days until
to pH <2. extraction, 40 days
after extraction.
119. Adsorbable Organic Halides (AOX) G...................... Cool, <6 [deg]C, 0.008% Hold at least 3 days,
Na2S2O3, HNO3 to pH <2. but not more than 6
months.
120. Chlorinated Phenolics........... G, FP-lined cap........ Cool, <6 [deg]C, 0.008% 30 days until
Na2S2O3, H2SO4 to pH acetylation, 30 days
<2. after acetylation.
----------------------------------------------------------------------------------------------------------------
Table ID--Pesticides Tests:
----------------------------------------------------------------------------------------------------------------
1-70. Pesticides \11\................ G, FP-lined cap........ Cool, <=6 [deg]C \18\, 7 days until
pH 5-9 \15\. extraction, 40 days
after extraction.
----------------------------------------------------------------------------------------------------------------
[[Page 9001]]
Table IE--Radiological Tests:
----------------------------------------------------------------------------------------------------------------
1-5. Alpha, beta, and radium......... P, FP, G............... HNO3 to pH <2.......... 6 months.
----------------------------------------------------------------------------------------------------------------
Table IH--Bacterial Tests:
----------------------------------------------------------------------------------------------------------------
1-4. Coliform, total, fecal.......... PA, G.................. Cool, <10 [deg]C, 8 hours \22\ \23\.
0.008% Na2S2O3\5\.
5. E. coli........................... PA, G.................. Cool, <10 [deg]C, 8 hours \22\.
0.008% Na2S2O3\5\.
6. Fecal streptococci................ PA, G.................. Cool, <10 [deg]C, 8 hours \22\.
0.008% Na2S2O3\5\.
7. Enterococci....................... PA, G.................. Cool, <10 [deg]C, 8 hours \22\.
0.008% Na2S2O3\5\.
----------------------------------------------------------------------------------------------------------------
Table IH--Protozoan Tests:
----------------------------------------------------------------------------------------------------------------
8. Cryptosporidium................... LDPE; field filtration. 1-10 [deg]C............ 96 hours \21\.
9. Giardia........................... LDPE; field filtration. 1-10 [deg]C............ 96 hours \21\.
----------------------------------------------------------------------------------------------------------------
\1\ ``P'' is for polyethylene; ``FP'' is fluoropolymer (polytetrafluoroethylene (PTFE); Teflon[supreg]), or
other fluoropolymer, unless stated otherwise in this Table II; ``G'' is glass; ``PA'' is any plastic that is
made of a sterilizable material (polypropylene or other autoclavable plastic); ``LDPE'' is low density
polyethylene.
\2\ Except where noted in this Table II and the method for the parameter, preserve each grab sample within 15
minutes of collection. For a composite sample collected with an automated sample (e.g., using a 24-hour
composite sample; see 40 CFR 122.21(g)(7)(i) or 40 CFR part 403, appendix E), refrigerate the sample at <= 6
[deg]C during collection unless specified otherwise in this Table II or in the method(s). For a composite
sample to be split into separate aliquots for preservation and/or analysis, maintain the sample at <= 6
[deg]C, unless specified otherwise in this Table II or in the method(s), until collection, splitting, and
preservation is completed. Add the preservative to the sample container prior to sample collection when the
preservative will not compromise the integrity of a grab sample, a composite sample, or aliquot split from a
composite sample within 15 minutes of collection. If a composite measurement is required but a composite
sample would compromise sample integrity, individual grab samples must be collected at prescribed time
intervals (e.g., 4 samples over the course of a day, at 6-hour intervals). Grab samples must be analyzed
separately and the concentrations averaged. Alternatively, grab samples may be collected in the field and
composited in the laboratory if the compositing procedure produces results equivalent to results produced by
arithmetic averaging of results of analysis of individual grab samples. For examples of laboratory compositing
procedures, see EPA Method 1664 Rev. A (oil and grease) and the procedures at 40 CFR 141.24(f)(14)(iv) and (v)
(volatile organics).
\3\ When any sample is to be shipped by common carrier or sent via the U.S. Postal Service, it must comply with
the Department of Transportation Hazardous Materials Regulations (49 CFR part 172). The person offering such
material for transportation is responsible for ensuring such compliance. For the preservation requirement of
Table II, the Office of Hazardous Materials, Materials Transportation Bureau, Department of Transportation has
determined that the Hazardous Materials Regulations do not apply to the following materials: Hydrochloric acid
(HCl) in water solutions at concentrations of 0.04% by weight or less (pH about 1.96 or greater; Nitric acid
(HNO3) in water solutions at concentrations of 0.15% by weight or less (pH about 1.62 or greater); Sulfuric
acid (H2SO4) in water solutions at concentrations of 0.35% by weight or less (pH about 1.15 or greater); and
Sodium hydroxide (NaOH) in water solutions at concentrations of 0.080% by weight or less (pH about 12.30 or
less).
\4\ Samples should be analyzed as soon as possible after collection. The times listed are the maximum times that
samples may be held before the start of analysis and still be considered valid. Samples may be held for longer
periods only if the permittee or monitoring laboratory have data on file to show that, for the specific types
of samples under study, the analytes are stable for the longer time, and has received a variance from the
Regional ATP Coordinator under Sec. 136.3(e). For a grab sample, the holding time begins at the time of
collection. For a composite sample collected with an automated sampler (e.g., using a 24-hour composite
sampler; see 40 CFR 122.21(g)(7)(i) or 40 CFR part 403, appendix E), the holding time begins at the time of
the end of collection of the composite sample. For a set of grab samples composited in the field or
laboratory, the holding time begins at the time of collection of the last grab sample in the set. Some samples
may not be stable for the maximum time period given in the table. A permittee or monitoring laboratory is
obligated to hold the sample for a shorter time if it knows that a shorter time is necessary to maintain
sample stability. See Sec. 136.3(e) for details. The date and time of collection of an individual grab
sample is the date and time at which the sample is collected. For a set of grab samples to be composited, and
that are all collected on the same calendar date, the date of collection is the date on which the samples are
collected. For a set of grab samples to be composited, and that are collected across two calendar dates, the
date of collection is the dates of the two days; e.g., November 14-15. For a composite sample collected
automatically on a given date, the date of collection is the date on which the sample is collected. For a
composite sample collected automatically, and that is collected across two calendar dates, the date of
collection is the dates of the two days; e.g., November 14-15. For static-renewal toxicity tests, each grab or
composite sample may also be used to prepare test solutions for renewal at 24 h, 48 h, and/or 72 h after first
use, if stored at 0-6 [deg]C, with minimum head space.
\5\ ASTM D7365-09a 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 (20th and 21st
editions) addresses dechlorination procedures for microbiological analyses.
\6\ Sampling, preservation and mitigating interferences in water samples for analysis of cyanide are described
in ASTM D7365-09a. There may be interferences that are not mitigated by the analytical test methods or D7365-
09a. Any technique for removal or suppression of interference may be employed, provided the laboratory
demonstrates that it more accurately measures cyanide through quality control measures described in the
analytical test method. Any removal or suppression technique not described in D7365-09a or the analytical test
method must be documented along with supporting data.
\7\ For dissolved metals, filter grab samples within 15 minutes of collection and before adding preservatives.
For a composite sample collected with an automated sampler (e.g., using a 24-hour composite sampler; see 40
CFR 122.21(g)(7)(i) or 40 CFR part 403, appendix E), filter the sample within 15 minutes after completion of
collection and before adding preservatives. If it is known or suspected that dissolved sample integrity will
be compromised during collection of a composite sample collected automatically over time (e.g., by interchange
of a metal between dissolved and suspended forms), collect and filter grab samples to be composited (footnote
2) in place of a composite sample collected automatically.
\8\ Guidance applies to samples to be analyzed by GC, LC, or GC/MS for specific compounds.
\9\ If the sample is not adjusted to pH 2, then the sample must be analyzed within seven days of sampling.
\10\ The pH adjustment is not required if acrolein will not be measured. Samples for acrolein receiving no pH
adjustment must be analyzed within 3 days of sampling.
[[Page 9002]]
\11\ When the extractable analytes of concern fall within a single chemical category, the specified preservative
and maximum holding times should be observed for optimum safeguard of sample integrity (i.e., use all
necessary preservatives and hold for the shortest time listed). When the analytes of concern fall within two
or more chemical categories, the sample may be preserved by cooling to <= 6 [deg]C, reducing residual chlorine
with 0.008% sodium thiosulfate, storing in the dark, and adjusting the pH to 6-9; samples preserved in this
manner may be held for seven days before extraction and for forty days after extraction. Exceptions to this
optional preservation and holding time procedure are noted in footnote 5 (regarding the requirement for
thiosulfate reduction), and footnotes 12, 13 (regarding the analysis of benzidine).
\12\ If 1,2-diphenylhydrazine is likely to be present, adjust the pH of the sample to 4.0 0.2 to
prevent rearrangement to benzidine.
\13\ Extracts may be stored up to 30 days at < 0 [deg]C.
\14\ For the analysis of diphenylnitrosamine, add 0.008% Na2S2O3 and adjust pH to 7-10 with NaOH within 24 hours
of sampling.
\15\ The pH adjustment may be performed upon receipt at the laboratory and may be omitted if the samples are
extracted within 72 hours of collection. For the analysis of aldrin, add 0.008% Na2S2O3.
\16\ Place sufficient ice with the samples in the shipping container to ensure that ice is still present when
the samples arrive at the laboratory. However, even if ice is present when the samples arrive, immediately
measure the temperature of the samples and confirm that the preservation temperature maximum has not been
exceeded. In the isolated cases where it can be documented that this holding temperature cannot be met, the
permittee can be given the option of on-site testing or can request a variance. The request for a variance
should include supportive data which show that the toxicity of the effluent samples is not reduced because of
the increased holding temperature. Aqueous samples must not be frozen. Hand-delivered samples used on the day
of collection do not need to be cooled to 0 to 6 [deg]C prior to test initiation.
\17\ Samples collected for the determination of trace level mercury (<100 ng/L) using EPA Method 1631 must be
collected in tightly-capped fluoropolymer or glass bottles and preserved with BrCl or HCl solution within 48
hours of sample collection. The time to preservation may be extended to 28 days if a sample is oxidized in the
sample bottle. A sample collected for dissolved trace level mercury should be filtered in the laboratory
within 24 hours of the time of collection. However, if circumstances preclude overnight shipment, the sample
should be filtered in a designated clean area in the field in accordance with procedures given in Method 1669.
If sample integrity will not be maintained by shipment to and filtration in the laboratory, the sample must be
filtered in a designated clean area in the field within the time period necessary to maintain sample
integrity. A sample that has been collected for determination of total or dissolved trace level mercury must
be analyzed within 90 days of sample collection.
\18\ Aqueous samples must be preserved at <= 6 [deg]C, and should not be frozen unless data demonstrating that
sample freezing does not adversely impact sample integrity is maintained on file and accepted as valid by the
regulatory authority. Also, for purposes of NPDES monitoring, the specification of ``<= [deg]C'' is used in
place of the ``4 [deg]C'' and ``< 4 [deg]C'' sample temperature requirements listed in some methods. It is not
necessary to measure the sample temperature to three significant figures (1/100th of 1 degree); rather, three
significant figures are specified so that rounding down to 6 [deg]C may not be used to meet the <=6 [deg]C
requirement. The preservation temperature does not apply to samples that are analyzed immediately (less than
15 minutes).
\19\ An aqueous sample may be collected and shipped without acid preservation. However, acid must be added at
least 24 hours before analysis to dissolve any metals that adsorb to the container walls. If the sample must
be analyzed within 24 hours of collection, add the acid immediately (see footnote 2). Soil and sediment
samples do not need to be preserved with acid. The allowances in this footnote supersede the preservation and
holding time requirements in the approved metals methods.
\20\ To achieve the 28-day holding time, use the ammonium sulfate buffer solution specified in EPA Method 218.6.
The allowance in this footnote supersedes preservation and holding time requirements in the approved
hexavalent chromium methods, unless this supersession would compromise the measurement, in which case
requirements in the method must be followed.
\21\ Holding time is calculated from time of sample collection to elution for samples shipped to the laboratory
in bulk and calculated from the time of sample filtration to elution for samples filtered in the field.
\22\ Sample analysis should begin as soon as possible after receipt; sample incubation must be started no later
than 8 hours from time of collection.
\23\ For fecal coliform samples for sewage sludge (biosolids) only, the holding time is extended to 24 hours for
the following sample types using either EPA Method 1680 (LTB-EC) or 1681 (A-1): Class A composted, Class B
aerobically digested, and Class B anaerobically digested.
\24\ The immediate filtration requirement in orthophosphate measurement is to assess the dissolved or bio-
available form of orthophosphorus (i.e., that which passes through a 0.45-micron filter), hence the
requirement to filter the sample immediately upon collection (i.e., within 15 minutes of collection).
0
5. Section 136.4 is amended by revising paragraphs (a) introductory
text, (b), and (c) to read as follows:
Sec. 136.4 Application for and approval of alternate test procedures
for nationwide use.
(a) A written application for review of an alternate test procedure
(alternate method) for nationwide use may be made by letter via email
or by hard copy in triplicate to the National Alternate Test Procedure
(ATP) Program Coordinator (National Coordinator), Office of Science and
Technology (4303T), Office of Water, U.S. Environmental Protection
Agency, 1200 Pennsylvania Ave. NW., Washington, DC 20460. Any
application for an ATP under this paragraph (a) shall:
* * * * *
(b) The National Coordinator may request additional information and
analyses from the applicant in order to evaluate whether the alternate
test procedure satisfies the applicable requirements of this part.
(c) Approval for nationwide use. (1) After a review of the
application and any additional analyses requested from the applicant,
the National Coordinator will notify the applicant, in writing, of
whether the National Coordinator will recommend approval or disapproval
of the alternate test procedure for nationwide use in CWA programs. If
the application is not recommended for approval, the National
Coordinator may specify what additional information might lead to a
reconsideration of the application and notify the Regional Alternate
Test Procedure Coordinators of the disapproval recommendation. Based on
the National Coordinator's recommended disapproval of a proposed
alternate test procedure and an assessment of any current approvals for
limited uses for the unapproved method, the Regional ATP Coordinator
may decide to withdraw approval of the method for limited use in the
Region.
(2) Where the National Coordinator has recommended approval of an
applicant's request for nationwide use of an alternate test procedure,
the National Coordinator will notify the applicant. The National
Coordinator will also notify the Regional ATP Coordinators that they
may consider approval of this alternate test procedure for limited use
in their Regions based on the information and data provided in the
application until the alternate test procedure is approved by
publication in a final rule in the Federal Register.
(3) EPA will propose to amend this part to include the alternate
test procedure in Sec. 136.3. EPA shall make available for review all
the factual bases for its proposal, including the method, any
performance data submitted by the applicant and any available EPA
analysis of those data.
(4) Following public comment, EPA shall publish in the Federal
Register a final decision on whether to amend this part to include the
alternate test procedure as an approved analytical method for
nationwide use.
(5) Whenever the National Coordinator has recommended approval of
an applicant's ATP request for nationwide use, any person may request
an approval of the method for limited use under Sec. 136.5 from the
EPA Region.
[[Page 9003]]
0
6. Section 136.5 is amended by revising paragraphs (a), (b), (c)(1),
and (d) to read as follows:
Sec. 136.5 Approval of alternate test procedures for limited use.
(a) Any person may request the Regional ATP Coordinator to approve
the use of an alternate test procedure in the Region.
(b) When the request for the use of an alternate test procedure
concerns use in a State with an NPDES permit program approved pursuant
to section 402 of the Act, the requestor shall first submit an
application for limited use to the Director of the State agency having
responsibility for issuance of NPDES permits within such State (i.e.,
permitting authority). The Director will forward the application to the
Regional ATP Coordinator with a recommendation for or against approval.
(c) * * *
(1) Provide the name and address of the applicant and the
applicable ID number of the existing or pending permit(s) and issuing
agency for which use of the alternate test procedure is requested, and
the discharge serial number.
* * * * *
(d) Approval for limited use. (1) The Regional ATP Coordinator will
review the application and notify the applicant and the appropriate
State agency of approval or rejection of the use of the alternate test
procedure. The approval may be restricted to use only with respect to a
specific discharge or facility (and its laboratory) or, at the
discretion of the Regional ATP Coordinator, to all dischargers or
facilities (and their associated laboratories) specified in the
approval for the Region. If the application is not approved, the
Regional ATP Coordinator shall specify what additional information
might lead to a reconsideration of the application.
(2) The Regional ATP Coordinator will forward a copy of every
approval and rejection notification to the National Alternate Test
Procedure Coordinator.
0
7. In Sec. 136.6:
0
a. Revise paragraphs (b)(1) and (2) introductory text.
0
b. Remove paragraph (b)(4)(xvi).
0
c. Redesignate paragraphs (b)(4)(xvii) through (xxii) as paragraphs
(b)(4)(xvi) through (xxi), respectively.
0
d. Add paragraph (c).
The revision and addition read as follows:
Sec. 136.6 Method modifications and analytical requirements.
* * * * *
(b) Method modifications. (1) If the underlying chemistry and
determinative technique in a modified method are essentially the same
as an approved part 136 method, then the modified method is an
equivalent and acceptable alternative to the approved method provided
the requirements of this section are met. However, those who develop or
use a modification to an approved (part 136) method must document that
the performance of the modified method, in the matrix to which the
modified method will be applied, is equivalent to the performance of
the approved method. If such a demonstration cannot be made and
documented, then the modified method is not an acceptable alternative
to the approved method. Supporting documentation must, if applicable,
include the routine initial demonstration of capability and ongoing QC
including determination of precision and accuracy, detection limits,
and matrix spike recoveries. Initial demonstration of capability
typically includes analysis of four replicates of a mid-level standard
and a method detection limit study. Ongoing quality control typically
includes method blanks, mid-level laboratory control samples, and
matrix spikes (QC is as specified in the method). The method is
considered equivalent if the quality control requirements in the
reference method are achieved. The method user's Standard Operating
Procedure (SOP) must clearly document the modifications made to the
reference method. Examples of allowed method modifications are listed
in this section. If the method user is uncertain whether a method
modification is allowed, the Regional ATP Coordinator or Director
should be contacted for approval prior to implementing the
modification. The method user should also complete necessary
performance checks to verify that acceptable performance is achieved
with the method modification prior to analyses of compliance samples.
(2) Requirements. The modified method must meet or exceed
performance of the approved method(s) for the analyte(s) of interest,
as documented by meeting the initial and ongoing quality control
requirements in the method.
* * * * *
(c) The permittee must notify their permitting authority of the
intent to use a modified method. Such notification should be of the
form ``Method xxx has been modified within the flexibility allowed in
40 CFR 136.6.'' The permittee may indicate the specific paragraph of
Sec. 136.6 allowing the method modification. Specific details of the
modification need not be provided, but must be documented in the
Standard Operating Procedure (SOP) and maintained by the analytical
laboratory that performs the analysis.
0
8. In Appendix A to part 136:
0
a. Revise Method 608.
0
b. Revise Method 611, section 1.1.
0
c. Revise Method 624.
0
d. Revise Method 625.
The revisions read as follows:
Appendix A to Part 136--Methods for Organic Chemical Analysis of
Municipal and Industrial Wastewater
* * * * *
Method 608.3--Organochlorine Pesticides And PCBs By GC/HSD
1. Scope and Application
1.1 This method is for determination of organochlorine pesticides
and polychlorinated biphenyls (PCBs) in industrial discharges and other
environmental samples by gas chromatography (GC) combined with a
halogen-specific detector (HSD; e.g., electron capture, electrolytic
conductivity), as provided under 40 CFR 136.1. This revision is based
on a previous protocol (Reference 1), on the revision promulgated
October 26, 1984 (49 FR 43234), on an inter-laboratory method
validation study (Reference 2), and on EPA Method 1656 (Reference 16).
The analytes that may be qualitatively and quantitatively determined
using this method and their CAS Registry numbers are listed in Table 1.
1.2 This method may be extended to determine the analytes listed in
Table 2. However, extraction or gas chromatography challenges for some
of these analytes may make quantitative determination difficult.
1.3 When this method is used to analyze unfamiliar samples for an
analyte listed in Table 1 or Table 2, analyte identification must be
supported by at least one additional qualitative technique. This method
gives analytical conditions for a second GC column that can be used to
confirm and quantify measurements.
Additionally, Method 625 provides gas chromatograph/mass
spectrometer (GC/MS) conditions appropriate for the qualitative
confirmation of results for the analytes listed in Tables 1 and 2 using
the extract produced by this method, and Method 1699 (Reference 18)
provides high resolution GC/MS conditions for qualitative confirmation
of results using the original sample. When such methods are used to
confirm the identifications of the target analytes, the quantitative
results should be derived from the procedure with the
[[Page 9004]]
calibration range and sensitivity that are most appropriate for the
intended application.
1.4 The large number of analytes in Tables 1 and 2 makes testing
difficult if all analytes are determined simultaneously. Therefore, it
is necessary to determine and perform quality control (QC) tests for
the ``analytes of interest'' only. The analytes of interest are those
required to be determined by a regulatory/control authority or in a
permit, or by a client. If a list of analytes is not specified, the
analytes in Table 1 must be determined, at a minimum, and QC testing
must be performed for these analytes. The analytes in Table 1 and some
of the analytes in Table 2 have been identified as Toxic Pollutants (40
CFR 401.15), expanded to a list of Priority Pollutants (40 CFR part
423, appendix A).
1.5 In this revision to Method 608, Chlordane has been listed as
the alpha- and gamma-isomers in Table 1. Reporting may be by the
individual isomers, or as the sum of the concentrations of these
isomers, as requested or required by a regulatory/control authority or
in a permit. Technical Chlordane is listed in Table 2 and may be used
in cases where historical reporting has only been the Technical
Chlordane. Toxaphene and the PCBs have been moved from Table 1 to Table
2 (Additional Analytes) to distinguish these analytes from the analytes
required in quality control tests (Table 1). QC acceptance criteria for
Toxaphene and the PCBs have been retained in Table 4 and may continue
to be applied if desired, or if these analytes are requested or
required by a regulatory/control authority or in a permit. Method 1668C
(Reference 17) may be useful for determination of PCBs as individual
chlorinated biphenyl congeners, and Method 1699 (Reference 18) may be
useful for determination of the pesticides listed in this method.
However, at the time of writing of this revision, Methods 1668C and
1699 had not been approved for use at 40 CFR part 136.
1.6 Method detection limits (MDLs; Reference 3) for the analytes in
Tables 1 and some of the analytes in Table 2 are listed in those
tables. These MDLs were determined in reagent water (Reference 3).
Advances in analytical technology, particularly the use of capillary
(open-tubular) columns, allowed laboratories to routinely achieve MDLs
for the analytes in this method that are 2-10 times lower than those in
the version promulgated in 1984 (40 FR 43234). The MDL for an analyte
in a specific wastewater may differ from those listed, depending upon
the nature of interferences in the sample matrix.
1.6.1 EPA has promulgated this method at 40 CFR part 136 for use in
wastewater compliance monitoring under the National Pollutant Discharge
Elimination System (NPDES). The data reporting practices described in
Section 15.2 are focused on such monitoring needs and may not be
relevant to other uses of the method.
1.6.2 This method includes ``reporting limits'' based on EPA's
``minimum level'' (ML) concept (see the glossary in Section 23). Tables
1 and 2 contain MDL values and ML values for many of the analytes. The
MDL for an analyte in a specific wastewater may differ from those
listed in Tables 1 or 2, depending upon the nature of interferences in
the sample matrix.
1.7 The separatory funnel and continuous liquid-liquid sample
extraction and concentration steps in this method are essentially the
same as those steps in Methods 606, 609, 611, and 612. Thus, a single
sample may be extracted to measure the analytes included in the scope
of each of these methods. Samples may also be extracted using a disk-
based solid-phase extraction (SPE) procedure developed by the 3M
Corporation and approved by EPA as an Alternate Test Procedure (ATP)
for wastewater analyses in 1995 (Reference 20).
1.8 This method is performance-based. It may be modified to improve
performance (e.g., to overcome interferences or improve the accuracy of
results) provided all performance requirements are met.
1.8.1 Examples of allowed method modifications are described at 40
CFR 136.6. Other examples of allowed modifications specific to this
method are described in Section 8.1.2.
1.8.2 Any modification beyond those expressly permitted at 40 CFR
136.6 or in Section 8.1.2 of this method shall be considered a major
modification subject to application and approval of an alternate test
procedure under 40 CFR 136.4 and 136.5.
1.8.3 For regulatory compliance, any modification must be
demonstrated to produce results equivalent or superior to results
produced by this method when applied to relevant wastewaters (Section
8.1.2).
1.9 This method is restricted to use by or under the supervision of
analysts experienced in the use of GC/HSD. The laboratory must
demonstrate the ability to generate acceptable results with this method
using the procedure in Section 8.2.
1.10 Terms and units of measure used in this method are given in
the glossary at the end of the method.
2. Summary of Method
2.1 A measured volume of sample, the amount required to meet an MDL
or reporting limit (nominally 1-L), is extracted with methylene
chloride using a separatory funnel, a continuous liquid/liquid
extractor, or disk-based solid-phase extraction equipment. The extract
is dried and concentrated for cleanup, if required. After cleanup, or
if cleanup is not required, the extract is exchanged into an
appropriate solvent and concentrated to the volume necessary to meet
the required compliance or detection limit, and analyzed by GC/HSD.
2.2 Qualitative identification of an analyte in the extract is
performed using the retention times on dissimilar GC columns.
Quantitative analysis is performed using the peak areas or peak heights
for the analyte on the dissimilar columns with either the external or
internal standard technique.
2.3 Florisil[supreg], alumina, a C18 solid-phase cleanup, and an
elemental sulfur cleanup procedure are provided to aid in elimination
of interferences that may be encountered. Other cleanup procedures may
be used if demonstrated to be effective for the analytes in a
wastewater matrix.
3. Contamination and Interferences
3.1 Solvents, reagents, glassware, and other sample processing lab
ware may yield artifacts, elevated baselines, or matrix interferences
causing misinterpretation of chromatograms. All materials used in the
analysis must be demonstrated free from contamination and interferences
by running blanks initially and with each extraction batch (samples
started through the extraction process in a given 24-hour period, to a
maximum of 20 samples). Specific selection of reagents and purification
of solvents by distillation in all-glass systems may be required. Where
possible, lab ware is cleaned by extraction or solvent rinse, or baking
in a kiln or oven. All materials used must be routinely demonstrated to
be free from interferences under the conditions of the analysis by
running blanks as described in Section 8.5.
3.2 Glassware must be scrupulously cleaned (Reference 4). Clean all
glassware as soon as possible after use by rinsing with the last
solvent used in it. Solvent rinsing should be followed by detergent
washing with hot water, and rinses with tap water and reagent water.
The glassware should then be drained dry, and heated at 400 [deg]C for
[[Page 9005]]
15-30 minutes. Some thermally stable materials, such as PCBs, may
require higher temperatures and longer baking times for removal.
Solvent rinses with pesticide quality acetone, hexane, or other
solvents may be substituted for heating. Volumetric lab ware should not
be heated excessively or for long periods of time. After drying and
cooling, glassware should be sealed and stored in a clean environment
to prevent accumulation of dust or other contaminants. Store inverted
or capped with aluminum foil.
3.3 Interferences by phthalate esters can pose a major problem in
pesticide analysis when using the electron capture detector. The
phthalate esters generally appear in the chromatogram as large late
eluting peaks, especially in the 15 and 50% fractions from
Florisil[supreg]. Common flexible plastics contain varying amounts of
phthalates that may be extracted or leached from such materials during
laboratory operations. Cross contamination of clean glassware routinely
occurs when plastics are handled during extraction steps, especially
when solvent-wetted surfaces are handled. Interferences from phthalates
can best be minimized by avoiding use of non-fluoropolymer plastics in
the laboratory. Exhaustive cleanup of reagents and glassware may be
required to eliminate background phthalate contamination (References 5
and 6). Interferences from phthalate esters can be avoided by using a
microcoulometric or electrolytic conductivity detector.
3.4 Matrix interferences may be caused by contaminants co-extracted
from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled.
Interferences extracted from samples high in total organic carbon (TOC)
may result in elevated baselines, or by enhancing or suppressing a
signal at or near the retention time of an analyte of interest.
Analyses of the matrix spike and duplicate (Section 8.3) may be useful
in identifying matrix interferences, and the cleanup procedures in
Section 11 may aid in eliminating these interferences. EPA has provided
guidance that may aid in overcoming matrix interferences (Reference 7);
however, unique samples may require additional cleanup approaches to
achieve the MDLs listed in Table 3.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible
level by whatever means available. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of safety data sheets (SDSs, OSHA, 29 CFR 1910.1200(g)) should
also be made available to all personnel involved in sample handling and
chemical analysis. Additional references to laboratory safety are
available and have been identified (References 8 and 9) for the
information of the analyst.
4.2 The following analytes covered by this method have been
tentatively classified as known or suspected human or mammalian
carcinogens: 4,4'-DDT, 4,4'-DDD, the BHCs, and the PCBs. Primary
standards of these toxic analytes should be prepared in a chemical fume
hood, and a NIOSH/MESA approved toxic gas respirator should be worn
when high concentrations are handled.
4.3 This method allows the use of hydrogen as a carrier gas in
place of helium (Section 5.8.2). The laboratory should take the
necessary precautions in dealing with hydrogen, and should limit
hydrogen flow at the source to prevent buildup of an explosive mixture
of hydrogen in air.
5. Apparatus and Materials
Note: Brand names and suppliers are for illustration purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and materials other than those specified
here. Demonstrating that the equipment and supplies used in the
laboratory achieve the required performance is the responsibility of
the laboratory. Suppliers for equipment and materials in this method
may be found through an on-line search. Please do not contact EPA
for supplier information.
5.1 Sampling equipment, for discrete or composite sampling
5.1.1 Grab sample bottle--amber glass bottle large enough to
contain the necessary sample volume (nominally 1 L), fitted with a
fluoropolymer-lined screw cap. Foil may be substituted for
fluoropolymer if the sample is not corrosive. If amber bottles are not
available, protect samples from light. Unless pre-cleaned, the bottle
and cap liner must be washed, rinsed with acetone or methylene
chloride, and dried before use to minimize contamination.
5.1.2 Automatic sampler (optional)--the sampler must use a glass or
fluoropolymer container and tubing for sample collection. If the
sampler uses a peristaltic pump, a minimum length of compressible
silicone rubber tubing may be used. Before use, however, the
compressible tubing should be thoroughly rinsed with methanol, followed
by repeated rinsing with reagent water to minimize the potential for
sample contamination. An integrating flow meter is required to collect
flow proportional composites. The sample container must be kept
refrigerated at <6 [deg]C and protected from light during compositing.
5.2. Lab ware
5.2.1 Extraction
5.2.1.1 pH measurement
5.2.1.1.1 pH meter, with combination glass electrode
5.2.1.1.2 pH paper, wide range (Hydrion Papers, or equivalent)
5.2.1.2 Separatory funnel--Size appropriate to hold the sample and
extraction solvent volumes, equipped with fluoropolymer stopcock.
5.2.1.3 Continuous liquid-liquid extractor--Equipped with
fluoropolymer or glass connecting joints and stopcocks requiring no
lubrication. (Hershberg-Wolf Extractor, Ace Glass Company, Vineland,
NJ, or equivalent.)
5.2.1.3.1 Round-bottom flask, 500-mL, with heating mantle
5.2.1.3.2 Condenser, Graham, to fit extractor
5.2.1.4 Solid-phase extractor--90-mm filter apparatus (Figure 2) or
multi-position manifold
5.2.1.4.1 Vacuum system--Capable of achieving 0.1 bar (25 inch) Hg
(house vacuum, vacuum pump, or water aspirator), equipped with shutoff
valve and vacuum gauge
5.2.1.4.2 Vacuum trap--Made from 500-mL sidearm flask fitted with
single-hole rubber stopper and glass tubing
Note: The approved ATP for solid-phase extraction is limited to
disk-based extraction media and associated peripheral equipment.
5.2.2 Filtration
5.2.2.1 Glass powder funnel, 125- to 250-mL
5.2.2.2 Filter paper for above, Whatman 41, or equivalent
5.2.2.3 Prefiltering aids--90-mm 1-[mu]m glass fiber filter or
Empore[supreg] Filter Aid 400
5.2.3 Drying column
5.2.3.1 Chromatographic column--approximately 400 mm long x 15 mm
ID, with fluoropolymer stopcock and coarse frit filter disc (Kontes or
equivalent).
5.2.3.2 Glass wool--Pyrex, extracted with methylene chloride or
baked at 450 [deg]C for 1 hour minimum
5.2.4 Column for Florisil[supreg] or alumina cleanup--approximately
300
[[Page 9006]]
mm long x 10 mm ID, with fluoropolymer stopcock. (This column is not
required if cartridges containing Florisil[supreg] are used.)
5.2.5 Concentration/evaporation
Note: Use of a solvent recovery system with the K-D or other
solvent evaporation apparatus is strongly recommended.
5.2.5.1 Kuderna-Danish concentrator
5.2.5.1.1 Concentrator tube, Kuderna-Danish--10-mL, graduated
(Kontes or equivalent). Calibration must be checked at the volumes
employed for extract volume measurement. A ground-glass stopper is used
to prevent evaporation of extracts.
5.2.5.1.2 Evaporative flask, Kuderna-Danish--500-mL (Kontes or
equivalent). Attach to concentrator tube with connectors.
5.2.5.1.3 Snyder column, Kuderna/Danish--Three-ball macro (Kontes
or equivalent)
5.2.5.1.4 Snyder column--Two-ball micro (Kontes or equivalent)
5.2.5.1.5 Water bath--Heated, with concentric ring cover, capable
of temperature control ( 2 [deg]C), installed in a hood
using appropriate engineering controls to limit exposure to solvent
vapors.
5.2.5.2 Nitrogen evaporation device--Equipped with heated bath that
can be maintained at an appropriate temperature for the solvent and
analytes. (N-Evap, Organomation Associates, Inc., or equivalent)
5.2.5.3 Rotary evaporator--Buchi/Brinkman-American Scientific or
equivalent, equipped with a variable temperature water bath, vacuum
source with shutoff valve at the evaporator, and vacuum gauge.
5.2.5.2.1 A recirculating water pump and chiller are recommended,
as use of tap water for cooling the evaporator wastes large volumes of
water and can lead to inconsistent performance as water temperatures
and pressures vary.
5.2.5.2.2 Round-bottom flask--100-mL and 500-mL or larger, with
ground-glass fitting compatible with the rotary evaporator
Note: This equipment is used to prepare copper foil or copper
powder for removing sulfur from sample extracts (see Section 6.7.4).
5.2.5.4 Automated concentrator--Equipped with glassware sufficient
to concentrate 3-400 mL extract to a final volume of 1-10 mL under
controlled conditions of temperature and nitrogen flow (Turbovap, or
equivalent). Follow manufacturer's directions and requirements.
5.2.5.5 Boiling chips--Glass, silicon carbide, or equivalent,
approximately 10/40 mesh. Heat at 400 [deg]C for 30 minutes, or solvent
rinse or Soxhlet extract with methylene chloride.
5.2.5 Solid-phase extraction disks--90-mm extraction disks
containing 2 g of 8-[mu]m octadecyl (C18) bonded silica uniformly
enmeshed in a matrix of inert PTFE fibrils (3M Empore[supreg] or
equivalent). The disks should not contain any organic compounds, either
from the PTFE or the bonded silica, which will leach into the methylene
chloride eluant. One liter of reagent water should pass through the
disks in 2-5 minutes, using a vacuum of at least 25 inches of mercury.
Note: Extraction disks from other manufacturers may be used in
this procedure, provided that they use the same solid phase
materials (i.e., octadecyl bonded silica). Disks of other diameters
also may be used, but may adversely affect the flow rate of the
sample through the disk.
5.3 Vials
5.3.1 Extract storage--10- to 15-mL, amber glass, with
fluoropolymer-lined screw cap
5.3.2 GC autosampler--1- to 5-mL, amber glass, with fluoropolymer-
lined screw- or crimp-cap, to fit GC autosampler
5.4 Balances
5.4.1 Analytical--capable of accurately weighing 0.1 mg
5.4.2 Top loading--capable of weighing 10 mg
5.5 Sample cleanup
5.5.1 Oven--For baking and storage of adsorbents, capable of
maintaining a constant temperature ( 5 [deg]C) in the range
of 105-250 [deg]C.
5.5.2 Muffle furnace--Capable of cleaning glassware or baking
sodium sulfate in the range of 400-450 [deg]C.
5.5.3 Vacuum system and cartridges for solid-phase cleanup (see
Section 11.2)
5.5.3.1 Vacuum system--Capable of achieving 0.1 bar (25 in.) Hg
(house vacuum, vacuum pump, or water aspirator), equipped with shutoff
valve and vacuum gauge
5.5.3.2 VacElute Manifold (Analytichem International, or
equivalent)
5.5.3.3 Vacuum trap--Made from 500-mL sidearm flask fitted with
single-hole rubber stopper and glass tubing
5.5.3.4 Rack for holding 50-mL volumetric flasks in the manifold
5.5.3.5 Cartridge--Mega Bond Elute, Non-polar, C18 Octadecyl, 10 g/
60 mL (Analytichem International or equivalent), used for solid-phase
cleanup of sample extracts (see Section 11.2)
5.5.3.5.1 Cartridge certification--Each cartridge lot must be
certified to ensure recovery of the analytes of interest and removal of
2,4,6-trichlorophenol. To make the test mixture, add the
trichlorophenol solution (Section 6.7.2.1) to the same standard used to
prepare the Quality Control Check Sample (Section 6.8.3). Transfer the
mixture to the column and dry the column. Pre-elute with three 10-mL
portions of elution solvent, drying the column between elutions. Elute
the cartridge with 10 mL each of methanol and water, as in Section
11.2.3.3.
5.5.3.5.2 Concentrate the eluant to per Section 10.3.3, exchange to
isooctane or hexane per Section 10.3.3, and inject 1.0 [mu]L of the
concentrated eluant into the GC using the procedure in Section 12. The
recovery of all analytes (including the unresolved GC peaks) shall be
within the ranges for calibration verification (Section 13.6 and Table
4), and the peak for trichlorophenol shall not be detectable; otherwise
the SPE cartridge is not performing properly and the cartridge lot
shall be rejected.
5.5.4 Sulfur removal tube--40- to 50-mL bottle, test tube, or
Erlenmeyer flask with fluoropolymer-lined screw cap
5.6 Centrifuge apparatus
5.6.1 Centrifuge--Capable of rotating 500-mL centrifuge bottles or
15-mL centrifuge tubes at 5,000 rpm minimum
5.6.2 Centrifuge bottle--500-mL, with screw cap, to fit centrifuge
5.6.3 Centrifuge tube--15-mL, with screw cap, to fit centrifuge
5.7 Miscellaneous lab ware--graduated cylinders, pipettes, beakers,
volumetric flasks, vials, syringes, and other lab ware necessary to
support the operations in this method
5.8 Gas chromatograph--Dual-column with simultaneous split/
splitless, temperature programmable split/splitless (PTV), or on-column
injection; temperature program with isothermal holds, and all required
accessories including syringes, analytical columns, gases, and
detectors. An autosampler is highly recommended because it injects
volumes more reproducibly than manual injection techniques.
Alternatively, two separate single-column gas chromatographic systems
may be employed.
5.8.1 Example columns and operating conditions
5.8.1.1 DB-608 (or equivalent), 30-m long x 0.53-mm ID fused-silica
capillary, 0.83-[mu]m film thickness.
5.8.1.2 DB-1701 (or equivalent), 30-m long x 0.53-mm ID fused-
silica capillary, 1.0-[mu]m film thickness.
5.8.1.3 Suggested operating conditions used to meet the retention
times shown in Table 3 are:
Carrier gas flow rate: approximately 7 mL/min
[[Page 9007]]
Initial temperature: 150 [deg]C for 0.5 minute,
Temperature program: 150-270 [deg]C at 5 [deg]C/min, and
Final temperature: 270 [deg]C, until trans-Permethrin elutes
Note: Other columns, internal diameters, film thicknesses, and
operating conditions may be used, provided that the performance
requirements in this method are met. However, the column pair chosen
must have dissimilar phases/chemical properties in order to separate
the compounds of interest in different retention time order. Columns
that only differ in the length, ID, or film thickness, but use the
same stationary phase do not qualify as ``dissimilar.''
5.8.2 Carrier gas--Helium or hydrogen. Data in the tables in this
method were obtained using helium carrier gas. If hydrogen is used,
analytical conditions may need to be adjusted for optimum performance,
and calibration and all QC tests must be performed with hydrogen
carrier gas. See Section 4.3 for precautions regarding the use of
hydrogen as a carrier gas.
5.8.3 Detector--Halogen-specific detector (electron capture
detector (ECD), electrolytic conductivity detector (ELCD), or
equivalent). The ECD has proven effective in the analysis of
wastewaters for the analytes listed in Tables 1 and 2, and was used to
develop the method performance data in Section 17 and Tables 4 and 5.
5.8.4 Data system--A computer system must be interfaced to the GC
that allows continuous acquisition and storage of data from the
detectors throughout the chromatographic program. The computer must
have software that allows searching GC data for specific analytes, and
for plotting responses versus time. Software must also be available
that allows integrating peak areas or peak heights in selected
retention time windows and calculating concentrations of the analytes.
6. Reagents and Standards
6.1 pH adjustment
6.1.1 Sodium hydroxide solutions
6.1.1.1 Concentrated (10 M)--Dissolve 40 g of NaOH (ACS) in reagent
water and dilute to 100 mL.
6.1.1.2 Dilute (1 M)--Dissolve 40 g NaOH in 1 L of reagent water.
6.1.2 Sulfuric acid (1 + 1)--Slowly add 50 mL of
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.1.3 Hydrochloric acid--Reagent grade, 6 N
6.2 Sodium thiosulfate--(ACS) granular.
6.3 Sodium sulfate--Sodium sulfate, reagent grade, granular
anhydrous (Baker or equivalent), rinsed with methylene chloride (20 mL/
g), baked in a shallow tray at 450 [deg]C for 1 hour minimum, cooled in
a desiccator, and stored in a pre-cleaned glass bottle with screw cap
which prevents moisture from entering. If, after heating, the sodium
sulfate develops a noticeable grayish cast (due to the presence of
carbon in the crystal matrix), that batch of reagent is not suitable
for use and should be discarded. Extraction with methylene chloride (as
opposed to simple rinsing) and baking at a lower temperature may
produce sodium sulfate suitable for use.
6.4 Reagent water--Reagent water is defined as water in which the
analytes of interest and interfering compounds are not observed at the
MDLs of the analytes in this method.
6.5 Solvents--methylene chloride, acetone, methanol, hexane,
acetonitrile, and isooctane, high purity pesticide quality, or
equivalent, demonstrated to be free of the analytes and interferences
(Section 3). Purification of solvents by distillation in all-glass
systems may be required.
Note: The standards and final sample extracts must be prepared
in the same final solvent.
6.6 Ethyl ether--Nanograde, redistilled in glass if necessary
Ethyl ether must be shown to be free of peroxides before use, as
indicated by EM Laboratories Quant test strips (available from
Scientific Products Co. and other suppliers). Procedures recommended
for removal of peroxides are provided with the test strips. After
removal of peroxides, add 20 mL of ethyl alcohol preservative to each
liter of ether.
6.7 Materials for sample cleanup
6.7.1 Florisil[supreg]--PR grade (60/100 mesh), activated at 650--
700 [deg]C, stored in the dark in a glass container with fluoropolymer-
lined screw cap. Activate each batch immediately prior to use for 16
hours minimum at 130 [deg]C in a foil-covered glass container and allow
to cool. Alternatively, 500 mg cartridges (J.T. Baker, or equivalent)
may be used.
6.7.2 Solutions for solid-phase cleanup
6.7.2.1 SPE cartridge calibration solution--2,4,6-trichlorophenol,
0.1 [mu]g/mL in acetone.
6.7.2.2 SPE elution solvent--methylene chloride:acetonitrile:hexane
(50:3:47).
6.7.3 Alumina, neutral, Brockman Activity I, 80-200 mesh (Fisher
Scientific certified, or equivalent). Heat in a glass bottle for 16
hours at 400 to 450 [deg]C. Seal and cool to room temperature. Add 7%
(w/w) reagent water and mix for 10 to 12 hours. Keep bottle tightly
sealed.
6.7.4 Sulfur removal
6.7.4.1 Copper foil or powder--Fisher, Alfa Aesar, or equivalent.
Cut copper foil into approximately 1-cm squares. Copper must be
activated on each day it will be used, as described below.
6.7.4.1.1 Place the quantity of copper needed for sulfur removal
(Section 11.5.1.3) in a ground-glass-stoppered Erlenmeyer flask or
bottle. Cover the foil or powder with methanol.
6.7.4.1.2 Add HCl dropwise (0.5--1.0 mL) while swirling, until the
copper brightens.
6.7.4.1.3 Pour off the methanol/HCl and rinse 3 times with reagent
water to remove all traces of acid, then 3 times with acetone, then 3
times with hexane.
6.7.4.1.4 For copper foil, cover with hexane after the final rinse.
Store in a stoppered flask under nitrogen until used. For the powder,
dry on a rotary evaporator. Store in a stoppered flask under nitrogen
until used.
6.7.4.2 Tetrabutylammonium sulfite (TBA sulfite)
6.7.4.2.1 Tetrabutylammonium hydrogen sulfate,
[CH3(CH2)3]4NHSO4
6.7.4.2.2 Sodium sulfite, Na2SO3
6.7.4.2.3 Dissolve approximately 3 g tetrabutylammonium hydrogen
sulfate in 100 mL of reagent water in an amber bottle with
fluoropolymer-lined screw cap. Extract with three 20-mL portions of
hexane and discard the hexane extracts.
6.7.4.2.4 Add 25 g sodium sulfite to produce a saturated solution.
Store at room temperature. Replace after 1 month.
6.8 Standard solutions--Purchase as solutions or mixtures with
certification to their purity, concentration, and authenticity, or
prepare from materials of known purity and composition. If compound
purity is 96% or greater, the weight may be used without correction to
compute the concentration of the standard. Store neat standards or
single analyte standards in the dark at -20 to -10 [deg]C in screw-cap
vials with fluoropolymer-lined caps. Store multi-analyte standards at 4
[deg]C or per manufacturer's recommendations. Place a mark on the vial
at the level of the solution so that solvent evaporation loss can be
detected. Bring the vial to room temperature prior to use to re-
dissolve any precipitate.
6.8.1 Stock standard solutions--Standard solutions may be prepared
from pure standard materials or purchased as certified solutions.
Traceability must be to a national standard, when available. Except as
noted below for solutions spiked into samples, prepare stock standards
in isooctane or hexane. Observe the safety
[[Page 9008]]
precautions in Section 4. The following procedure may be used to
prepare standards from neat materials.
6.8.1.1 Dissolve an appropriate amount of assayed reference
material in solvent. For example, weigh 10 mg of aldrin in a 10-mL
ground-glass-stoppered volumetric flask and fill to the mark with
isooctane or hexane. Larger volumes may be used at the convenience of
the laboratory. After the aldrin is completely dissolved, transfer the
solution to a 15-mL vial with fluoropolymer-lined cap.
6.8.1.2 Check for signs of degradation prior to preparation of
calibration or performance-test standards.
6.8.1.3 Replace stock solutions after 12 months, or sooner if
comparison with quality control check standards indicates a change in
concentration.
6.8.2 Calibration solutions--It is necessary to prepare calibration
solutions for the analytes of interest (Section 1.4) only using an
appropriate solvent (isooctane or hexane may be used). Whatever solvent
is used, both the calibration standards and the final sample extracts
must use the same solvent. Other analytes may be included as desired.
6.8.2.1 Prepare calibration standards for the single-component
analytes of interest and surrogates at a minimum of three concentration
levels (five are suggested) by adding appropriate volumes of one or
more stock standards to volumetric flasks. One of the calibration
standards should be at a concentration of the analyte near the ML in
Table 1 or 2. The ML value may be rounded to a whole number that is
more convenient for preparing the standard, but must not exceed the ML
values listed in Tables 1 or 2 for those analytes which list ML values.
Alternatively, the laboratory may establish the ML for each analyte
based on the concentration of the lowest calibration standard in a
series of standards obtained from a commercial vendor, again, provided
that the ML values does not exceed the MLs in Table 1 and 2, and
provided that the resulting calibration meets the acceptance criteria
in Section 7.5.2. based on the RSD, RSE, or R\2\.
The other concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range
of the GC system. A minimum of six concentration levels is required for
a second order, non-linear (e.g., quadratic; ax\2\ + bx + c)
calibration. Calibrations higher than second order are not allowed.
Given the number of analytes included in this method, it is highly
likely that some will coelute on one or both of the GC columns used for
the analysis. Therefore, divide the analytes two or more groups and
prepare separate calibration standards for each group, at multiple
concentrations (e.g., a five-point calibration will require ten
solutions to cover two groups of analytes).
Note: Many commercially available standards are divided into
separate mixtures to address this issue.
The other concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range
of the GC system. A separate standard near the MDL may be analyzed as a
check on sensitivity, but should not be included in the linearity
assessment. A minimum of six concentration levels is required for a
non-linear (e.g., quadratic) calibration (Section 7.5.2 or 7.6.2). The
solvent for the standards must match the final solvent for the sample
extracts (e.g., isooctane or hexane).
Note: The option for non-linear calibration may be necessary to
address specific instrumental techniques. However, it is not EPA's
intent to allow non-linear calibration to be used to compensate for
detector saturation or to avoid proper instrument maintenance.
6.8.2.2 Multi-component analytes (e.g., PCBs as Aroclors, and
Toxaphene)
6.8.2.2.1 A standard containing a mixture of Aroclor 1016 and
Aroclor 1260 will include many of the peaks represented in the other
Aroclor mixtures. As a result, a multi-point initial calibration
employing a mixture of Aroclors 1016 and 1260 at three to five
concentrations should be sufficient to demonstrate the linearity of the
detector response without the necessity of performing multi-point
initial calibrations for each of the seven Aroclors. In addition, such
a mixture can be used as a standard to demonstrate that a sample does
not contain peaks that represent any one of the Aroclors. This standard
can also be used to determine the concentrations of either Aroclor 1016
or Aroclor 1260, should they be present in a sample.
Therefore, prepare a minimum of three calibration standards
containing equal concentrations of both Aroclor 1016 and Aroclor 1260
by dilution of the stock standard with isooctane or hexane. The
concentrations should correspond to the expected range of
concentrations found in real samples and should bracket the linear
range of the detector.
6.8.2.2.2 Single standards of each of the other five Aroclors are
required to aid the analyst in pattern recognition. Assuming that the
Aroclor 1016/1260 standards described in Section 6.8.2.2.1 have been
used to demonstrate the linearity of the detector, these single
standards of the remaining five Aroclors also may be used to determine
the calibration factor for each Aroclor. Prepare a standard for each of
the other Aroclors. The concentrations should generally correspond to
the mid-point of the linear range of the detector, but lower
concentrations may be employed at the discretion of the analyst based
on project requirements.
6.8.2.2.3 For Toxaphene, prepare a minimum of three calibration
standards containing Toxaphene by dilution of the stock standard with
isooctane or hexane. The concentrations should correspond to the
expected range of concentrations found in real samples and should
bracket the linear range of the detector.
6.8.3 Quality Control (QC) Check Sample--Also known as the
Laboratory Control Sample (LCS). Prepare a mid-level standard mixture
in acetone (or water miscible solvent) from a stock solution from the
same source as the calibration standards. This standard will be used to
generate extracts to evaluate the capability of the laboratory.
6.8.4 Second Source Standard--Obtain standards from a second source
(different manufacturer or different certified lot), and prepare a mid-
level standard mixture in isooctane or hexane. This standard will be
analyzed with the calibration curve to verify the accuracy of the
calibration.
6.8.5 Internal standard solution--If the internal standard
calibration technique is to be used, prepare pentachloronitrobenzene
(PCNB) at a concentration of 10 [mu]g/mL in ethyl acetate. Alternative
and multiple internal standards; e.g., tetrachloro-m-xylene, 4,4'-
dibromobiphenyl, and/or decachlorobiphenyl may be used provided that
the laboratory performs all QC tests and meets all QC acceptance
criteria with the alternate or additional internal standard(s) as an
integral part of this method.
6.8.6 Surrogate solution--Prepare a solution containing one or more
surrogates at a concentration of 2 [mu]g/mL in acetone. Potential
surrogates include: Dibutyl chlorendate (DBC), tetrachloro-m-xylene
(TCMX), 4,4'-dibromobiphenyl, or decachlorobiphenyl provided that the
laboratory performs all QC tests and meets all QC acceptance criteria
with the alternative surrogate(s) as an integral part of this method.
If the internal standard calibration technique is used, do not use the
internal standard as a surrogate.
[[Page 9009]]
6.8.7 DDT and endrin decomposition (breakdown) solution--Prepare a
solution containing endrin at a concentration of 1 [mu]g/mL and 4,4'-
DDT at a concentration of 2 [mu]g/mL, in isooctane or hexane.
6.8.8 Quality control check sample (laboratory control sample; LCS)
concentrate--See Sections 8.2.1 and 8.4.
6.8.9 Stability of solutions--Analyze all standard solutions
(Sections 6.8.1 through 6.8.8) within 48 hours of preparation. Replace
purchased certified stock standard solutions per the expiration date.
Replace stock standard solutions prepared by the laboratory or mixed
with purchased solutions after one year, or sooner if comparison with
QC check samples indicates a problem.
7. Calibration
7.1 Establish gas chromatographic operating conditions equivalent
to those in Section 5.8.1 and Footnote 2 to Table 3. Alternative
temperature program and flow rate conditions may be used. The system
may be calibrated using the external standard technique (Section 7.5)
or the internal standard technique (Section 7.6). It is necessary to
calibrate the system for the analytes of interest (Section 1.4) only.
7.2 Separately inject the mid-level calibration standard for each
calibration mixture. Store the retention time on each GC column.
7.3 Demonstrate that each column/detector system meets the MDLs in
Table 3 or demonstrates sufficient sensitivity for the intended
application and passes the DDT/endrin decomposition test (Section
13.5).
7.4 Injection of calibration solutions--Inject a constant volume in
the range of 0.5 to 2.0 [mu]L of each calibration solution into the GC
column/detector pairs. Beginning with the lowest level mixture and
proceeding to the highest level mixture may limit the risk of carryover
from one standard to the next, but other sequences may be used. A blank
sample should be analyzed after the highest standard to demonstrate
that there is no carry-over within the system for this calibration
range. For each analyte, compute, record, and store, as a function of
the concentration injected, the retention time and peak area on each
column/detector system. If multi-component analytes are to be analyzed,
store the retention time and peak area for the three to five exclusive
(unique large) peaks for each PCB or technical chlordane. Use four to
six peaks for toxaphene.
7.5 External standard calibration
7.5.1 From the calibration data (Section 7.4), calculate the
calibration factor (CF) for each analyte at each concentration
according to the following equation:
[GRAPHIC] [TIFF OMITTED] TP19FE15.000
where:
Cs = Concentration of the analyte in the standard (ng/mL)
As = Peak height or area
For multi-component analytes, choose a series of characteristic
peaks for each analyte (3 to 5 for each Aroclor, 4 to 6 for toxaphene)
and calculate individual calibration factors for each peak.
Alternatively, for toxaphene, sum the areas of all of the peaks in the
standard chromatogram and use the summed area to determine the
calibration factor. (If this alternative is used, the same approach
must be used to quantitate the analyte in the samples.)
7.5.2 Calculate the mean (average) and relative standard deviation
(RSD) of the calibration factors. If the RSD is less than 20%,
linearity through the origin can be assumed and the average CF can be
used for calculations. Alternatively, the results can be used to fit a
linear or quadratic regression of response ratios, As/
Ais, vs. concentration ratios Cs/Cis.
If used, the regression must be weighted inversely proportional to
concentration. The coefficient of determination (R \2\) of the weighted
regression must be greater than 0.99. Alternatively, the relative
standard error (Reference 10) may be used as an acceptance criterion.
As with the RSD, the RSE must be less than 20%. If an RSE less than 20%
cannot be achieved for a quadratic regression, system performance is
unacceptable and the system must be adjusted and re-calibrated.
Note: Regression calculations are not included in this method
because the calculations are cumbersome and because many GC/ECD data
systems allow selection of weighted regression for calibration and
calculation of analyte concentrations.
7.6 Internal standard calibration
7.6.1 From the calibration data (Section 7.4), calculate the
response factor (RF) for each analyte at each concentration according
to the following equation:
[GRAPHIC] [TIFF OMITTED] TP19FE15.001
where:
As = Response for the analyte to be measured.
Ais = Response for the internal standard.
Cis = Concentration of the internal standard (ng/mL)
Cs = Concentration of the analyte to be measured (ng/mL).
7.6.2 Calculate the mean (average) and relative standard deviation
(RSD) of the response factors. If the RSD is less than 15%, linearity
through the origin can be assumed and the average RF can be used for
calculations. Alternatively, the results can be used to prepare a
calibration curve of response ratios, As/Ais, vs.
concentration ratios, Cs/Cis, for the analyte. A
minimum of six concentration levels is required for a non-linear (e.g.,
quadratic) regression. If used, the regression must be weighted
inversely proportional to concentration, and the correlation
coefficient of the weighted regression must be greater than 0.99. The
relative standard error (Reference 11) may also be used as an
acceptance criterion. As with the RSD, the RSE must be less than 15%.
If an RSE less than 15% cannot be achieved for a quadratic regression,
system performance is unacceptable and the system must be adjusted and
re-calibrated.
7.7 Second source standard--After the calibration curves are
analyzed, analyze a second source standard at the mid-level
concentration. This standard confirms the accuracy of the calibration
curve. The concentrations must be within 20% difference of the true
value. If the observed concentration exceeds this criteria, a third
source may be analyzed to determine which standard was not accurate,
and subsequent corrective actions taken.
7.8 The working calibration curve, CF, or RF must be verified at
the beginning and end of each 24-hour shift by the analysis of a mid-
level calibration standard or the combined QC standard (Section
6.8.2.1.3). Requirements for calibration verification are given in
Section 13.6 and Table 4. Alternatively, calibration verification may
be performed after a set number of injections (e.g., every 20
injections), to include injection of extracts of field samples, QC
samples, instrument blanks, etc. (i.e., it is based on the number of
injections performed, not sample extracts).
Note: The 24-hour shift begins after analysis of the combined
QC standard (calibration verification) and ends 24 hours later. The
ending calibration verification standard is run immediately after
the last sample run during the 24-hour shift, so the beginning and
ending calibration verifications are outside of the 24-hour shift.
If calibration verification is based on the number of injections
instead of time, then the ending verification standard for one group
of 20 injections may be used as the beginning
[[Page 9010]]
verification for the next group of 20 injections.
7.9 Florisil[supreg] calibration--The column cleanup procedure in
Section 11.3 utilizes Florisil column chromatography. Florisil[supreg]
from different batches or sources may vary in adsorptive capacity. To
standardize the amount of Florisil[supreg] which is used, use of the
lauric acid value (Reference 11) is suggested. The referenced procedure
determines the adsorption from a hexane solution of lauric acid (mg)
per g of Florisil[supreg]. The amount of Florisil[supreg] to be used
for each column is calculated by dividing 110 by this ratio and
multiplying by 20 g. If cartridges containing Florisil[supreg] are
used, then this step is not necessary.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality assurance program. The minimum requirements of this
program consist of an initial demonstration of laboratory capability
and ongoing analysis of spiked samples and blanks to evaluate and
document data quality. The laboratory must maintain records to document
the quality of data generated. Ongoing data quality checks are compared
with established performance criteria to determine if the results of
analyses meet performance requirements of this method. A quality
control check standard (LCS, Section 8.4) must be prepared and analyzed
with each batch of samples to confirm that the measurements were
performed in an in-control mode of operation. A laboratory may develop
its own performance criteria (as QC acceptance criteria), provided such
criteria are as or more restrictive than the criteria in this method.
8.1.1 The laboratory must make an initial demonstration of the
capability (IDC) to generate acceptable precision and recovery with
this method. This demonstration is detailed in Section 8.2. On a
continuing basis, the laboratory should repeat demonstration of
capability (DOC) annually.
8.1.2 In recognition of advances that are occurring in analytical
technology, and to overcome matrix interferences, the laboratory is
permitted certain options (Section 1.8 and 40 CFR 136.6(b) [Reference
12]) to improve separations or lower the costs of measurements. These
options may include alternative extraction (e.g., other solid-phase
extraction materials and formats), concentration, and cleanup
procedures, and changes in GC columns (Reference 12). Alternative
determinative techniques, such as the substitution of spectroscopic or
immunoassay techniques, and changes that degrade method performance,
are not allowed. If an analytical technique other than the techniques
specified in this method is used, that technique must have a
specificity equal to or greater than the specificity of the techniques
in this method for the analytes of interest. The laboratory is also
encouraged to participate in performance evaluation studies (see
Section 8.8).
8.1.2.1 Each time a modification listed above is made to this
method, the laboratory is required to repeat the procedure in Section
8.2. If the detection limit of the method will be affected by the
change, the laboratory is required to demonstrate that the MDLs (40 CFR
part 136, appendix B) are lower than one-third the regulatory
compliance limit or as low as the MDLs in this method, whichever are
greater. If calibration will be affected by the change, the instrument
must be recalibrated per Section 7. Once the modification is
demonstrated to produce results equivalent or superior to results
produced by this method as written, that modification may be used
routinely thereafter, so long as the other requirements in this method
are met (e.g., matrix spike/matrix spike duplicate recovery and
relative percent difference).
8.1.2.1.1 If an allowed method modification, is to be applied to a
specific discharge, the laboratory must prepare and analyze matrix
spike/matrix spike duplicate (MS/MSD) samples (Section 8.3) and LCS
samples (Section 8.4). The laboratory must include surrogates (Section
8.7) in each of the samples. The MS/MSD and LCS samples must be
fortified with the analytes of interest (Section 1.4). If the
modification is for nationwide use, MS/MSD samples must be prepared
from a minimum of nine different discharges (See Section 8.1.2.1.2),
and all QC acceptance criteria in this method must be met. This
evaluation only needs to be performed once other than for the routine
QC required by this method (for example it could be performed by the
vendor of an alternate material) but any laboratory using that specific
material must have the results of the study available. This includes a
full data package with the raw data that will allow an independent
reviewer to verify each determination and calculation performed by the
laboratory (see Section 8.1.2.2.5, items a-q).
8.1.2.1.2 Sample matrices on which MS/MSD tests must be performed
for nationwide use of an allowed modification:
(a) Effluent from a POTW
(b) ASTM D5905 Standard Specification for Substitute Wastewater
(c) Sewage sludge, if sewage sludge will be in the permit
(d) ASTM D1141 Standard Specification for Substitute Ocean Water,
if ocean water will be in the permit
(e) Untreated and treated wastewaters up to a total of nine matrix
types (see http://water.epa.gov/scitech/wastetech/guide/industry.cfm)
for a list of industrial categories with existing effluent guidelines).
At least one of the above wastewater matrix types must have at
least one of the following characteristics:
(i) Total suspended solids greater than 40 mg/L
(ii) Total dissolved solids greater than 100 mg/L
(iii) Oil and grease greater than 20 mg/L
(iv) NaCl greater than 120 mg/L
(v) CaCO3 greater than 140 mg/L
The interim acceptance criteria for MS, MSD recoveries that do not
have recovery limits specified in Table 5, and recoveries for
surrogates that do not have recovery limits specified in Table 8, must
be no wider than 60-140%, and the relative percent difference (RPD) of
the concentrations in the MS and MSD that do not have RPD limits
specified in Table 5 must be less than 30%. Alternatively, the
laboratory may use the laboratory's in-house limits if they are
tighter.
(f) A proficiency testing (PT) sample from a recognized provider,
in addition to tests of the nine matrices (Section 8.1.2.1.1).
8.1.2.2 The laboratory must maintain records of modifications made
to this method. These records include the following, at a minimum:
8.1.2.2.1 The names, titles, street addresses, telephone numbers,
and email addresses of the analyst(s) that performed the analyses and
modification, and of the quality control officer that witnessed and
will verify the analyses and modifications.
8.1.2.2.2 A list of analytes, by name and CAS Registry number.
8.1.2.2.3 A narrative stating reason(s) for the modifications.
8.1.2.2.4 Results from all quality control (QC) tests comparing the
modified method to this method, including:
(a) Calibration (Section 7).
(b) Calibration verification (Section 13.6).
(c) Initial demonstration of capability (Section 8.2).
(d) Analysis of blanks (Section 8.5).
(e) Matrix spike/matrix spike duplicate analysis (Section 8.3).
[[Page 9011]]
(f) Laboratory control sample analysis (Section 8.4).
8.1.2.2.5 Data that will allow an independent reviewer to validate
each determination by tracing the instrument output (peak height, area,
or other signal) to the final result. These data are to include:
(a) Sample numbers and other identifiers.
(b) Extraction dates.
(c) Analysis dates and times.
(d) Analysis sequence/run chronology.
(e) Sample weight or volume (Section 10).
(f) Extract volume prior to each cleanup step (Sections 10 and 11).
(g) Extract volume after each cleanup step (Section 11).
(h) Final extract volume prior to injection (Sections 10 and 12).
(i) Injection volume (Sections 12.3 and 13.2).
(j) Sample or extract dilution (Section 15.4).
(k) Instrument and operating conditions.
(l) Column (dimensions, material, etc).
(m) Operating conditions (temperatures, flow rates, etc).
(n) Detector (type, operating conditions, etc).
(o) Chromatograms and other recordings of raw data.
(p) Quantitation reports, data system outputs, and other data to
link the raw data to the results reported.
(q) A written Standard Operating Procedure (SOP)
8.1.2.2.6 Each individual laboratory wishing to use a given
modification must perform the start-up tests in Section 8.1.2 (e.g.,
DOC, MDL), with the modification as an integral part of this method
prior to applying the modification to specific discharges. Results of
the DOC must meet the QC acceptance criteria in Table 5 for the
analytes of interest (Section 1.4), and the MDLs must be equal to or
lower than the MDLs in Table 3 for the analytes of interest.
8.1.3 Before analyzing samples, the laboratory must analyze a blank
to demonstrate that interferences from the analytical system, lab ware,
and reagents, are under control. Each time a batch of samples is
extracted or reagents are changed, a blank must be extracted and
analyzed as a safeguard against laboratory contamination. Requirements
for the blank are given in Section 8.5.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of 5% of all samples in a batch (Section 22.2) or from a given
site or discharge, in duplicate, to monitor and evaluate method and
laboratory performance on the sample matrix. This procedure is
described in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
analysis of a quality control check sample (laboratory control sample,
LCS; on-going precision and recovery sample, OPR) that the measurement
system is in control. This procedure is described in Section 8.4.
8.1.6 The laboratory should maintain performance records to
document the quality of data that is generated. This procedure is given
in Section 8.7.
8.1.7 The large number of analytes tested in performance tests in
this method present a substantial probability that one or more will
fail acceptance criteria when all analytes are tested simultaneously,
and a re-test (reanalysis) is allowed if this situation should occur.
If, however, continued re-testing results in further repeated failures,
the laboratory should document the failures and either avoid reporting
results for the analytes that failed or report the problem and failures
with the data. A QC failure does not relieve a discharger or permittee
of reporting timely results.
8.2 Demonstration of capability (DOC)--To establish the ability to
generate acceptable recovery and precision, the laboratory must perform
the DOC in Sections 8.2.1 through 8.2.6 for the analytes of interest
initially and in an on-going manner at least annually. The laboratory
must also establish MDLs for the analytes of interest using the MDL
procedure at 40 CFR part 136, appendix B. The laboratory's MDLs must be
equal to or lower than those listed in Table 3 or lower than one-third
the regulatory compliance limit, whichever is greater. For MDLs not
listed in Tables 1 or 2, the laboratory must determine the MDLs using
the MDL procedure at 40 CFR part 136, appendix B under the same
conditions used to determine the MDLs for the analytes listed in Tables
1 and 2. All procedures used in the analysis, including cleanup
procedures, must be included in the DOC.
8.2.1 For the DOC, a QC check sample concentrate containing each
analyte of interest (Section 1.4) is prepared in a water-miscible
solvent using the solution in Section 6.8.3. The QC check sample
concentrate must be prepared independently from those used for
calibration, but should be from the same source and prepared in a
water-miscible solvent. The concentrate should produce concentrations
of the analytes of interest in water at or below the mid-point of the
calibration range. Multiple solutions may be required.
Note: QC check sample concentrates are no longer available from
EPA.
8.2.2 Using a pipet or syringe, prepare four QC check samples by
adding an appropriate volume of the concentrate and of the surrogate(s)
to each of four 1-L aliquots of reagent water. Swirl or stir to mix.
8.2.3 Extract and analyze the well-mixed QC check samples according
to the method beginning in Section 10.
8.2.4 Calculate the average percent recovery (XX) and the standard
deviation (s) of the percent recovery for each analyte using the four
results.
8.2.5 For each analyte, compare s and XX with the corresponding
acceptance criteria for precision and recovery in Table 4. For analytes
in Table 2 that are not listed in Table 4, QC acceptance criteria must
be developed by the laboratory. EPA has provided guidance for
development of QC acceptance criteria (References 12 and 13). If s and
XX for all analytes of interest meet the acceptance criteria, system
performance is acceptable and analysis of blanks and samples can begin.
If any individuals exceeds the precision limit or any individual XX
falls outside the range for recovery, system performance is
unacceptable for that analyte.
Note: The large number of analytes in Tables 1 and 2 present a
substantial probability that one or more will fail at least one of
the acceptance criteria when many or all analytes are determined
simultaneously.
8.2.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, repeat the test for only the analytes that
failed. If results for these analytes pass, system performance is
acceptable and analysis of samples and blanks may proceed. If one or
more of the analytes again fail, system performance is unacceptable for
the analytes that failed the acceptance criteria. Correct the problem
and repeat the test (Section 8.2). See Section 8.1.7 for disposition of
repeated failures.
Note: To maintain the validity of the test and re-test, system
maintenance and/or adjustment is not permitted between this pair of
tests.
8.3 Matrix spike and matrix spike duplicate (MS/MSD)--The
laboratory must, on an ongoing basis, spike at least 5% of the samples
in duplicate from each sample site being monitored to assess accuracy
(recovery and precision). The data user should identify the sample and
the analytes of interest (Section 1.4) to be spiked. If direction
cannot be obtained, the laboratory must spike at least one
[[Page 9012]]
sample in duplicate per extraction batch of up to 20 samples (Section
22.2) with the analytes in Table 1. Spiked sample results should be
reported only to the data user whose sample was spiked, or as requested
or required by a regulatory/control authority.
8.3.1. If, as in compliance monitoring, the concentration of a
specific analyte will be checked against a regulatory concentration
limit, the concentration of the spike should be at that limit;
otherwise, the concentration of the spike should be one to five times
higher than the background concentration determined in Section 8.3.2,
at or near the midpoint of the calibration range, or at the
concentration in the LCS (Section 8.4) whichever concentration would be
larger. When no information is available, the mid-point of the
calibration may be used, as long as it is the same or less than the
regulatory limit.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of the each analyte of interest. If necessary to meet
the requirement in Section 8.3.1, prepare a new check sample
concentrate (Section 8.2.1) appropriate for the background
concentration. Spike and analyze two additional sample aliquots of the
same volume as the original sample, and determine the concentrations
after spiking (A1 and A2) of each analyte.
Calculate the percent recoveries (P1 and P2) as:
[GRAPHIC] [TIFF OMITTED] TP19FE15.002
where T is the known true value of the spike.
Also calculate the relative percent difference (RPD) between the
concentrations (A1 and A2):
[GRAPHIC] [TIFF OMITTED] TP19FE15.003
8.3.3 Compare the percent recoveries (P1 and
P2) and the RPD for each analyte in the MS/MSD aliquots with
the corresponding QC acceptance criteria for recovery (P) and RPD in
Table 4.
If any individual P falls outside the designated range for recovery
in either aliquot, or the RPD limit is exceeded, the result for the
analyte in the unspiked sample is suspect and may not be reported or
used for permitting or regulatory compliance. See Section 8.1.7 for
disposition of failures.
For analytes in Table 2 not listed in Table 5, QC acceptance
criteria must be developed by the laboratory. EPA has provided guidance
for development of QC acceptance criteria (References 12 and 13).
8.3.4 After analysis of a minimum of 20 MS/MSD samples for each
target analyte and surrogate, the laboratory must calculate and apply
in-house QC limits for recovery and RPD of future MS/MSD samples
(Section 8.3). The QC limits for recovery are calculated as the mean
observed recovery 3 standard deviations, and the upper QC
limit for RPD is calculated as the mean RPD plus 3 standard deviations
of the RPDs. The in-house QC limits must be updated at least every two
years and re-established after any major change in the analytical
instrumentation or process. At least 80% of the analytes tested in the
MS/MSD must have in-house QC acceptance criteria that are tighter than
those in Table 4. If an in-house QC limit for the RPD is greater than
the limit in Table 4, then the limit in Table 4 must be used.
Similarly, if an in-house lower limit for recovery is below the lower
limit in Table 4, then the lower limit in Table 4 must be used, and if
an in-house upper limit for recovery is above the upper limit in Table
4, then the upper limit in Table 4 must be used. The laboratory must
evaluate surrogate recovery data in each sample against its in-house
surrogate recovery limits. The laboratory may use 60-140% as interim
acceptance criteria for surrogate recoveries until in-house limits are
developed.
8.4 Laboratory control sample (LCS)--A QC check sample (laboratory
control sample, LCS; on-going precision and recovery sample, OPR)
containing each single-component analyte of interest (Section 1.4) must
be extracted, concentrated, and analyzed with each extraction batch of
up to 20 samples (Section 3.1) to demonstrate acceptable recovery of
the analytes of interest from a clean sample matrix. If multi-peak
analytes are required, extract and prepare at least one as an LCS for
each batch. Alternatively, the laboratory may set up a program where
multi-peak LCS is rotated with a single-peak LCS.
8.4.1 Prepare the LCS by adding QC check sample concentrate
(Section 8.2.1) to reagent water. Include all analytes of interest
(Section 1.4) in the LCS. The volume of reagent water must be the same
as the nominal volume used for the sample, the DOC (Section 8.2), the
blank (Section 8.5), and the MS/MSD (Section 8.3). Also add a volume of
the surrogate solution (Section 6.8.6).
8.4.2 Analyze the LCS prior to analysis of samples in the
extraction batch (Section 3.1). Determine the concentration (A) of each
analyte. Calculate the percent recovery as:
[GRAPHIC] [TIFF OMITTED] TP19FE15.004
where T is the true value of the concentration in the LCS.
8.4.3 For each analyte, compare the percent recovery (P) with its
corresponding QC acceptance criterion in Table 4. For analytes of
interest in Table 2 not listed in Table 4, use the QC acceptance
criteria developed for the MS/MSD (Section 8.3.3.2). If the recoveries
for all analytes of interest fall within the designated ranges,
analysis of blanks and field samples may proceed. If any individual
recovery falls outside the range, proceed according to Section 8.4.4.
Note: The large number of analytes in Tables 1 and 2 present a
substantial probability that one or more will fail the acceptance
criteria when all analytes are tested simultaneously. Because a re-
test is allowed in event of failure (Sections 8.1.7 and 8.4.4), it
may be prudent to extract and analyze two LCSs together and evaluate
results of the second analysis against the QC acceptance criteria
only if an analyte fails the first test.
8.4.4 Repeat the test only for those analytes that failed to meet
the acceptance criteria (P). If these analytes now pass, system
performance is acceptable and analysis of blanks and samples may
proceed. Repeated failure, however, will confirm a general problem with
the measurement system. If this occurs, repeat the test using a fresh
LCS (Section 8.2.1) or an LCS prepared with a fresh QC check sample
concentrate (Section 8.2.1), or perform and document system repair.
Subsequent to repair, repeat the LCS test (Section 8.4). See Section
8.1.7 for disposition of repeated failures.
8.4.5 After analysis of 20 LCS samples, the laboratory must
calculate and apply in-house QC limits for recovery to future LCS
samples (Section 8.4). Limits for recovery in the LCS are calculated as
the mean recovery 3 standard deviations. A minimum of 80%
of the analytes tested for in the LCS must have QC acceptance criteria
tighter than those in Table 4. As noted in Section 8.6, each laboratory
must develop QC acceptance criteria for the surrogates they employ. The
laboratory should use 60-140% as interim acceptance criteria for
recoveries of spiked analytes and surrogates until in-house LCS and
surrogate limits are developed. If an in-house lower limit for LCS
recovery is lower than the lower limit in Table 4, the lower limit in
Table 4 must be used, and if an in-house upper limit for recovery is
higher than the upper limit in Table 4, the upper limit in Table 4 must
be used.
[[Page 9013]]
8.5 Blank--Extract and analyze a blank with each extraction batch
(Section 22.2) to demonstrate that the reagents and equipment used for
preparation and analysis are free from contamination.
8.5.1 Prepare the blank from reagent water and spike it with the
surrogates. The volume of reagent water must be the same as the volume
used for samples, the DOC (Section 8.2), the LCS (Section 8.4), and the
MS/MSD (Section 8.3). Extract, concentrate, and analyze the blank using
the same procedures and reagents used for the samples, LCS, and MS/MSD
in the batch. Analyze the blank immediately after analysis of the LCS
(Section 8.4) and prior to analysis of the MS/MSD and samples to
demonstrate freedom from contamination.
8.5.2 If any analyte of interest is found in the blank at a
concentration greater than the MDL for the analyte, at a concentration
greater than one-third the regulatory compliance limit, or at a
concentration greater than one-tenth the concentration in a sample in
the batch (Section 3.1), whichever is greatest, analysis of samples
must be halted and samples in the batch must be re-extracted and the
extracts reanalyzed. Samples in a batch must be associated with an
uncontaminated blank before the results for those samples may be
reported or used for permitting or regulatory compliance purposes. If
re-testing of blanks results in repeated failures, the laboratory
should document the failures and report the problem and failures with
the data.
8.6 Surrogate recovery--As a quality control check, the laboratory
must spike all samples with the surrogate standard spiking solution
(Section 6.8.6) per Section 10.2.2 or 10.4.2, analyze the samples, and
calculate the percent recovery of each surrogate. QC acceptance
criteria for surrogates must be developed by the laboratory. EPA has
provided guidance for development of QC acceptance criteria (References
12 and 13). If any recovery fails its criterion, attempt to find and
correct the cause of the failure, and if sufficient volume is
available, re-extract another aliquot of the affected sample. Surrogate
recoveries from the blank and LCS may be used as pass/fail criteria by
the laboratory or as required by a regulatory authority, or may be used
to diagnose problems with the analytical system.
8.7 As part of the QC program for the laboratory, it is suggested
but not required that method accuracy for wastewater samples be
assessed and records maintained. After analysis of five or more spiked
wastewater samples as in Section 8.4, calculate the average percent
recovery (XX) and the standard deviation of the percent recovery (sp).
Express the accuracy assessment as a percent interval from XX -2sp to
XX + 2sp. For example, if XX = 90% and sp = 10%, the accuracy interval
is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis to ensure process control (e.g., after each
5-10 new accuracy measurements).
8.8 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and
the nature of the samples. Field duplicates may be analyzed to assess
the precision of environmental measurements. When doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques
such as gas chromatography with another dissimilar column, specific
element detector, or mass spectrometer must be used. Whenever possible,
the laboratory should analyze standard reference materials and
participate in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Collect samples as grab samples in glass bottles, or in
refrigerated bottles using automatic sampling equipment. Collect 1-L of
ambient waters, effluents, and other aqueous samples. If high
concentrations of the analytes of interest are expected (e.g., for
untreated effluents or in-process waters), collect a smaller volume
(e.g., 250 mL), but not less than 100 mL, in addition to the 1-L
sample. Follow conventional sampling practices, except do not pre-rinse
the bottle with sample before collection. Automatic sampling equipment
must be as free as possible of polyvinyl chloride or other tubing or
other potential sources of contamination. If needed, collect additional
sample(s) for the MS/MSD (Section 8.3).
9.2 Ice or refrigerate the sample at <6 [deg]C from the time of
collection until extraction, but do not freeze. If aldrin is to be
determined and residual chlorine is present, add 80 mg/L of sodium
thiosulfate but do not add excess. Any method suitable for field use
may be employed to test for residual chlorine (Reference 14). If sodium
thiosulfate interferes in the determination of the analytes, an
alternative preservative (e.g., ascorbic acid or sodium sulfite) may be
used.
9.3 Extract all samples within seven days of collection and
completely analyze within 40 days of extraction (Reference 1). If the
sample will not be extracted within 72 hours of collection, adjust the
sample pH to range of 5.0-9.0 with sodium hydroxide solution or
sulfuric acid. Record the volume of acid or base used.
10. Sample Extraction
10.1 This section contains procedures for separatory funnel liquid-
liquid extraction (SFLLE, Section 10.2), continuous liquid-liquid
extraction (CLLE, Section 10.4), and disk-based solid-phase extraction
(SPE, Section 10.5). SFLLE is faster, but may not be as effective as
CLLE for extracting polar analytes. SFLLE is labor intensive and may
result in formation of emulsions that are difficult to break. CLLE is
less labor intensive, avoids emulsion formation, but requires more time
(18-24 hours), more hood space, and may require more solvent. SPE can
be faster, unless the particulate load in an aqueous sample is so high
that it slows the filtration process. If an alternative extraction
scheme to those detailed in this method is used, all QC tests must be
performed and all QC acceptance criteria must be met with that
extraction scheme as an integral part of this method.
10.2 Separatory funnel liquid-liquid extraction (SFLLE).
10.2.1 The SFLLE procedure below assumes a sample volume of 1 L.
When a different sample volume is extracted, adjust the volume of
methylene chloride accordingly.
10.2.2 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into the
separatory funnel. Pipet the surrogate standard spiking solution
(Section 6.8.6) into the separatory funnel. If the sample will be used
for the LCS or MS or MSD, pipet the appropriate QC check sample
concentrate (Section 8.2.1) into the separatory funnel. Mix well. If
the sample arrives in a larger sample bottle, 1 L may be measured in a
graduated cylinder, then added to the separatory funnel.
Note: Instances in which the sample is collected in an
oversized bottle should be reported by the laboratory to the data
user. Of particular concern is that fact that this practice
precludes rinsing the empty bottle with solvent as described below,
which could leave hydrophobic pesticides on the wall of the bottle,
and underestimate the actual sample concentrations.
10.2.3 Add 60 mL of methylene chloride to the sample bottle, seal,
and shake for 30 seconds to rinse the inner surface. Transfer the
solvent to the separatory funnel and extract the sample by shaking the
funnel for two
[[Page 9014]]
minutes with periodic venting to release excess pressure. Allow the
organic layer to separate from the water phase for a minimum of 10
minutes. If an emulsion forms and the emulsion interface between the
layers is more than one-third the volume of the solvent layer, employ
mechanical techniques to complete the phase separation. The optimum
technique depends upon the sample, but may include stirring, filtration
of the emulsion through glass wool, centrifugation, freezing, or other
physical methods. Collect the methylene chloride extract in a flask. If
the emulsion cannot be broken (recovery of less than 80% of the
methylene chloride, corrected for the water solubility of methylene
chloride), transfer the sample, solvent, and emulsion into the
extraction chamber of a continuous extractor and proceed as described
in Section 10.4.
10.2.4 Add a second 60-mL volume of methylene chloride to the
sample bottle and repeat the extraction procedure a second time,
combining the extracts in the flask. Perform a third extraction in the
same manner. Proceed to macro-concentration (Section 10.3.1).
10.2.5 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to an appropriately
sized graduated cylinder. Record the sample volume to the nearest 5 mL.
Sample volumes may also be determined by weighing the container before
and after extraction or filling to the mark with water.
10.3 Concentration.
10.3.1 Macro concentration.
10.3.1.1 Assemble a Kuderna-Danish (K-D) concentrator by attaching
a 10-mL concentrator tube to a 500-mL evaporative flask. Other
concentration devices or techniques may be used in place of the K-D
concentrator so long as the requirements of Section 8.2 are met.
10.3.1.2 Pour the extract through a solvent-rinsed drying column
containing about 10 cm of anhydrous sodium sulfate, and collect the
extract in the K-D concentrator. Rinse the flask and column with 20-30
mL of methylene chloride to complete the quantitative transfer.
10.3.1.3 If no cleanup is to be performed on the sample, add 500
[micro]L (0.5 mL) of isooctane to the extract to act as a keeper during
concentration.
10.3.1.4 Add one or two clean boiling chips and attach a three-ball
Snyder column to the K-D evaporative flask. Pre-wet the Snyder column
by adding about 1 mL of methylene chloride to the top. Place the K-D
apparatus on a hot water bath (60-65 [deg]C) so that the concentrator
tube is partially immersed in the hot water, and the entire lower
rounded surface of the flask is bathed with hot vapor. Adjust the
vertical position of the apparatus and the water temperature as
required to complete the concentration in 15-20 minutes. At the proper
rate of evaporation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the apparent
volume of liquid reaches 1 mL or other determined amount, remove the K-
D apparatus from the water bath and allow it to drain and cool for at
least 10 minutes.
10.3.1.5 If the extract is to be cleaned up by a procedure for
sulfur removal, remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1 to 2 mL of methylene
chloride. A 5-mL syringe is recommended for this operation. Adjust the
final volume to 10 mL in methylene chloride and proceed to sulfur
removal (Section 11.5). If the extract is to cleaned up using one of
the other cleanup procedures or is to be injected into the GC, proceed
to Kuderna-Danish micro-concentration (Section 10.3.2) or nitrogen
evaporation and solvent exchange (Section 10.3.3).
10.3.2 Kuderna-Danish micro concentration.
10.3.2.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two-ball micro-Snyder column. Pre-wet
the Snyder column by adding about 0.5 mL of methylene chloride to the
top. Place the K-D apparatus on a hot water bath (60-65 [deg]C) so that
the concentrator tube is partially immersed in hot water. Adjust the
vertical position of the apparatus and the water temperature as
required to complete the concentration in 5-10 minutes. At the proper
rate of distillation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the apparent
volume of liquid reaches approximately 1 mL or other required amount,
remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 minutes. Remove the Snyder column and rinse the
flask and its lower joint into the concentrator tube with approximately
0.2 mL of methylene chloride, and proceed to Section 10.3.3 for
nitrogen evaporation and solvent exchange.
10.3.3 Nitrogen evaporation and solvent exchange--Extracts to be
subjected to solid-phase cleanup (SPE) are exchanged into 1.0 mL of the
SPE elution solvent (Section 6.7.2.2). Extracts to be subjected to
Florisil[supreg] or alumina cleanups are exchanged into hexane.
Extracts that have been cleaned up and are ready for analysis are
exchanged into isooctane or hexane, to match the solvent used for the
calibration standards.
10.3.3.1 Transfer the vial containing the sample extract to the
nitrogen evaporation (blowdown) device (Section 5.2.5.2). Lower the
vial into a 50-55 [deg]C water bath and begin concentrating. During the
solvent evaporation process, do not allow the extract to become dry.
Adjust the flow of nitrogen so that the surface of the solvent is just
visibly disturbed. A large vortex in the solvent may cause analyte
loss.
10.3.3.2 Solvent exchange.
10.3.3.2.1 When the volume of the liquid is approximately 500
[mu]L, add 2 to 3 mL of the desired solvent (SPE elution solvent for
SPE cleanup, hexane for Florisil or alumina, or isooctane for final
injection into the GC) and continue concentrating to approximately 500
[mu]L. Repeat the addition of solvent and concentrate once more.
10.3.3.3.2 Adjust the volume of an extract to be cleaned up by SPE,
Florisil[supreg], or alumina to 1.0 mL. Proceed to extract cleanup
(Section 11).
10.3.3.3 Extracts that have been cleaned up and are ready for
analysis--Adjust the final extract volume to be consistent with the
volume extracted and the sensitivity desired. The goal is for a full-
volume sample (e.g., 1-L) to have a final extract volume of 10 mL, but
other volumes may be used.
10.3.4 Transfer the concentrated extract to a vial with
fluoropolymer-lined cap. Seal the vial and label with the sample
number. Store in the dark at room temperature until ready for GC
analysis. If GC analysis will not be performed on the same day, store
the vial in the dark at 4 [deg]C. Analyze the extract by GC per the
procedure in Section 12.
10.4 Continuous liquid/liquid extraction (CLLE).
10.4.1 Use CLLE when experience with a sample from a given source
indicates an emulsion problem, or when an emulsion is encountered using
SFLLE. CLLE may be used for all samples, if desired.
10.4.2 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Transfer the sample to the
continuous extractor and, using a pipet, add surrogate standard spiking
solution. If the sample will be used for the LCS, MS, or MSD, pipet the
appropriate check sample concentrate (Section 8.2.1 or 8.3.2) into the
separatory funnel. Mix well. Add 60 mL of methylene chloride to the
sample bottle, seal, and shake for 30 seconds to rinse the inner
surface. Transfer the solvent to the extractor.
10.4.3 Repeat the sample bottle rinse with two additional 50-100 mL
portions
[[Page 9015]]
of methylene chloride and add the rinses to the extractor.
10.4.4 Add a suitable volume of methylene chloride to the
distilling flask (generally 200-500 mL) and sufficient reagent water to
ensure proper operation of the extractor, and extract the sample for
18-24 hours. A shorter or longer extraction time may be used if all QC
acceptance criteria are met. Test and, if necessary, adjust the pH of
the water during the second or third hour of the extraction. After
extraction, allow the apparatus to cool, then detach the distilling
flask. Dry, concentrate, solvent exchange, and transfer the extract to
a vial with fluoropolymer-lined cap, per Section 10.3.
10.4.5 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to an appropriately
sized graduated cylinder. Record the sample volume to the nearest 5 mL.
Sample volumes may also be determined by weighing the container before
and after extraction or filling to the mark with water.
10.5 Solid-phase extraction of aqueous samples.
The steps in this section address the extraction of aqueous field
samples using disk-based solid-phase extraction (SPE) media, based on
an ATP approved by EPA in 1995 (Reference 20). This application of SPE
is distinct from that used in this method for the cleanup of sample
extracts in Section 11.2. Analysts must be careful not to confuse the
equipment, supplies, or the procedural steps from these two different
uses of SPE.
Note: Changes to the extraction conditions described below may
be made by the laboratory under the allowance for method flexibility
described in Section 8.1, provided that the performance requirements
in Section 8.2 are met. However, changes in SPE materials, formats,
and solvents must meet the requirements in Section 8.1.2 and its
subsections.
10.5.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. If the sample contains
particulates, let stand to settle out the particulates before
extraction.
10.5.2 Extract the sample as follows:
10.5.2.1 Place a 90-mm standard filter apparatus on a vacuum
filtration flask or manifold and attach to a vacuum source. The vacuum
gauge should read at least 25 in. of mercury when all valves are
closed. Position a 90-mm C18 extraction disk onto the filter screen.
Wet the entire disk with methanol. To aid in filtering samples with
particulates, a 1-[mu]m glass fiber filter or Empore[supreg] Filter Aid
400 can be placed on the top of the disk and wetted with methanol.
Install the reservoir and clamp. Resume vacuum to dry the disk.
Interrupt the vacuum. Wash the disk and reservoir with 20 mL of
methylene chloride. Resume the vacuum briefly to pull methylene
chloride through the disk. Interrupt the vacuum and allow the disk to
soak for about a minute. Resume vacuum and completely dry the disk.
10.5.2.2 Condition the disk with 20 mL of methanol. Apply vacuum
until nearly all the solvent has passed through the disk, interrupting
it while solvent remains on the disk. Allow the disk to soak for about
a minute. Resume vacuum to pull most of the methanol through, but
interrupting it to leave a layer of methanol on the surface of the
disk. Do not allow disk to dry.
For uniform flow and good recovery, it is critical the disk not be
allowed to dry from now until the end of the extraction. Discard waste
solvent. Rinse the disk with 20 mL of deionized water. Resume vacuum to
pull most of the water through, but interrupt it to leave a layer of
water on the surface of the disk. Do not allow the disk to dry. If disk
does dry, recondition with methanol as above.
10.5.2.3 Add the water sample to the reservoir and immediately
apply the vacuum. If particulates have settled in the sample, gently
decant the clear layer into the apparatus until most of the sample has
been processed. Then pour the remainder including the particulates into
the reservoir. Empty the sample bottle completely. When the filtration
is complete, dry the disk for three minutes. Turn off the vacuum.
10.5.3 Discard sample filtrate. Insert tube to collect the eluant.
The tube should fit around the drip tip of the base. Reassemble the
apparatus. Add 5.0 mL of acetone to the center of the disk, allowing it
to spread evenly over the disk. Turn the vacuum on and quickly off when
the filter surface nears dryness but still remains wet. Allow to soak
for 15 seconds. Add 20 mL of methylene chloride to the sample bottle,
seal and shake to rinse the inside of the bottle. Transfer the
methylene chloride from the bottle to the filter. Resume the vacuum
slowly so as to avoid splashing.
Interrupt the vacuum when the filter surface nears dryness but
still remains wet. Allow disk to soak in solvent for 20 seconds. Rinse
the reservoir glass and disk with 10 mL of methylene chloride. Resume
vacuum slowly. Interrupt vacuum when disk is covered with solvent.
Allow to soak for 20 seconds. Resume vacuum to dry the disk. Remove the
sample tube.
10.5.4 Dry, concentrate, solvent exchange, and transfer the extract
to a vial with fluoropolymer-lined cap, per Section 10.3.
10.5.5 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to an appropriately
sized graduated cylinder. Record the sample volume to the nearest 5 mL.
Sample volumes may also be determined by weighing the container before
and after extraction or filling to the mark with water.
11. Extract Cleanup
11.1 Cleanup may not be necessary for a relatively clean sample
matrix. If particular circumstances require the use of a cleanup
procedure, the laboratory may use any or all of the procedures below or
any other appropriate procedure (e.g., gel permeation chromatography).
However, the laboratory must first repeat the tests in Sections 8.2,
8.3, and 8.4 to demonstrate that the requirements of those sections can
be met using the cleanup procedure(s) as an integral part of this
method. This is particularly important when the target analytes for the
analysis include any of the single component pesticides in Table 2,
because some cleanups have not been optimized for all of those
analytes.
11.1.1 The solid-phase cartridge (Section 11.2) removes polar
organic compounds such as phenols.
11.1.2 The Florisil[supreg] column (Section 11.3) allows for
selected fractionation of the organochlorine analytes and will also
eliminate polar interferences.
11.1.3 Alumina column cleanup (Section 11.4) also removes polar
materials.
11.1.4 Elemental sulfur, which interferes with the electron capture
gas chromatography of some of the pesticides, may be removed using
activated copper, or TBA sulfite. Sulfur removal (Section 11.5) is
required when sulfur is known or suspected to be present. Some
chlorinated pesticides which also contain sulfur may be removed by this
cleanup.
11.2 Solid-phase extraction (SPE) as a cleanup.
In order to use the C18 SPE cartridge in Section 5.5.3.5 as a
cleanup procedure, the sample extract must be exchanged from methylene
chloride to methylene chloride: acetonitrile:hexane. Follow the solvent
exchange steps in Section 10.3.3.2 prior to attempting solid-phase
cleanup.
Note: This application of SPE is distinct from that used in
this method for the extraction of aqueous samples in Section 10.5.
Analysts must be careful not to confuse the equipment, supplies, or
procedural steps from these two different uses of SPE.
11.2.1 Setup.
[[Page 9016]]
11.2.1.1 Attach the VacElute Manifold (Section 5.5.3.2) to a water
aspirator or vacuum pump with the trap and gauge installed between the
manifold and vacuum source.
11.2.1.2 Place the SPE cartridges in the manifold, turn on the
vacuum source, and adjust the vacuum to 5 to 10 psi.
11.2.2 Cartridge washing--Pre-elute each cartridge prior to use
sequentially with 10-mL portions each of hexane, methanol, and water
using vacuum for 30 seconds after each eluting solvent. Follow this
pre-elution with 1 mL methylene chloride and three 10-mL portions of
the elution solvent (Section 6.7.2.2) using vacuum for 5 minutes after
each eluting solvent. Tap the cartridge lightly while under vacuum to
dry between solvent rinses. The three portions of elution solvent may
be collected and used as a cartridge blank, if desired. Finally, elute
the cartridge with 10 mL each of methanol and water, using the vacuum
for 30 seconds after each eluant.
11.2.3 Extract cleanup.
11.2.3.1 After cartridge washing (Section 11.2.2), release the
vacuum and place the rack containing the 50-mL volumetric flasks
(Section 5.5.3.4) in the vacuum manifold. Re-establish the vacuum at 5
to 10 psi.
11.2.3.2 Using a pipette or a 1-mL syringe, transfer 1.0 mL of
extract to the SPE cartridge. Apply vacuum for five minutes to dry the
cartridge. Tap gently to aid in drying.
11.2.3.3 Elute each cartridge into its volumetric flask
sequentially with three 10-mL portions of the methylene
chloride:acetonitrile:hexane (50:3:47) elution solvent (Section
6.7.2.2), using vacuum for five minutes after each portion. Collect the
eluants in the 50-mL volumetric flasks.
11.2.3.4 Release the vacuum and remove the 50-mL volumetric flasks.
11.2.3.5 Concentrate the eluted extracts per Section 10.3.
11.3 Florisil[supreg].
In order to use Florisil cleanup, the sample extract must be
exchanged from methylene chloride to hexane. Follow the solvent
exchange steps in Section 10.3.3.2 prior to attempting Florisil[supreg]
cleanup.
Note: Alternative formats for this cleanup may be used by the
laboratory, including cartridges containing Florisil[supreg]. If an
alternative format is used, consult the manufacturer's instructions
and develop a formal documented procedure to replace the steps in
Section 11.3 of this method and demonstrate that the alternative
meets the relevant quality control requirements of this method.
11.3.1 If the chromatographic column does not contain a frit at the
bottom, place a small plug of pre-cleaned glass wool in the column
(Section 5.2.4) to retain the Florisil[supreg]. Place the mass of
Florisil[supreg] (nominally 20 g) predetermined by calibration (Section
7.9 and Table 6) in a chromatographic column. Tap the column to settle
the Florisil[supreg] and add 1 to 2 cm of granular anhydrous sodium
sulfate to the top.
11.3.2 Add 60 mL of hexane to wet and rinse the sodium sulfate and
Florisil[supreg]. Just prior to exposure of the sodium sulfate layer to
the air, stop the elution of the hexane by closing the stopcock on the
chromatographic column. Discard the eluant.
11.3.3 Transfer the concentrated extract (Section 10.3.3) onto the
column. Complete the transfer with two 1-mL hexane rinses, drawing the
extract and rinses down to the level of the sodium sulfate.
11.3.4 Place a clean 500-mL K-D flask and concentrator tube under
the column. Elute Fraction 1 with 200 mL of 6% (v/v) ethyl ether in
hexane at a rate of approximately 5 mL/min. Remove the K-D flask and
set it aside for later concentration. Elute Fraction 2 with 200 mL of
15% (v/v) ethyl ether in hexane into a second K-D flask. Elute Fraction
3 with 200 mL of 50% (v/v) ethyl ether in hexane into a third K-D
flask. The elution patterns for the pesticides and PCBs are shown in
Table 6.
11.3.5 Concentrate the fractions as in Section 10.3, except use
hexane to prewet the column and set the water bath at about 85 [deg]C.
When the apparatus is cool, remove the Snyder column and rinse the
flask and its lower joint into the concentrator tube with hexane.
Adjust the volume of Fraction 1 to approximately 10 mL for sulfur
removal (Section 11.5), if required; otherwise, adjust the volume of
the fractions to 10 mL, 1.0 mL, or other volume needed for the
sensitivity desired. Analyze the concentrated extract by gas
chromatography (Section 12).
11.4 Alumina.
The sample extract must be exchanged from methylene chloride to
hexane. Follow the solvent exchange steps in Section 10.3.3.2 prior to
attempting alumina cleanup.
11.4.1 If the chromatographic column does not contain a frit at the
bottom, place a small plug of pre-cleaned glass wool in the
chromatographic column (Section 5.2.4) to retain the alumina. Add 10 g
of alumina (Section 6.7.3) on top of the plug. Tap the column to settle
the alumina. Place 1-2 g of anhydrous sodium sulfate on top of the
alumina.
11.4.2 Close the stopcock and fill the column to just above the
sodium sulfate with hexane. Add 25 mL of hexane. Open the stopcock and
adjust the flow rate of hexane to approximately 2 mL/min. Do not allow
the column to go dry throughout the elutions.
11.4.3 When the level of the hexane is at the top of the column,
quantitatively transfer the extract to the column. When the level of
the extract is at the top of the column, slowly add 25 mL of hexane and
elute the column to the level of the sodium sulfate. Discard the
hexane.
11.4.4 Place a K-D flask (Section 5.2.5.1.2) under the column and
elute the pesticides with approximately 150 mL of hexane:ethyl ether
(80:20 v/v). It may be necessary to adjust the volume of elution
solvent for slightly different alumina activities.
11.4.5 Concentrate the extract per Section 10.3.
11.5 Sulfur removal--Elemental sulfur will usually elute in
Fraction 1 of the Florisil[supreg] column cleanup. If Florisil[supreg]
cleanup is not used, or to remove sulfur from any of the
Florisil[supreg] fractions, use one of the sulfur removal procedures
below. These procedures may be applied to extracts in hexane, ethyl
ether, or methylene chloride.
Note: Separate procedures using copper or TBA sulfite are
provided in this section for sulfur removal. They may be used
separately or in combination, if desired.
11.5.1 Removal with copper (Reference 15).
Note: Some of the analytes in Table 2 are not amenable to sulfur
removal with copper (e.g., atrazine and diazinon). Therefore, before
using copper to remove sulfur from an extract that will be analyzed
for any of the non-PCB analytes in Table 2, the laboratory must
demonstrate that the analytes can be extracted from an aqueous
sample matrix that contains sulfur and recovered from an extract
treated with copper. Acceptable performance can be demonstrated
through the preparation and analysis of a matrix spike sample that
meets the QC requirements for recovery.
11.5.1.1 Quantitatively transfer the extract to a 40- to 50-mL
flask or bottle. If there is evidence of water in the K-D or round-
bottom flask after the transfer, rinse the flask with small portions of
hexane:acetone (40:60) and add to the flask or bottle. Mark and set
aside the concentration flask for future use.
11.5.1.2 Add 10-20 g of granular anhydrous sodium sulfate to the
flask. Swirl to dry the extract.
11.5.1.3 Add activated copper (Section 6.7.4.1.4) and allow to
stand for 30-60 minutes, swirling occasionally. If
[[Page 9017]]
the copper does not remain bright, add more and swirl occasionally for
another 30-60 minutes.
11.5.1.4 After drying and sulfur removal, quantitatively transfer
the extract to a nitrogen-evaporation vial or tube and proceed to
Section 10.3.3 for nitrogen evaporation and solvent exchange, taking
care to leave the sodium sulfate and copper foil in the flask.
11.5.2 Removal with TBA sulfite.
11.5.2.1 Using small volumes of hexane, quantitatively transfer the
extract to a 40- to 50-mL centrifuge tube with fluoropolymer-lined
screw cap.
11.5.2.2 Add 1-2 mL of TBA sulfite reagent (Section 6.7.4.2.4), 2-3
mL of 2-propanol, and approximately 0.7 g of sodium sulfite (Section
6.7.4.2.2) crystals to the tube. Cap and shake for 1-2 minutes. If the
sample is colorless or if the initial color is unchanged, and if clear
crystals (precipitated sodium sulfite) are observed, sufficient sodium
sulfite is present. If the precipitated sodium sulfite disappears, add
more crystalline sodium sulfite in approximately 0.5-g portions until a
solid residue remains after repeated shaking.
11.5.2.3 Add 5-10 mL of reagent water and shake for 1-2 minutes.
Centrifuge to settle the solids.
11.5.2.4 Quantitatively transfer the hexane (top) layer through a
small funnel containing a few grams of granular anhydrous sodium
sulfate to a nitrogen-evaporation vial or tube and proceed to Section
10.3.3 for micro-concentration and solvent exchange.
12. Gas Chromatography
12.1 Establish the same operating conditions used in Section 7.1
for instrument calibration.
12.2 If the internal standard calibration procedure is used, add
the internal standard solution (Section 6.9.3) to the extract as close
as possible to the time of injection to minimize the possibility of
loss by evaporation, adsorption, or reaction. For example, add 1
[micro]L of 10 [micro]g/mL internal standard solution into the extract,
assuming no dilutions. Mix thoroughly.
12.3 Simultaneously inject an appropriate volume of the sample
extract or standard solution onto both columns, using split, splitless,
solvent purge, large-volume, or on-column injection. Alternatively, if
using a single-column GC configuration, inject an appropriate volume of
the sample extract or standard solution onto each GC column
independently. If the sample is injected manually, the solvent-flush
technique should be used. The injection volume depends upon the
technique used and the sensitivity needed to meet MDLs or reporting
limits for regulatory compliance. Injected volumes must be the same for
all standards and sample extracts. Record the volume injected to the
nearest 0.05 [micro]L.
12.4 Set the data system or GC control to start the temperature
program upon sample injection, and begin data collection after the
solvent peak elutes. Set the data system to stop data collection after
the last analyte is expected to elute and to return the column to the
initial temperature.
12.5 Perform all qualitative and quantitative measurements as
described in Sections 14 and 15. When standards and extracts are not
being used for analyses, store them refrigerated at <6 [deg]C,
protected from light, in screw-cap vials equipped with un-pierced
fluoropolymer-lined septa.
13. System and Laboratory Performance
13.1 At the beginning of each shift during which standards or
extracts are analyzed, GC system performance and calibration must be
verified for all analytes and surrogates on both column/detector
systems. Adjustment and/or recalibration (per Section 7) are performed
until all performance criteria are met. Only after all performance
criteria are met may samples, blanks and other QC samples, and
standards be analyzed.
13.2 Inject an aliquot of the combined QC standard (Section 6.8.4)
on both columns. Inject an aliquot of each of the multi-component
standards.
13.3 Retention times--The absolute retention times of the peak
maxima shall be within 2 seconds of the retention times in
the calibration verification (Section 7.8).
13.4 GC resolution--Resolution is acceptable if the valley height
between two peaks (as measured from the baseline) is less than 40% of
the shorter of the two peaks.
13.4.1 DB-608 column--DDT and endrin aldehyde.
13.4.2 DB-1701 column--alpha and gamma chlordane.
Note: If using other GC columns or stationary phases, these
resolution criteria apply to these four target analytes and any
other closely eluting analytes on those other GC columns.
13.5 Decomposition of DDT and endrin--If DDT, endrin, or their
breakdown products are to be determined, this test must be performed
prior to calibration verification (Section 13.6). DDT decomposes to DDE
and DDD. Endrin decomposes to endrin aldehyde and endrin ketone.
13.5.1 Inject 1 [mu]L of the DDT and endrin decomposition solution
(Section 6.9.5).
13.5.2 Measure the areas of the peaks for DDT, DDE, DDD, Endrin,
Endrin aldehyde, and Endrin ketone in the chromatogram and calculate
the percent breakdown as shown in the equations below:
[GRAPHIC] [TIFF OMITTED] TP19FE15.005
13.5.3 Both the % breakdown of DDT and of Endrin must be less than
20%, otherwise the system is not performing acceptably for DDT and
endrin. In this case, repair the GC column system that failed and
repeat the performance tests (Sections 13.2 to 13.6) until the
specification is met.
Note: DDT and endrin decomposition are usually caused by
accumulations of particulates in the injector and in the front end
of the column. Cleaning and silanizing the injection port liner, and
breaking off a short section of the front end of the column will
usually eliminate the decomposition problem. Either of these
corrective actions may affect retention times, GC resolution, and
calibration linearity.
13.6 Calibration verification.
13.6.1 Compute the percent recovery of each analyte and of the
coeluting analytes, based on the initial calibration data (Section 7.5
or 7.6).
13.6.2 For each analyte or for coeluting analytes, compare the
concentration with the limits for calibration verification in Table 4.
For coeluting analytes, use the coeluting analyte with the least
restrictive
[[Page 9018]]
specification (the widest range). For analytes in Table 2 not listed in
Table 4, QC acceptance criteria must be developed by the laboratory.
EPA has provided guidance for development of QC acceptance criteria
(References 13 and 14). If the recoveries for all analytes meet the
acceptance criteria, system performance is acceptable and analysis of
blanks and samples may continue. If, however, any recovery falls
outside the calibration verification range, system performance is
unacceptable for that analyte. If this occurs, repair the system and
repeat the test (Section 13.6), or prepare a fresh calibration standard
and repeat the test, or recalibrate (Section 7). See Section 8.1.7 for
information on repeated test failures.
13.7 Laboratory control sample.
13.7.1 Analyze the extract of the combined QC standard (a.k.a. LCS)
(Section 6.8.3) extracted with each sample batch (Section 8.4).
13.7.2 Compute the percent recovery of each analyte and of the
coeluting analytes.
13.7.3 For each analyte or coeluting analytes, compare the percent
recovery with the limits for ``P'' in Table 4. For coeluting analytes,
use the coeluting analyte with the least restrictive specification
(widest range). If all analytes pass, the extraction, concentration,
and cleanup processes are in control and analysis of blanks and samples
may proceed. If, however, any of the analytes fail, these processes are
not in control. In this event, correct the problem, re-extract the
sample batch, and repeat the ongoing precision and recovery test.
13.7.4 It is suggested, but not required, that the laboratory
update statements of data quality. Add results that pass the
specifications in Section 13.7.3 to initial (Section 8.7) and previous
ongoing data. Update QC charts to form a graphic representation of
continued laboratory performance. Develop a statement of laboratory
data quality for each analyte by calculating the average percent
recovery (R) and the standard deviation of percent recovery, sr.
Express the accuracy as a recovery interval from R-2sr to R + 2sr. For
example, if R = 95% and sr = 5%, the accuracy is 85 to 105%.
13.8 Internal standard response--If internal standard calibration
is used, verify that detector sensitivity has not changed by comparing
the response (area or height) of each internal standard in the sample,
blank, LCS, MS, and MSD to the response in the combined QC standard
(Section 6.8.3). The peak area or height of the internal standard
should be within 50% to 200% (\1/2\ to 2x) of its respective peak area
or height in the verification standard. If the area or height is not
within this range, compute the concentration of the analytes using the
external standard method (Section 7.5).
14. Qualitative Identification
14.1 Identification is accomplished by comparison of data from
analysis of a sample, blank, or other QC sample with data from
calibration verification (Section 7.7.1 or 13.5), and with data stored
in the retention-time and calibration libraries (Section 7.7). The
retention time window is determined as described in Section 14.2.
Identification is confirmed when retention time agrees on both GC
columns, as described below.
14.2 Establishing retention time windows.
14.2.1 Using the data from the multi-point initial calibration
(Section 7.4), determine the retention time in decimal minutes (not
minutes:seconds) of each peak representing a single-component target
analyte on each column/detector system. For the multi-component
analytes, use the retention times of the five largest peaks in the
chromatograms on each column/detector system.
14.2.2 Calculate the standard deviation of the retention times for
each single-component analyte on each column/detector system and for
the three to five exclusive (unique large) peaks for each multi-
component analyte.
14.2.3 Define the width of the retention time window as three times
that standard deviation. Establish the center of the retention time
window for each analyte by using the absolute retention time for each
analyte from the calibration verification standard at the beginning of
the analytical shift. For samples run during the same shift as an
initial calibration, use the retention time of the mid-point standard
of the initial calibration. If the calculated RT window is less than
0.02 minutes, then use 0.02 minutes as the window.
Note: Procedures for establishing retention time windows from
other sources may be employed provided that they are clearly
documented and provide acceptable performance. Such performance may
be evaluated using the results for the spiked QC samples described
in this method, such as laboratory control samples and matrix spike
samples.
14.2.4 New retention time windows must be established when a new GC
column is installed or if a GC column has been shortened during
maintenance to a degree that the retention times of analytes in the
calibration verification standard have shifted close to the lower
limits of the established retention time windows.
14.2.5 RT windows should be checked periodically by examining the
peaks in spiked samples such as the LCS or MS/MSD to confirm that peaks
for known analytes are properly identified.
14.2.6 If the retention time of an analyte in the initial
calibration data has been evaluated as described in Section 7.4.1 and
it varied by more than 5 seconds across the calibration range as a
function of the concentration of the standard (see Section 7.4.2), then
using the standard deviation of the retention times to set the width of
the retention time window may not adequately serve to identify the
analyte in question under routine conditions. In such cases, data from
additional analyses of standards may be required to adequately model
the chromatographic behavior of the analyte.
14.3 Identifying the analyte in a sample.
14.3.1 In order to identify a single-component analyte from
analysis of a sample, blank, or other QC sample, the peak representing
the analyst must fall within its respective retention time windows on
both column/detector systems (as defined in Section 14.2). That
identification is further supported by the comparison of the numerical
results on both columns, as described in Section 15.7.
14.3.2 In order to identify a multi-component analyte, pattern
matching (fingerprinting) may be used, or the three to five exclusive
(unique, baseline resolved, and largest) peaks for that analyte must
fall within their respective retention time windows on both column/
detector systems (as defined in Section 14.2). That identification is
further supported by the comparison of the numerical results on both
columns, as described in Section 15.7.
14.4 GC/MS confirmation.
When the concentration of an analyte is sufficient, or if the
presence or identity is suspect, its presence should be confirmed by
GC/MS. In order to match the sensitivity of the GC/ECD, confirmation
will have to be by SIM-GC/MS, or estimated the concentration would have
to be 100 times higher than the GC/ECD calibration range.
14.5 Additional information that may aid the laboratory in the
identification of an analyte.
The occurrence of peaks eluting near the retention time of an
analyte of interest increases the probability of a false positive for
the analyte. If the concentration is insufficient for confirmation by
GC/MS, the laboratory may use the cleanup procedures in this
[[Page 9019]]
method (Section 11) on a new sample aliquot to attempt to remove the
interferent. After attempts at cleanup are exhausted, the following
steps may be helpful to assure that the substance that appears in the
RT windows on both columns is the analyte of interest.
14.5.1 Determine the consistency of the RT data for the analyte on
each column. For example, if the RT is very stable (i.e., varies by no
more than a few seconds) for the calibration, calibration verification,
blank, LCS, and MS/MSD, the RT for the analyte of interest in the
sample should be within this variation regardless of the window
established in Section 14.2. If the analyte is not within this
variation on both columns, it is likely not present.
14.5.2 The possibility exists that the RT for the analyte in a
sample could shift if extraneous materials are present. This
possibility may be able to be confirmed or refuted by the behavior of
the surrogates in the sample. If multiple surrogates are used that span
the length of the chromatographic run, the RTs for the surrogates on
both columns are consistent with their RTs in calibration, calibration
verification, blank, LCS, and MS/MSD, it is unlikely that the RT for
the analyte of interest has shifted.
14.5.3 If the RT for the analyte is shifted slightly later on one
column and earlier on the other, and the surrogates have not shifted,
it is highly unlikely that the analyte is present, because shifts
nearly always occur in the same direction on both columns.
15. Quantitative Determination
15.1 External standard quantitation--Calculate the concentration of
the analyte in the extract using the calibration curve or average
calibration factor determined in calibration (Section 7.5.2) and the
following equation:
[GRAPHIC] [TIFF OMITTED] TP19FE15.006
where:
Cex = Concentration of the analyte in the extract (ng/mL)
As = Peak height or area for the analyte in the standard
or sample
CF = Calibration factor, as defined in Section 7.5.1
15.2 Internal standard quantitation--Calculate the concentration of
the analyte in the extract using the calibration curve or average
response factor determined in calibration (Section 7.6.2) and the
following equation:
[GRAPHIC] [TIFF OMITTED] TP19FE15.007
where:
Cex = Concentration of the analyte in the extract (ng/mL)
As = Peak height or area for the analyte in the standard
or sample
Cis = Concentration of the internal standard (ng/mL)
Ais = Area of the internal standard
RF = Response factor, as defined in Section 7.6.1
15.3 Calculate the concentration of the analyte in the sample using
the concentration in the extract, the extract volume, the sample
volume, and the dilution factor, per the following equation:
[GRAPHIC] [TIFF OMITTED] TP19FE15.008
where:
Cs = Concentration of the analyte in the sample
([micro]g/L)
Vex = Final extract volume (mL)
Cex = Concentration in the extract (ng/mL)
Vs = Volume of sample (L)
DF = Dilution factor
and the factor of 1,000 in the denominator converts the final units
from ng/L to [micro]g/L
15.4 If the concentration of any target analyte exceeds the
calibration range, either extract and analyze a smaller sample volume,
or dilute and analyze the diluted extract.
15.5 Quantitation of multi-component analytes
15.5.1 PCBs as Aroclors
Quantify an Aroclor by comparing the sample chromatogram to that of
the most similar Aroclor standard as indicated in Section 14.3.2.
Compare the responses of 3 to 5 major peaks in the calibration standard
for that Aroclor with the peaks observed in the sample extract. The
amount of Aroclor is calculated using the individual calibration factor
for each of the 3 to 5 characteristic peaks chosen in Sec. 7.5.1.
Determine the concentration of each of the characteristic peaks, using
the average calibration factor calculated for that peak in Sec. 7.5.2,
and then those 3 to 5 concentrations are averaged to determine the
concentration of that Aroclor.
15.5.2 Other multi-component analytes
Quantify any other multi-component analytes (technical chlordane or
toxaphene) using the same peaks used to develop the average calibration
factors in Section 7.5.2. Determine the concentration of each of the
characteristic peaks, and then the concentrations represented by those
characteristic peaks are averaged to determine the concentration of the
analyte. Alternatively, for toxaphene, the analyst may determine the
calibration factor in Section 7.5.2 by summing the areas of all of the
peaks for the analyte and using the summed of the peak areas in the
sample chromatogram to determine the concentration. However, the
approach used for toxaphene must be the same for the calibration and
the sample analyses.
15.6 Reporting of results.
As noted in Section 1.6.1, EPA has promulgated this method at 40
CFR part 136 for use in wastewater compliance monitoring under the
National Pollutant Discharge Elimination System (NPDES). The data
reporting practices described here are focused on such monitoring needs
and may not be relevant to other uses of the method.
15.6.1 Report results for wastewater samples in [micro]g/L without
correction for recovery. (Other units may be used if required by in a
permit.) Report all QC data with the sample results.
15.6.2 Reporting level.
Unless otherwise specified in by a regulatory authority or in a
discharge permit, results for analytes that meet the identification
criteria are reported down to the concentration of the ML established
by the laboratory through calibration of the instrument (see Section
7.5 or 7.6 and the glossary for the derivation of the ML). EPA
considers the terms ``reporting limit,'' ``quantitation limit,'' and
``minimum level'' to be synonymous.
15.6.2.1 Report the lower result from the two columns (see Section
15.7 below) for each analyte in each sample, blank, or standard at or
above the ML to 3 significant figures. Report a result for each analyte
found in each sample below the ML as ``ML,'' or as required by the
regulatory authority or permit. Results are reported without blank
subtraction unless requested or required by a regulatory authority or
in a permit. In this case, both the sample result and the blank results
must be reported together.
15.6.2.2 In addition to reporting results for samples and blank(s)
separately, the concentration of each analyte in a blank or field blank
associated with that sample may be subtracted from the result for that
sample, but only if requested or required by a regulatory authority or
in a permit. In this case, both the sample result and the blank results
must be reported together.
15.6.2.3 Report the result for an analyte in a sample or extract
that has been diluted at the least dilute level at which the peak area
is within the calibration range (i.e., above the ML for the analyte)
and the MS/MSD recovery and RPD are within their respective QC
acceptance criteria (Table 4). This may
[[Page 9020]]
require reporting results for some analytes from different analyses.
The results for each analyte in the MS/MSD samples should be
reported from the same GC column as used to report the results for that
analyte in the unspiked sample. If the MS/MSD recoveries and RPDs
calculated in this manner do not meet the acceptance criteria in Table
4, then the analyst may use the results from the other GC column to
determine if the MS/MSD results meet the acceptance criteria. If such a
situation occurs, the results for the sample should be recalculated
using the same GC column data as used for the MS/MSD samples, and
reported with appropriate annotations that alert the data user of the
issue.
15.6.2.4 Results from tests performed with an analytical system
that is not in control (i.e., that does not meet acceptance criteria
for all of QC tests in this method) must not be reported or otherwise
used for permitting or regulatory compliance purposes, but do not
relieve a discharger or permittee of reporting timely results. If the
holding time would be exceeded for a re-analysis of the sample, the
regulatory/control authority should be consulted for disposition.
15.6.3 Analyze the sample by GC/MS or on a third column when
analytes have co-eluted or interfere with determination on both
columns.
Note: Dichlone and kepone do not elute from the DB-1701 column
and must be confirmed on a DB-5 column, or by GC/MS.
15.7 Quantitative information that may aid in the confirmation of
the presence of an analyte
15.7.1 As noted in Section 14.3, the relative agreement between the
numerical results from the two GC columns may be used to support the
identification of the target analyte by providing evidence that that
co-eluting interferences are not present at the retention time of the
target analyte. Calculate the percent difference (%D) between the
results for the analyte from both columns, as follows:
[GRAPHIC] [TIFF OMITTED] TP19FE15.009
In general, if the %D of the two results is less than 50% (e.g., a
factor of 2), then the pesticide is present. This %D is generous and
allows for the pesticide that has the largest measurement error.
Note: Laboratories may employ metrics less than 50% for this
comparison, including those specified in other analytical methods
for these pesticides (e.g., CLP or SW-846).
15.7.2 If the amounts do not agree, and the RT data indicate the
presence of the analyte (per Section 14), it is likely that a positive
interference is present on the column that yielded the higher result.
That interferent may be represented by a separate peak on the other
column that does not coincide with the retention time of any of the
target analytes. If the interfering peak is evident on the other
column, report the result from that column and advise the data user
that the interference resulted in a %D value greater than 50%.
If an interferent is not identifiable on the second column, then
the results must be reported as ``not detected'' at the lower
concentration. In this event, the pesticide is not confirmed and the
reporting limit is elevated.
Note: The resulting elevation of the reporting limit may not
meet the requirements for compliance monitoring and the use of
additional cleanup procedures may be required.
16. Analysis of Complex Samples
16.1 Some samples may contain high levels (greater than 1 [micro]g/
L) of the analytes of interest, interfering analytes, and/or polymeric
materials. Some samples may not concentrate to 1.0 mL (Section
10.3.3.3.2); others may overload the GC column and/or detector.
16.2 When an interference is known or suspected to be present, the
laboratory should attempt to clean up the sample extract using the SPE
cartridge (Section 11.2), by Florisil[supreg] (Section 11.3), Alumina
(Section 11.4), sulfur removal (Section 11.5), or another clean up
procedure appropriate to the analytes of interest. If these techniques
do not remove the interference, the extract is diluted by a known
factor and reanalyzed (Section 12). Dilution until the extract is
lightly colored is preferable. Typical dilution factors are 2, 5, and
10.
16.3 Recovery of surrogate(s)--In most samples, surrogate
recoveries will be similar to those from reagent water. If surrogate
recovery is outside the range developed in Section 8.6, the sample is
re-extracted and reanalyzed if there is sufficient sample and if it is
within the 7-day extraction holding time. If the surrogate recovery is
still outside this range, extract and analyze one-tenth the volume of
sample to overcome any matrix interference problems. If a sample is
highly colored or suspected to be high in concentration, a 1-L sample
aliquot and a 100-mL sample aliquot could be extracted simultaneously
and still meet the holding time criteria, while providing information
about a complex matrix.
16.4 Recovery of the matrix spike and matrix spike duplicate (MS/
MSD)--In most samples, MS/MSD recoveries will be similar to those from
reagent water. If either the MS or MSD recovery is outside the range
specified in Section 8.3.3, one-tenth the volume of sample is spiked
and analyzed. If the matrix spike recovery is still outside the range,
the result for the unspiked sample may not be reported or used for
permitting or regulatory compliance purposes. Poor matrix spike
recovery does not relieve a discharger or permittee of reporting timely
results.
17. Method Performance
17.1 This method was tested for linearity of spike recovery from
reagent water and has been demonstrated to be applicable over the
concentration range from 4x MDL to 1000x MDL with the following
exceptions: Chlordane recovery at 4x MDL was low (60%); Toxaphene
recovery was demonstrated linear over the range of 10x MDL to 1000x MDL
(Reference 3).
17.2 The 1984 version of this method was tested by 20 laboratories
using reagent water, drinking water, surface water, and three
industrial wastewaters spiked at six concentrations (Reference 2).
Concentrations used in the study ranged from 0.5 to 30 [mu]g/L for
single-component pesticides and from 8.5 to 400 [mu]g/L for multi-
component analytes. These data are for a subset of analytes described
in the current version of the method.
17.3 During the development of Method 1656, a similar EPA procedure
for the organochlorine pesticides, single-operator precision, overall
precision, and method accuracy were found to be directly related to the
concentration of the analyte and essentially independent of the sample
matrix. Linear equations to describe these relationships are presented
in Table 5.
[[Page 9021]]
18. Pollution Prevention
18.1 Pollution prevention encompasses any technique that reduces or
eliminates the quantity or toxicity of waste at the point of
generation. Many opportunities for pollution prevention exist in
laboratory operations. EPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention as
the management option of first choice. Whenever feasible, the
laboratory should use pollution prevention techniques to address waste
generation. When wastes cannot be reduced at the source, the Agency
recommends recycling as the next best option.
18.2 The analytes in this method are used in extremely small
amounts and pose little threat to the environment when managed
properly. Standards should be prepared in volumes consistent with
laboratory use to minimize the disposal of excess volumes of expired
standards. This method utilizes significant quantities of methylene
chloride. Laboratories are encouraged to recover and recycle this and
other solvents during extract concentration.
18.3 For information about pollution prevention that may be applied
to laboratories and research institutions, consult Less is Better:
Laboratory Chemical Management for Waste Reduction (Reference 19).
19. Waste Management
19.1 The laboratory is responsible for complying with all Federal,
State, and local regulations governing waste management, particularly
the hazardous waste identification rules and land disposal
restrictions, and to protect the air, water, and land by minimizing and
controlling all releases from fume hoods and bench operations.
Compliance is also required with any sewage discharge permits and
regulations. An overview of requirements can be found in Environmental
Management Guide for Small Laboratories (EPA 233-B-98-001).
19.2 Samples at pH <2, or pH >12 are hazardous and must be
neutralized before being poured down a drain, or must be handled as
hazardous waste.
19.3 Many analytes in this method decompose above 500 [ordm]C. Low-
level waste such as absorbent paper, tissues, animal remains, and
plastic gloves may be burned in an appropriate incinerator. Gross
quantities of neat or highly concentrated solutions of toxic or
hazardous chemicals should be packaged securely and disposed of through
commercial or governmental channels that are capable of handling toxic
wastes.
20. References
1. ``Determination of Pesticides and PCBs in Industrial and Municipal
Wastewaters,'' EPA 600/4-82-023, National Technical Information
Service, PB82-214222, Springfield, Virginia 22161, April 1982.
2. ``EPA Method Study 18 Method 608-Organochlorine Pesticides and
PCBs,'' EPA 600/4-84-061, National Technical Information Service, PB84-
211358, Springfield, Virginia 22161, June 1984.
3. ``Method Detection Limit and Analytical Curve Studies, EPA Methods
606, 607, and 608,'' Special letter report for EPA Contract 68-03-2606,
U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio 45268, June 1980.
4. ASTM Annual Book of Standards, Part 31, D3694-78. ``Standard
Practice for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
5. Giam, C.S., Chan, H.S., and Nef, G.S. ``Sensitive Method for
Determination of Phthalate Ester Plasticizers in Open-Ocean Biota
Samples,'' Analytical Chemistry, 47, 2225 (1975).
6. Giam, C.S. and Chan, H.S. ``Control of Blanks in the Analysis of
Phthalates in Air and Ocean Biota Samples,'' U.S. National Bureau of
Standards, Special Publication 442, pp. 701-708, 1976.
7. Solutions to Analytical Chemistry Problems with Clean Water Act
Methods, EPA 821-R-07-002, March 2007.
8. ``Carcinogens-Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
9. ``Occupational Exposure to Hazardous Chemicals in Laboratories,''
(29 CFR part 1910, subpart 1450), Occupational Safety and Health
Administration, OSHA.
10. 40 CFR 136.6(b)(4)(j).
11. Mills, P.A. ``Variation of Florisil Activity: Simple Method for
Measuring Absorbent Capacity and Its Use in Standardizing Florisil
Columns,'' Journal of the Association of Official Analytical Chemists,
51, 29, (1968).
12. 40 CFR 136.6(b)(2)(i).
13. Protocol for EPA Approval of New Methods for Organic and Inorganic
Analytes in Wastewater and Drinking Water (EPA-821-B-98-003) March
1999.
14. Methods 4500 Cl F and 4500 Cl G, Standard Methods for the
Examination of Water and Wastewater, published jointly by the American
Public Health Association, American Water Works Association, and Water
Environment Federation, 1015 Fifteenth St. Washington, DC 20005, 20th
Edition, 2000.
15. ``Manual of Analytical Methods for the Analysis of Pesticides in
Human and Environmental Samples,'' EPA-600/8-80-038, U.S. Environmental
Protection Agency, Health Effects Research Laboratory, Research
Triangle Park, North Carolina.
16. USEPA, 2000, Method 1656 Organo-Halide Pesticides In Wastewater,
Soil, Sludge, Sediment, and Tissue by GC/HSD, EPA-821-R-00-017,
September 2000.
17. USEPA, 2010, Method 1668C Chlorinated Biphenyl Congeners in Water,
Soil, Sediment, Biosolids, and Tissue by HRGC/HRMS, EPA-820-R-10-005,
April 2010.
18. USEPA, 2007, Method 1699: Pesticides in Water, Soil, Sediment,
Biosolids, and Tissue by HRGC/HRMS, EPA-821-R-08-001, December 2007.
19. ``Less is Better,'' American Chemical Society on-line publication,
http://www.acs.org/content/dam/acsorg/about/governance/committees/chemicalsafety/publications/less-is-better.pdf.
20. EPA Method 608 ATP 3M0222, An alternative test procedure for the
measurement of organochlorine pesticides and polychlorinated biphenyls
in waste water. Federal Register/Vol. 60, No. 148 August 2, 1995.
[[Page 9022]]
21. Tables
Table 1--Pesticides \1\
----------------------------------------------------------------------------------------------------------------
Analyte CAS No. MDL \2\ (ng/L) ML \3\ (ng/L)
----------------------------------------------------------------------------------------------------------------
Aldrin.......................................................... 309-00-2 8 24
alpha-BHC....................................................... 319-84-6 6 18
beta-BHC........................................................ 319-85-7 7 21
delta-BHC....................................................... 319-86-8 5 15
gamma-BHC (Lindane)............................................. 58-89-9 1 33
alpha-Chlordane................................................. 5103-71-9 9 27
gamma-Chlordane................................................. 5103-74-2 8 24
4,4'-DDD........................................................ 72-54-8 5 15
4,4'-DDE........................................................ 72-55-9 10 30
4,4'-DDT........................................................ 50-29-3 12 36
Dieldrin........................................................ 60-57-1 6 18
Endosulfan I.................................................... 959-98-8 11 33
Endosulfan II................................................... 33213-65-9 8 24
Endosulfan sulfate.............................................. 1031-07-8 7 21
Endrin.......................................................... 72-20-8 4 12
Endrin aldehyde................................................. 7421-93-4 11 33
Heptachlor...................................................... 76-44-8 5 15
Heptachlor epoxide.............................................. 1024-57-3 12 36
----------------------------------------------------------------------------------------------------------------
\1\ All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A).
\2\ 40 CFR 136, Appendix B. MDLs were obtained by a single laboratory with an electrolytic conductivity
detector, and are estimates of what can be achieved using an electron capture detector.
\3\ ML = Minimum Level--see Glossary for definition and derivation.
Table 2--Additional Analytes
----------------------------------------------------------------------------------------------------------------
Analyte CAS No. MDL \3\ (ng/L) ML \4\ (ng/L)
----------------------------------------------------------------------------------------------------------------
Acephate........................................................ 30560-19-1 2,000 6,000
Alachlor........................................................ 15972-60-8 20 60
Atrazine........................................................ 1912-24-9 500 1,500
Benfluralin (Benefin)........................................... 1861-40-1 20 60
Bromacil........................................................ 314-40-9 70 210
Bromoxynil octanoate............................................ 1689-99-2 30 90
Butachlor....................................................... 23184-66-9 30 90
Captafol........................................................ 2425-06-1 100 300
Captan.......................................................... 133-06-2 100 300
Carbophenothion (Trithion)...................................... 786-19-6 50 150
Chlorobenzilate................................................. 510-15-6 25 75
Chloroneb (Terraneb)............................................ 2675-77-6 .............. ..............
Chloropropylate (Acaralate)..................................... 5836-10-2 .............. ..............
Chlorothalonil.................................................. 1897-45-6 15 45
Cyanazine....................................................... 21725-46-2 .............. ..............
DCPA (Dacthal).................................................. 1861-32-1 3 9
2,4'-DDD........................................................ 53-19-0 .............. ..............
2,4'-DDE........................................................ 3424-82-6 .............. ..............
2,4'-DDT........................................................ 789-02-6 .............. ..............
Diallate (Avadex)............................................... 2303-16-4 45 135
1,2-Dibromo-3-chloropropane (DBCP).............................. 96-12-8 .............. ..............
Dichlone........................................................ 117-80-6 .............. ..............
Dichloran....................................................... 99-30-9 .............. ..............
Dicofol......................................................... 115-32-2 .............. ..............
Endrin ketone................................................... 53494-70-5 8 24
Ethalfluralin (Sonalan)......................................... 55283-68-6 5 15
Etridiazole..................................................... 2593-15-9 .............. ..............
Fenarimol (Rubigan)............................................. 60168-88-9 20 30
Hexachlorobenzene \1\........................................... 118-74-1 .............. ..............
Hexachlorocyclopentadiene \1\................................... 77-47-4 .............. ..............
Isodrin......................................................... 465-73-6 13 39
Isopropalin (Paarlan)........................................... 33820-53-0 20 60
Kepone.......................................................... 143-50-0 100 300
Methoxychlor.................................................... 72-43-5 30 90
Metolachlor..................................................... 51218-45-2 .............. ..............
Metribuzin...................................................... 21087-64-9 5 15
Mirex........................................................... 2385-85-5 4 12
Nitrofen (TOK).................................................. 1836-75-5 13 39
cis-Nonachlor................................................... 5103-73-1 .............. ..............
trans-Nonachlor................................................. 39765-80-5 .............. ..............
Norfluorazon.................................................... 27314-13-2 50 150
[[Page 9023]]
Octachlorostyrene............................................... 29082-74-4 .............. ..............
Oxychlordane.................................................... 27304-13-8 .............. ..............
PCNB (Pentachloronitrobenzene).................................. 82-68-8 6 18
Pendamethalin (Prowl)........................................... 40487-42-1 .............. ..............
cis-Permethrin.................................................. 61949-76-6 200 600
trans-Permethrin................................................ 61949-77-7 200 600
Perthane (Ethylan).............................................. 72-56-0 .............. ..............
Propachlor...................................................... 1918-16-7 .............. ..............
Propanil........................................................ 709-98-8 .............. ..............
Propazine....................................................... 139-40-2 .............. ..............
Quintozene...................................................... 82-68-8 .............. ..............
Simazine........................................................ 122-34-9 400 1,200
Strobane........................................................ 8001-50-1 .............. ..............
Technazene...................................................... 117-18-0 .............. ..............
Technical Chlordane \2\......................................... .............. .............. ..............
Terbacil........................................................ 5902-51-2 200 600
Terbuthylazine.................................................. 5915-41-3 300 900
Toxaphene \1\................................................... 8001-35-2 910 2,730
Trifluralin..................................................... 1582-09-8 50 150
PCB-1016 \1\.................................................... 12674-11-2 150 450
PCB-1221 \1\.................................................... 11104-28-2 150 450
PCB-1232 \1\.................................................... 11141-16-5 150 450
PCB-1242 \1\.................................................... 53469-21-9 150 450
PCB-1248 \1\.................................................... 12672-29-6 150 450
PCB-1254 \1\.................................................... 11097-69-1 150 450
PCB-1260 \1\.................................................... 11096-82-5 140 420
----------------------------------------------------------------------------------------------------------------
\1\ Priority Pollutants (40 CFR part 423, appendix A).
\2\ Technical Chlordane may be used in cases where historical reporting has only been for this form of
Chlordane.
\3\ 40 CFR part 136, appendix B. MDLs were obtained by a single laboratory with an electrolytic conductivity
detector, and are estimates of what can be achieved using an electron capture detector.
\4\ ML = Minimum Level--see Glossary for definition and derivation.
Table 3--Example Retention Times \1\
------------------------------------------------------------------------
Retention time (min)
\2\
Analyte ---------------------
DB-608 DB-1701
------------------------------------------------------------------------
Acephate.......................................... 5.03 (\3\)
Trifluralin....................................... 5.16 6.79
Ethalfluralin..................................... 5.28 6.49
Benfluralin....................................... 5.53 6.87
Diallate-A........................................ 7.15 6.23
Diallate-B........................................ 7.42 6.77
alpha-BHC......................................... 8.14 7.44
PCNB.............................................. 9.03 7.58
Simazine.......................................... 9.06 9.29
Atrazine.......................................... 9.12 9.12
Terbuthylazine.................................... 9.17 9.46
gamma-BHC (Lindane)............................... 9.52 9.91
beta-BHC.......................................... 9.86 11.90
Heptachlor........................................ 10.66 10.55
Chlorothalonil.................................... 10.66 10.96
Dichlone.......................................... 10.80 (\4\)
Terbacil.......................................... 11.11 12.63
delta-BHC......................................... 11.20 12.98
Alachlor.......................................... 11.57 11.06
Propanil.......................................... 11.60 14.10
Aldrin............................................ 11.84 11.46
DCPA.............................................. 12.18 12.09
Metribuzin........................................ 12.80 11.68
Triadimefon....................................... 12.99 13.57
Isopropalin....................................... 13.06 13.37
Isodrin........................................... 13.47 11.12
Heptachlor epoxide................................ 13.97 12.56
Pendamethalin..................................... 14.21 13.46
Bromacil.......................................... 14.39 (\3\)
alpha-Chlordane................................... 14.63 14.20
Butachlor......................................... 15.03 15.69
gamma-Chlordane................................... 15.24 14.36
Endosulfan I...................................... 15.25 13.87
4,4'-DDE.......................................... 16.34 14.84
Dieldrin.......................................... 16.41 15.25
Captan............................................ 16.83 15.43
Chlorobenzilate................................... 17.58 17.28
Endrin............................................ 17.80 15.86
Nitrofen (TOK).................................... 17.86 17.47
Kepone............................................ 17.92 (3 5)
4,4'-DDD.......................................... 18.43 17.77
Endosulfan II..................................... 18.45 18.57
Bromoxynil octanoate.............................. 18.85 18.57
4,4'-DDT.......................................... 19.48 18.32
Carbophenothion................................... 19.65 18.21
Endrin aldehyde................................... 19.72 19.18
Endosulfan sulfate................................ 20.21 20.37
Captafol.......................................... 22.51 21.22
Norfluorazon...................................... 20.68 22.01
Mirex............................................. 22.75 19.79
Methoxychlor...................................... 22.80 20.68
Endrin ketone..................................... 23.00 21.79
Fenarimol......................................... 24.53 23.79
cis-Permethrin.................................... 25.00 23.59
trans-Permethrin.................................. 25.62 23.92
PCB-1242..........................................
PCB-1232..........................................
PCB-1016..........................................
PCB-1221..........................................
PCB-1248..........................................
PCB-1254..........................................
PCB-1260 (5 peaks)................................ 15.44 14.64
15.73 15.36
16.94 16.53
17.28 18.70
19.17 19.92
Toxaphene (5 peaks)............................... 16.60 16.60
17.37 17.52
18.11 17.92
19.46 18.73
19.69 19.00
------------------------------------------------------------------------
\1\ Data from EPA Method 1656 (Reference 16).
\2\ Columns: 30-m long x 0.53-mm ID fused-silica capillary; DB-608, 0.83
[mu]m; and DB-1701, 1.0 [mu]m.
Conditions suggested to meet retention times shown: 150 [deg]C for 0.5
minute, 150-270 [deg]C at 5 [deg]C/min, and 270 [deg]C until trans-
Permethrin elutes.
Carrier gas flow rates approximately 7 mL/min.
\3\ Does not elute from DB-1701 column at level tested.
\4\ Not recovered from water at the levels tested.
\5\ Dichlone and Kepone do not elute from the DB-1701 column and should
be confirmed on DB-5.
[[Page 9024]]
Table 4--QC Acceptance Criteria
--------------------------------------------------------------------------------------------------------------------------------------------------------
Calibration Test
Analyte verification concentration Limit for s Range for X Range for P Maximum MS/
(%) ([mu]g/L) (% SD) (%) (%) MSD RPD (%)
--------------------------------------------------------------------------------------------------------------------------------------------------------
Aldrin...................................................... 75-125 2.0 25 54-130 42-140 35
alpha-BHC................................................... 69-125 2.0 28 49-130 37-140 36
beta-BHC.................................................... 75-125 2.0 38 39-130 17-147 44
delta-BHC................................................... 75-125 2.0 43 51-130 19-140 52
gamma-BHC................................................... 75-125 2.0 29 43-130 32-140 39
alpha-Chlordane............................................. 73-125 50.0 24 55-130 45-140 35
gamma-Chlordane............................................. 75-125 50.0 24 55-130 45-140 35
4,4'-DDD.................................................... 75-125 10.0 32 48-130 31-141 39
4,4'-DDE.................................................... 75-125 2.0 30 54-130 30-145 35
4,4'-DDT.................................................... 75-125 10.0 39 46-137 25-160 42
Dieldrin.................................................... 48-125 2.0 42 58-130 36-146 49
Endosulfan I................................................ 75-125 2.0 25 57-141 45-153 28
Endosulfan II............................................... 75-125 10.0 63 22-171 D-202 53
Endosulfan sulfate.......................................... 70-125 10.0 32 38-132 26-144 38
Endrin...................................................... 5-125 10.0 42 51-130 30-147 48
Heptachlor.................................................. 75-125 2.0 28 43-130 34-140 43
Heptachlor epoxide.......................................... 75-125 2.0 22 57-132 37-142 26
Toxaphene................................................... 68-134 50.0 30 56-130 41-140 41
PCB-1016.................................................... 75-125 50.0 24 61-103 50-140 36
PCB-1221.................................................... 75-125 50.0 50 44-150 15-178 48
PCB-1232.................................................... 75-125 50.0 32 28-197 10-215 25
PCB-1242.................................................... 75-125 50.0 26 50-139 39-150 29
PCB-1248.................................................... 75-125 50.0 32 58-140 38-158 35
PCB-1254.................................................... 75-125 50.0 34 44-130 29-140 45
PCB-1260.................................................... 75-125 50.0 28 37-130 8-140 38
--------------------------------------------------------------------------------------------------------------------------------------------------------
S = Standard deviation of four recovery measurements (Section 8.2.4).
Note: These criteria were developed from data in Table 5 (Reference 2). Where necessary, limits for recovery have been broadened to assure applicability
to concentrations below those in Table 5.
Table 5--Precision and Recovery as Functions of Concentration
----------------------------------------------------------------------------------------------------------------
Single analyst Overall
Analyte Recovery, X' precision, sr' precision, S'
([mu]g/L) ([mu]g/L) ([mu]g/L)
----------------------------------------------------------------------------------------------------------------
Aldrin................................................. 0.81C + 0.04 0.16(X) - 0.04 0.20(X) - 0.01
alpha-BHC.............................................. 0.84C + 0.03 0.13(X) + 0.04 0.23(X) - 0.00
beta-BHC............................................... 0.81C + 0.07 0.22(X) - 0.02 0.33(X) - 0.05
delta-BHC.............................................. 0.81C + 0.07 0.18(X) + 0.09 0.25(X) + 0.03
gamma-BHC (Lindane).................................... 0.82C - 0.05 0.12(X) + 0.06 0.22(X) + 0.04
Chlordane.............................................. 0.82C - 0.04 0.13 (X) + 0.13 0.18(X) + 0.18
4,4'-DDD............................................... 0.84C + 0.30 0.20(X) - 0.18 0.27(X) - 0.14
4,4'-DDE............................................... 0.85C + 0.14 0.13(X) + 0.06 0.28(X) - 0.09
4,4'-DDT............................................... 0.93C - 0.13 0.17(X) + 0.39 0.31(X) - 0.21
Dieldrin............................................... 0.90C + 0.02 0.12(X) + 0.19 0.16(X) + 0.16
Endosulfan I........................................... 0.97C + 0.04 0.10(X) + 0.07 0.18(X) + 0.08
Endosulfan II.......................................... 0.93C + 0.34 0.41(X) - 0.65 0.47(X) - 0.20
Endosulfan sulfate..................................... 0.89C - 0.37 0.13(X) + 0.33 0.24(X) + 0.35
Endrin................................................. 0.89C - 0.04 0.20(X) + 0.25 0.24(X) + 0.25
Heptachlor............................................. 0.69C + 0.04 0.06(X) + 0.13 0.16(X) + 0.08
Heptachlor epoxide..................................... 0.89C + 0.10 0.18(X) - 0.11 0.25(X) - 0.08
Toxaphene.............................................. 0.80C + 1.74 0.09(X) + 3.20 0.20(X) + 0.22
PCB-1016............................................... 0.81C + 0.50 0.13(X) + 0.15 0.15(X) + 0.45
PCB-1221............................................... 0.96C + 0.65 0.29(X) - 0.76 0.35(X) - 0.62
PCB-1232............................................... 0.91C + 10.8 0.21(X) - 1.93 0.31(X) + 3.50
PCB-1242............................................... 0.93C + 0.70 0.11(X) + 1.40 0.21(X) + 1.52
PCB-1248............................................... 0.97C + 1.06 0.17(X) + 0.41 0.25(X) - 0.37
PCB-1254............................................... 0.76C + 2.07 0.15(X) + 1.66 0.17(X) + 3.62
PCB-1260............................................... 0.66C + 3.76 0.22(X) - 2.37 0.39(X) - 4.86
----------------------------------------------------------------------------------------------------------------
X' = Expected recovery for one or more measurements of a sample containing a concentration of C, in [mu]g/L.
[[Page 9025]]
Table 6--Distribution of Chlorinated Pesticides and PCBs Into
Florisil[supreg] Column Fractions
------------------------------------------------------------------------
Percent recovery by
fraction \1\
Analyte --------------------
1 2 3
------------------------------------------------------------------------
Aldrin............................................. 100
alpha-BHC.......................................... 100
beta-BHC........................................... 97
delta-BHC.......................................... 98
gamma-BHC (Lindane)................................ 100
Chlordane.......................................... 100
4,4'-DDD........................................... 99
4,4'-DDE........................................... ..... 98
4,4'-DDT........................................... 100
Dieldrin........................................... 0 100
Endosulfan I....................................... 37 64 .....
Endosulfan II...................................... 0 7 91
Endosulfan sulfate................................. 0 0 106
Endrin............................................. 4 96
Endrin aldehyde.................................... 0 68 26
Heptachlor......................................... 100
Heptachlor epoxide................................. 100
Toxaphene.......................................... 96
PCB-1016........................................... 97
PCB-1221........................................... 97
PCB-1232........................................... 95 4
PCB-1242........................................... 97
PCB-1248........................................... 103
PCB-1254........................................... 90
PCB-1260...........................................
------------------------------------------------------------------------
\1\ Eluant composition:
Fraction 1--6% ethyl ether in hexane
Fraction 2--15% ethyl ether in hexane
Fraction 3--50% ethyl ether in hexane.
BILLING CODE 6560-50-P
[GRAPHIC] [TIFF OMITTED] TP19FE15.010
[[Page 9026]]
[GRAPHIC] [TIFF OMITTED] TP19FE15.011
23. Glossary
These definitions and purposes are specific to this method but have
been conformed to common usage to the extent possible.
23.1 Units of weight and measure and their abbreviations.
23.1.1 Symbols
[deg]C degrees Celsius
[micro]g microgram
[mu]L microliter
< less than
<= less than or equal to
> greater than
% percent
23.1.2 Abbreviations (in alphabetical order)
cm centimeter
g gram
[[Page 9027]]
hr hour
ID inside diameter
in. inch
L liter
M molar solution--one mole or gram molecular weight of solute in one
liter of solution
mg milligram
min minute
mL milliliter
mm millimeter
N Normality--one equivalent of solute in one liter of solution
ng nanogram
psia pounds-per-square inch absolute
psig pounds-per-square inch gauge
v/v volume per unit volume
w/v weight per unit volume
23.2 Definitions and acronyms (in alphabetical order)
Analyte--A compound or mixture of compounds (e.g., PCBs) tested for
by this method. The analytes are listed in Tables 1 and 2.
Analytical batch--The set of samples analyzed on a given instrument
during a 24-hour period that begins and ends with calibration
verification (Sections 7.8 and 13). See also ``Extraction batch.''
Blank (method blank; laboratory blank)--An aliquot of reagent water
that is treated exactly as a sample including exposure to all
glassware, equipment, solvents, reagents, internal standards, and
surrogates that are used with samples. The blank is used to determine
if analytes or interferences are present in the laboratory environment,
the reagents, or the apparatus.
Calibration factor (CF)--See Section 7.5.1.
Calibration standard--A solution prepared from stock solutions and/
or a secondary standards and containing the analytes of interest,
surrogates, and internal standards. This standard is used to model the
response of the GC instrument against analyte concentration.
Calibration verification--The process of confirming that the
response of the analytical system remains within specified limits of
the calibration.
Calibration verification standard--The combined QC standard
(Section 7.7) used to verify calibration (Section 13.5) and for LCS
tests (Section 8.4).
Extraction Batch--A set of up to 20 field samples (not including QC
samples) started through the extraction process in a given 24-hour
shift. Each extraction batch of 20 or fewer samples must be accompanied
by a blank (Section 8.5), a laboratory control sample (LCS, Section
8.4), a matrix spike and duplicate (MS/MSD; Section 8.3), resulting in
a minimum of five samples (1 field sample, 1 blank, 1 LCS, 1 MS, and 1
MSD) and a maximum of 24 samples (20 field samples, 1 blank, 1 LCS, 1
MS, and 1 MSD) for the batch. If greater than 20 samples are to be
extracted in a 24-hour shift, the samples must be separated into
extraction batches of 20 or fewer samples.
Field Duplicates--Two samples collected at the same time and place
under identical conditions, and treated identically throughout field
and laboratory procedures. Results of analyses the field duplicates
provide an estimate of the precision associated with sample collection,
preservation, and storage, as well as with laboratory procedures.
Field blank--An aliquot of reagent water or other reference matrix
that is placed in a sample container in the field, and treated as a
sample in all respects, including exposure to sampling site conditions,
storage, preservation, and all analytical procedures. The purpose of
the field blank is to determine if the field or sample transporting
procedures and environments have contaminated the sample. See also
``Blank.''
GC--Gas chromatograph or gas chromatography
Gel-permeation chromatography (GPC)--A form of liquid
chromatography in which the analytes are separated based on exclusion
from the solid phase by size.
Internal standard--A compound added to an extract or standard
solution in a known amount and used as a reference for quantitation of
the analytes of interest and surrogates. Also see Internal standard
quantitation.
Internal standard quantitation--A means of determining the
concentration of an analyte of interest (Tables 1 and 2) by reference
to a compound not expected to be found in a sample.
IDC--Initial Demonstration of Capability (Section 8.2); four
aliquots of a reference matrix spiked with the analytes of interest and
analyzed to establish the ability of the laboratory to generate
acceptable precision and recovery. An IDC is performed prior to the
first time this method is used and any time the method or
instrumentation is modified.
Laboratory Control Sample (LCS; laboratory fortified blank; Section
8.4)--An aliquot of reagent water spiked with known quantities of the
analytes of interest and surrogates. The LCS is analyzed exactly like a
sample. Its purpose is to assure that the results produced by the
laboratory remain within the limits specified in this method for
precision and recovery.
Laboratory Fortified Sample Matrix--See Matrix spike.
Laboratory reagent blank--See blank.
Matrix spike (MS) and matrix spike duplicate (MSD) (laboratory
fortified sample matrix and duplicate)--Two aliquots of an
environmental sample to which known quantities of the analytes of
interest and surrogates are added in the laboratory. The MS/MSD are
prepared and analyzed exactly like a field sample. Their purpose is to
quantify any additional bias and imprecision caused by the sample
matrix. The background concentrations of the analytes in the sample
matrix must be determined in a separate aliquot and the measured values
in the MS/MSD corrected for background concentrations.
May--This action, activity, or procedural step is neither required
nor prohibited.
May not--This action, activity, or procedural step is prohibited.
Method detection limit (MDL)--A detection limit determined by the
procedure at 40 CFR part 136, appendix B. The MDLs determined by EPA
are listed in Tables 1 and 2. As noted in Sec. 1.6, use the MDLs in
Tables 1 and 2 in conjunction with current MDL data from the laboratory
actually analyzing samples to assess the sensitivity of this procedure
relative to project objectives and regulatory requirements (where
applicable).
Minimum level (ML)--The term ``minimum level'' refers to either the
sample concentration equivalent to the lowest calibration point in a
method or a multiple of the method detection limit (MDL), whichever is
higher. Minimum levels may be obtained in several ways: They may be
published in a method; they may be based on the lowest acceptable
calibration point used by a laboratory; or they may be calculated by
multiplying the MDL in a method, or the MDL determined by a laboratory,
by a factor of 3. For the purposes of NPDES compliance monitoring, EPA
considers the following terms to be synonymous: ``quantitation limit,''
``reporting limit,'' and ``minimum level.''
MS--Mass spectrometer or mass spectrometry.
Must--This action, activity, or procedural step is required.
Preparation blank--See blank.
Quality control sample (QCS)--A sample containing analytes of
interest at known concentrations. The QCS is obtained from a source
external to the laboratory or is prepared from standards obtained from
a different source than the calibration standards. The purpose is to
check laboratory performance using test materials that have been
prepared independent of the normal preparation process.
[[Page 9028]]
Reagent water--Water demonstrated to be free from the analytes of
interest and potentially interfering substances at the MDLs for the
analytes in this method.
Regulatory compliance limit--A limit on the concentration or amount
of a pollutant or contaminant specified in a nationwide standard, in a
permit, or otherwise established by a regulatory/control authority.
Relative standard deviation (RSD)--The standard deviation times 100
divided by the mean. Also termed ``coefficient of variation.''
RF--Response factor. See Section 7.6.2.
RPD--Relative percent difference.
RSD--See relative standard deviation.
Safety Data Sheet (SDS)--Written information on a chemical's
toxicity, health hazards, physical properties, fire, and reactivity,
including storage, spill, and handling precautions that meet the
requirements of OSHA, 29 CFR 1910.1200(g) and appendix D to Sec.
1910.1200. United Nations Globally Harmonized System of Classification
and Labelling of Chemicals (GHS), third revised edition, United
Nations, 2009.
Should--This action, activity, or procedural step is suggested but
not required.
SPE--Solid-phase extraction; a sample extraction or extract cleanup
technique in which an analyte is selectively removed from a sample or
extract by passage over or through a material capable of reversibly
adsorbing the analyte.
Stock solution--A solution containing an analyte that is prepared
using a reference material traceable to EPA, the National Institute of
Science and Technology (NIST), or a source that will attest to the
purity and authenticity of the reference material.
Surrogate--A compound unlikely to be found in a sample, which is
spiked into the sample in a known amount before extraction, and which
is quantified with the same procedures used to quantify other sample
components. The purpose of the surrogate is to monitor method
performance with each sample.
* * * * *
Method 611--Haloethers
1. Scope and Application
1.1 This method covers the determination of certain haloethers. The
following parameters can be determined by this method:
------------------------------------------------------------------------
Parameter STORET No. CAS No.
------------------------------------------------------------------------
Bis(2-chloroethyl) ether................ 34273 111-44-4
Bis(2-chloroethoxy) methane............. 34278 111-91-1
2, 2'-oxybis (1-chloropropane).......... 34283 108-60-1
4-Bromophenyl phenyl ether.............. 34636 101-55-3
4-Chlorophenyl phenyl either............ 34641 7005-72-3
------------------------------------------------------------------------
* * * * *
Method 624.1--Purgeables by GC/MS
1. Scope and Application
1.1 This method is for determination of purgeable organic
pollutants in industrial discharges and other environmental samples by
gas chromatography combined with mass spectrometry (GC/MS), as provided
under 40 CFR 136.1. This revision is based on previous protocols
(References 1-3), on the revision promulgated October 26, 1984 (49 FR
43234), and on an interlaboratory method validation study (Reference
4). Although this method was validated through an interlaboratory study
conducted more than 29 years ago, the fundamental chemistry principles
used in this method remain sound and continue to apply.
1.2 The analytes that may be qualitatively and quantitatively
determined using this method and their CAS Registry numbers are listed
in Table 1. The method may be extended to determine the analytes listed
in Table 2; however, poor purging efficiency or gas chromatography of
some of these analytes may make quantitative determination difficult.
For example, an elevated temperature may be required to purge some
analytes from water. If an elevated temperature is used, calibration
and all quality control (QC) tests must be performed at the elevated
temperature. EPA encourages the use of this method to determine
additional compounds amenable to purge-and-trap GC/MS.
1.3 The large number of analytes in Tables 1 and 2 of this method
makes testing difficult if all analytes are determined simultaneously.
Therefore, it is necessary to determine and perform QC tests for
``analytes of interest'' only. Analytes of interest are those required
to be determined by a regulatory/control authority or in a permit, or
by a client. If a list of analytes is not specified, the analytes in
Table 1 must be determined, at a minimum, and QC testing must be
performed for these analytes. The analytes in Table 1 and some of the
analytes in Table 2 have been identified as Toxic Pollutants (40 CFR
401.15), expanded to a list of Priority Pollutants (40 CFR part 423,
appendix A).
1.4 Method detection limits (MDLs; Reference 5) for the analytes in
Table 1 are listed in that table. These MDLs were determined in reagent
water (Reference 6). Advances in analytical technology, particularly
the use of capillary (open-tubular) columns, allowed laboratories to
routinely achieve MDLs for the analytes in this method that are 2-10
times lower than those in the version promulgated in 1984 (40 FR
43234). The MDL for a specific wastewater may differ from those listed,
depending on the nature of interferences in the sample matrix.
1.4.1 EPA has promulgated this method at 40 CFR part 136 for use in
wastewater compliance monitoring under the National Pollutant Discharge
Elimination System (NPDES). The data reporting practices described in
Section 13.2 are focused on such monitoring needs and may not be
relevant to other uses of the method.
1.4.2 This method includes ``reporting limits'' based on EPA's
``minimum level'' (ML) concept (see the glossary in Section 20). Table
1 contains MDL values and ML values for many of the analytes. The MDL
for an analyte in a specific wastewater may differ from that listed in
Table 1, depending upon the nature of interferences in the sample
matrix.
1.5 This method is performance-based. It may be modified to improve
performance (e.g., to overcome interferences or improve the accuracy of
results) provided all performance requirements are met.
1.5.1 Examples of allowed method modifications are described at 40
CFR 136.6. Other examples of allowed modifications specific to this
method are described in Section 8.1.2.
1.5.2 Any modification beyond those expressly allowed at 40 CFR
136.6 or in Section 8.1.2 of this method shall be considered a major
modification that is subject to application and approval of an
alternate test procedure under 40 CFR 136.4 and 136.5.
[[Page 9029]]
1.5.3 For regulatory compliance, any modification must be
demonstrated to produce results equivalent or superior to results
produced by this method when applied to relevant wastewaters (Section
8.3).
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the operation of a purge-and-trap system and a
gas chromatograph/mass spectrometer and in the interpretation of mass
spectra. Each analyst must demonstrate the ability to generate
acceptable results with this method using the procedure in Section 8.2.
1.7 Terms and units of measure used in this method are given in the
glossary at the end of the method.
2. Summary of Method
2.1 A gas is bubbled through a measured volume of water in a
specially-designed purging chamber (Figure 1). The purgeables are
efficiently transferred from the aqueous phase to the vapor phase. The
vapor is swept through a sorbent trap where the purgeables are trapped
(Figure 2). After purging is completed, the trap is heated and
backflushed with the gas to desorb the purgeables onto a gas
chromatographic column (Figures 3 and 4). The column is temperature
programmed to separate the purgeables which are then detected with a
mass spectrometer.
2.2 Different sample sizes in the range of 5-25 mL are allowed in
order to meet differing sensitivity requirements. Calibration and QC
samples must have the same volume as field samples.
3. Interferences
3.1 Impurities in the purge gas, organic compounds outgassing from
the plumbing ahead of the trap, and solvent vapors in the laboratory
account for the majority of contamination problems. The analytical
system must be demonstrated to be free from contamination under the
conditions of the analysis by analyzing blanks as described in Section
8.5. Fluoropolymer tubing, fittings, and thread sealant should be used
to avoid contamination.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons and methylene chloride) through the septum
seal into the sample during shipment and storage. Protect samples from
sources of volatiles during collection, shipment, and storage. A
reagent water field blank carried through sampling and analysis can
serve as a check on such contamination.
3.3 Contamination by carry-over can occur whenever high level and
low level samples are analyzed sequentially. To reduce the potential
for carry-over, the purging device and sample syringe must be rinsed
with reagent water between sample analyses. Whenever an unusually
concentrated sample is encountered, it should be followed by an
analysis of a blank to check for cross contamination. For samples
containing large amounts of water-soluble materials, suspended solids,
high boiling compounds or high purgeable levels, it may be necessary to
wash the purging device with a detergent solution, rinse it with
distilled water, and then dry it in a 105 [deg]C oven between analyses.
The trap and other parts of the system are also subject to
contamination; therefore, frequent bakeout and purging of the entire
system may be required. Screening samples at high dilution may prevent
introduction of contaminants into the system.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this viewpoint,
exposure to these chemicals must be reduced to the lowest possible
level. The laboratory is responsible for maintaining a current
awareness file of OSHA regulations regarding the safe handling of the
chemicals specified in this method. A reference file of safety data
sheets (SDSs, OSHA, 29 CFR 1910.1200(g)) should also be made available
to all personnel involved in sample handling and chemical analysis.
Additional references to laboratory safety are available and have been
identified (References 7-9) for the information of the analyst.
4.2. The following analytes covered by this method have been
tentatively classified as known or suspected human or mammalian
carcinogens: Benzene; carbon tetrachloride; chloroform; 1,4-
dichlorobenzene; 1,2-dichloroethane; 1,2-dichloropropane; methylene
chloride; tetrachloroethylene; trichloroethylene; and vinyl chloride.
Primary standards of these toxic compounds should be prepared in a
chemical fume hood, and a NIOSH/MESA approved toxic gas respirator
should be worn when handling high concentrations of these compounds.
4.3 This method allows the use of hydrogen as a carrier gas in
place of helium (Section 5.3.1.2). The laboratory should take the
necessary precautions in dealing with hydrogen, and should limit
hydrogen flow at the source to prevent buildup of an explosive mixture
of hydrogen in air.
5. Apparatus and Materials
Note: Brand names, suppliers, and part numbers are cited for
illustration purposes only. No endorsement is implied. Equivalent
performance may be achieved using equipment and materials other than
those specified here. Demonstration of equivalent performance that
meets the requirements of this method is the responsibility of the
laboratory. Suppliers for equipment and materials in this method may
be found through an on-line search.
5.1 Sampling equipment for discrete sampling.
5.1.1 Vial--25 or 40 mL capacity, or larger, with screw cap with a
hole in the center (Pierce #13075 or equivalent). Unless pre-cleaned,
detergent wash, rinse with tap and reagent water, and dry at 105 [deg]C
before use.
5.1.2 Septum--Fluoropolymer-faced silicone (Pierce #12722 or
equivalent). Unless pre-cleaned, detergent wash, rinse with tap and
reagent water, and dry at 105 5 [deg]C for one hour before
use.
5.2 Purge-and-trap system--The purge-and-trap system consists of
three separate pieces of equipment: A purging device, trap, and
desorber. Several complete systems are commercially available. Any
system that meets the performance requirements in this method may be
used.
5.2.1 The purging device should accept 5- to 25-mL samples with a
water column at least 3 cm deep. The purge gas must pass though the
water column as finely divided bubbles. The purge gas must be
introduced no more than 5 mm from the base of the water column. The
purging device illustrated in Figure 1 meets these design criteria.
Purge devices of a different volume may be used so long as the
performance requirements in this method are met.
5.2.2 The trap should be at least 25 cm long and have an inside
diameter of at least 0.105 in. The trap should be packed to contain the
following minimum lengths of adsorbents: 1.0 cm of methyl silicone
coated packing (Section 6.3.2), 15 cm of 2,6-diphenylene oxide polymer
(Section 6.3.1), and 8 cm of silica gel (Section 6.3.3). The minimum
specifications for the trap are illustrated in Figure 2. A trap with
different dimensions and packing materials is acceptable so long as the
performance requirements in this method are met.
5.2.3 The desorber should be capable of rapidly heating the trap to
the temperature necessary to desorb the analytes of interest, and of
maintaining
[[Page 9030]]
this temperature during desorption. The trap should not be heated
higher than the maximum temperature recommended by the manufacturer.
The desorber illustrated in Figure 2 meets these design criteria.
5.2.4 The purge-and-trap system may be assembled as a separate unit
or coupled to a gas chromatograph as illustrated in Figures 3 and 4.
5.3 GC/MS system.
5.3.1 Gas chromatograph (GC)--An analytical system complete with a
temperature programmable gas chromatograph and all required
accessories, including syringes and analytical columns. Autosamplers
designed for purge-and-trap analysis of volatiles also may be used.
5.3.1.1 Injection port--Volatiles interface, split, splitless,
temperature programmable split/splitless (PTV), large volume, on-
column, backflushed, or other.
5.3.1.2 Carrier gas--Data in the tables in this method were
obtained using helium carrier gas. If another carrier gas is used,
analytical conditions may need to be adjusted for optimum performance,
and calibration and all QC tests must be performed with the alternate
carrier gas. See Section 4.3 for precautions regarding the use of
hydrogen as a carrier gas.
5.3.2 GC column--See the footnote to Table 3. Other columns or
column systems may be used provided all requirements in this method are
met.
5.3.3 Mass spectrometer--Capable of repetitively scanning from 35-
260 Daltons (amu) every 2 seconds or less, utilizing a 70 eV (nominal)
electron energy in the electron impact ionization mode, and producing a
mass spectrum which meets all criteria in Table 4 when 50 ng or less of
4-bromofluorobenzene (BFB) is injected through the GC inlet. If
acrolein, acrylonitrile, chloromethane, and vinyl chloride are to be
determined, it may be necessary to scan from below 25 Daltons to
measure the peaks in the 26--35 Dalton range for reliable
identification.
5.3.4 GC/MS interface--Any GC to MS interface that meets all
performance requirements in this method may be used.
5.3.5 Data system--A computer system must be interfaced to the mass
spectrometer that allows continuous acquisition and storage of mass
spectra throughout the chromatographic program. The computer must have
software that allows searching any GC/MS data file for specific m/z's
(masses) and plotting m/z abundances versus time or scan number. This
type of plot is defined as an extracted ion current profile (EICP).
Software must also be available that allows integrating the abundance
at any EICP between specified time or scan number limits.
5.4 Syringes--Graduated, 5-25 mL, glass hypodermic with Luerlok
tip, compatible with the purging device.
5.5 Micro syringes--Graduated, 25-1000 [mu]L, with 0.006 in. ID
needle.
5.6 Syringe valve--Two-way, with Luer ends.
5.7 Syringe--5 mL, gas-tight with shut-off valve.
5.8 Bottle--15 mL, screw-cap, with Teflon cap liner.
5.9 Balance--Analytical, capable of accurately weighing 0.0001 g.
6. Reagents
6.1 Reagent water--Reagent water is defined as water in which the
analytes of interest and interfering compounds are not detected at the
MDLs of the analytes of interest. It may be generated by passing
deionized water, distilled water, or tap water through a carbon bed,
passing the water through a water purifier, or heating the water to
between 90 and 100 [deg]C while bubbling contaminant free gas through
it for approximately 1 hour. While still hot, transfer the water to
screw-cap bottles and seal with a fluoropolymer-lined cap.
6.2 Sodium thiosulfate--(ACS) Granular.
6.3 Trap materials.
6.3.1 2,6-Diphenylene oxide polymer--Tenax, 60/80 mesh,
chromatographic grade, or equivalent.
6.3.2 Methyl silicone packing--3% OV-1 on Chromosorb-W, 60/80 mesh,
or equivalent.
6.3.3 Silica gel--35/60 mesh, Davison, Grade-15 or equivalent.
Other trap materials are acceptable if performance requirements in
this method are met.
6.4 Methanol--Demonstrated to be free from the target analytes and
potentially interfering compounds.
6.5 Stock standard solutions--Stock standard solutions may be
prepared from pure materials, or purchased as certified solutions.
Traceability must be to the National Institute of Standards and
Technology (NIST) or other national standard. Stock solution
concentrations alternate to those below may be used. Prepare stock
standard solutions in methanol using assayed liquids or gases as
appropriate. Because some of the compounds in this method are known to
be toxic, primary dilutions should be prepared in a hood, and a NIOSH/
MESA approved toxic gas respirator should be worn when high
concentrations of neat materials are handled. The following procedure
may be used to prepare standards from neat materials:
6.5.1 Place about 9.8 mL of methanol in a 10-mL ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes or until all alcohol wetted surfaces have dried. Weigh
the flask to the nearest 0.1 mg.
6.5.2 Add the assayed reference material.
6.5.2.1 Liquids--Using a 100 [mu]L syringe, immediately add two or
more drops of assayed reference material to the flask. Be sure that the
drops fall directly into the alcohol without contacting the neck of the
flask. Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in [mu]g/[mu]L from
the net gain in weight.
6.5.2.2 Gases--To prepare standards for any of compounds that boil
below 30 [deg]C, fill a 5-mL valved gas-tight syringe with reference
standard vapor to the 5.0 mL mark. Lower the needle to 5 mm above the
methanol meniscus. Slowly introduce the vapor above the surface of the
liquid (the vapor will rapidly dissolve in the methanol). Reweigh,
dilute to volume, stopper, then mix by inverting the flask several
times. Calculate the concentration in [mu]g/[mu]L from the net gain in
weight.
6.5.3 When compound purity is assayed to be 96% or greater, the
weight may be used without correction to calculate the concentration of
the stock standard. Commercially prepared stock standards may be used
at any concentration if they are certified by the manufacturer or by an
independent source.
6.5.4 Prepare fresh standards weekly for the gases and 2-
chloroethylvinyl ether. All standards should be replaced after one
month, or sooner if the concentration of an analyte changes by more
than 10 percent.
Note: 2-Chloroethylvinyl ether has been shown to be stable for
as long as one month if prepared as a separate standard, and the
other analytes have been shown to be stable for as long as 2 months
if stored at less than -10 [deg]C with minimal headspace in sealed,
miniature inert-valved vials.
6.6 Secondary dilution standards--Using stock solutions, prepare
secondary dilution standards in methanol that contain the compounds of
interest, either singly or mixed. Secondary dilution standards should
be prepared at concentrations such that the aqueous calibration
standards prepared in Section 7.3.2 will bracket the working range of
the analytical system.
6.7 Surrogate standard spiking solution--Select a minimum of three
surrogate compounds from Table 5. The surrogates selected should match
the purging characteristics of the analytes of interest as closely as
possible. Prepare a stock standard solution for each
[[Page 9031]]
surrogate in methanol as described in Section 6.5, and prepare a
solution for spiking the surrogates into all blanks, LCSs, and MS/MSDs.
The spiking solution should be prepared such that spiking a small
volume will result in surrogate concentrations near the mid-point of
the calibration range. For example, adding 10 [mu]L of a spiking
solution containing the surrogates at a concentration of 15 [mu]g/mL in
methanol to a 5-mL aliquot of water would result in a concentration of
30 [mu]g/L for each surrogate. Other surrogate concentrations may be
used.
6.8 BFB standard--Prepare a solution of BFB in methanol as
described in Sections 6.5 and 6.6. The solution should be prepared such
that an injection or purging from water will result in introduction of
<=50 ng into the GC. BFB may be included in a mixture with the internal
standards and/or surrogates.
6.9 Quality control check sample concentrate--See Section 8.2.1.
6.10 Storage--When not being used, store standard solutions
(Sections 6.5-6.9) at -10 to -20 [deg]C, protected from light, in
fluoropolymer-sealed glass containers with minimal headspace.
7. Calibration
7.1 Assemble a purge-and-trap system that meets the specifications
in Section 5.2. Prior to first use, condition the trap overnight at 180
[deg]C by backflushing with gas at a flow rate of at least 20 mL/min.
Condition the trap daily prior to use.
7.2 Connect the purge-and-trap system to the gas chromatograph. The
gas chromatograph should be operated using temperature and flow rate
conditions equivalent to those given in the footnotes to Table 3.
Alternative temperature and flow rate conditions may be used provided
that performance requirements in this method are met.
7.3 Internal standard calibration.
7.3.1 Internal standards.
7.3.1.1 Select three or more internal standards similar in
chromatographic behavior to the compounds of interest. Suggested
internal standards are listed in Table 5. Use the base peak m/z as the
primary m/z for quantification of the standards. If interferences are
found at the base peak, use one of the next two most intense m/z's for
quantitation. Demonstrate that measurement of the internal standards
are not affected by method or matrix interferences.
7.3.1.2 To assure accurate analyte identification, particularly
when selected ion monitoring (SIM) is used, it may be advantageous to
include more internal standards than those suggested in Section
7.3.1.1. An analyte will be located most accurately if its retention
time relative to an internal standard is in the range of 0.8 to 1.2.
7.3.1.3 Prepare a stock standard solution for each internal
standard surrogate in methanol as described in Section 6.5, and prepare
a solution for spiking the internal standards into all blanks, LCSs,
and MS/MSDs. The spiking solution should be prepared such that spiking
a small volume will result in internal standard concentrations near the
mid-point of the calibration range. For example, adding 10 [mu]L of a
spiking solution containing the internal standards at a concentration
of 15 [mu]g/mL in methanol to a 5-mL aliquot of water would result in a
concentration of 30 [mu]g/L for each internal standard. Other
concentrations may be used. The internal standard solution and the
surrogate standard spiking solution (Section 6.7) may be combined, if
desired. Store the solution at <6 [deg]C in fluoropolymer-sealed glass
containers with a minimum of headspace. Replace the solution after 1
month, or more frequently if comparison with QC standards indicates a
problem.
7.3.2 Calibration.
7.3.2.1 Calibration standards.
7.3.2.1.1 Prepare calibration standards at a minimum of five
concentration levels for each analyte of interest by adding appropriate
volumes of one or more stock standards to a fixed volume (e.g., 40 mL)
of reagent water in volumetric glassware. Fewer levels may be necessary
for some analytes based on the sensitivity of the MS. The concentration
of the lowest calibration standard for an analyte should be at or near
the ML value in Table 1 for an analyte listed in that table. The ML
value may be rounded to a whole number that is more convenient for
preparing the standard, but must not exceed the ML values listed in
Table 1 for those analytes which list ML values. Alternatively, the
laboratory may establish the ML for each analyte based on the
concentration of the lowest calibration standard in a series of
standards obtained from a commercial vendor, again, provided that the
ML values does not exceed the MLs in Table 1, and provided that the
resulting calibration meets the acceptance criteria in Section 7.3.4,
based on the RSD, RSE, or R\2\.
The concentrations of the higher standards should correspond to the
expected range of concentrations found in real samples, or should
define the working range of the GC/MS system for full-scan and/or SIM
operation, as appropriate. A minimum of six concentration levels is
required for a second order, non-linear (e.g., quadratic; ax\2\ + bx +
c) calibration. Calibrations higher than second order are not allowed.
7.3.2.1.2 To each calibration standard or standard mixture, add a
known constant volume of the internal standard spiking solution
(Section 7.3.1.3) and surrogate standard spiking solution (Section 6.7)
or the combined internal standard solution and surrogate spiking
solution (Section 7.3.1.3). Aqueous standards may be stored up to 24
hours, if held in sealed vials with zero headspace as described in
Section 9.1. If not so stored, they must be discarded after one hour.
7.3.2.2 Prior to analysis of the calibration standards, analyze the
BFB standard (Section 6.8) and adjust the scan rate of the MS to
produce a minimum of 5 mass spectra across the BFB GC peak, but do not
exceed 2 seconds per scan. Adjust instrument conditions until the BFB
criteria in Table 4 are met.
Note: The BFB spectrum may be evaluated by summing the
intensities of the m/z's across the GC peak, subtracting the
background at each m/z in a region of the chromatogram within 20
scans of but not including any part of the BFB peak. The BFB
spectrum may also be evaluated by fitting a Gaussian to each m/z and
using the intensity at the maximum for each Gaussian, or by
integrating the area at each m/z and using the integrated areas.
Other means may be used for evaluation of the BFB spectrum so long
as the spectrum is not distorted to meet the criteria in Table 4.
7.3.2.3 Analyze the mid-point standard and enter or review the
retention time, relative retention time, mass spectrum, and
quantitation m/z in the data system for each analyte of interest,
surrogate, and internal standard. If additional analytes (Table 2) are
to be quantified, include these analytes in the standard. The mass
spectrum for each analyte must be comprised of a minimum of 2 m/z's; 3
to 5 m/z's assure more reliable analyte identification. Suggested
quantitation m/z's are shown in Table 6 as the primary m/z. For
analytes in Table 6 that do not have a secondary m/z, acquire a mass
spectrum and enter one or more secondary m/z's for more reliable
identification. If an interference occurs at the primary m/z, use one
of the secondary m/z's or an alternate m/z. A single m/z only is
required for quantitation.
7.3.2.4 For SIM operation, determine the analytes in each
descriptor, the quantitation m/z for each analyte (the quantitation m/z
can be the same as for full-scan operation; Section 7.3.2.3), the dwell
time on each m/z for each analyte,
[[Page 9032]]
and the beginning and ending retention time for each descriptor.
Analyze the verification standard in scan mode to verify m/z's and
establish retention times for the analytes. There must be a minimum of
two m/z's for each analyte to assure analyte identification. To
maintain sensitivity, the number of m/z's in a descriptor should be
limited. For example, for a descriptor with 10 m/z's and a
chromatographic peak width of 5 sec, a dwell time of 100 ms at each m/z
would result in a scan time of 1 second and provide 5 scans across the
GC peak. The quantitation m/z will usually be the most intense peak in
the mass spectrum. The quantitation m/z and dwell time may be optimized
for each analyte. However, if a GC peak spans two (or more)
descriptors, the dwell time and cycle time (scans/sec) should be set to
the same value in both segments in order to maintain equivalent
response. The acquisition table used for SIM must take into account the
mass defect (usually less than 0.2 Dalton) that can occur at each m/z
monitored.
7.3.2.5 For combined scan and SIM operation, set up the scan
segments and descriptors to meet requirements in Sections 7.3.2.2-
7.3.2.4.
7.3.3 Analyze each calibration standard according to Section 10 and
tabulate the area at the quantitation m/z against concentration for
each analyte of interest, surrogate, and internal standard. Calculate
the response factor (RF) for each compound at each concentration using
Equation 1.
[GRAPHIC] [TIFF OMITTED] TP19FE15.012
Where:
As = Area of the characteristic m/z for the analyte to be
measured.
Ais = Area of the characteristic m/z for the internal
standard.
Cis = Concentration of the internal standard ([mu]g/L).
Cs = Concentration of the analyte to be measured ([mu]g/
L).
7.3.4 Calculate the mean (average) and relative standard deviation
(RSD) of the response factors. If the RSD is less than 35%, the RF can
be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to fit a linear or
quadratic regression of response ratios, As/Ais,
vs. concentration ratios Cs/Cis. If used, the regression must be
weighted inversely proportional to concentration (1/C). The coefficient
of determination (R\2\) of the weighted regression must be greater than
0.920 (this value roughly corresponds to the RSD limit of 35%).
Alternatively, the relative standard error (Reference 10) may be used
as an acceptance criterion. As with the RSD, the RSE must be less than
35%. If an RSE less than 35% cannot be achieved for a quadratic
regression, system performance is unacceptable, and the system must be
adjusted and re-calibrated.
Note: Using capillary columns and current instrumentation, it
is quite likely that a laboratory can calibrate the target analytes
in this method and achieve a linearity metric (either RSD or RSE)
well below 35%. Therefore, laboratories are permitted to use more
stringent acceptance criteria for calibration than described here,
for example, to harmonize their application of this method with
those from other sources.
7.4 Calibration verification--Because the analytical system is
calibrated by purge of the analytes from water, calibration
verification is performed using the laboratory control sample (LCS).
See Section 8.4 for requirements for calibration verification using the
LCS, and the Glossary for further definition.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality assurance program. The minimum requirements of this
program consist of an initial demonstration of laboratory capability
and ongoing analysis of spiked samples and blanks to evaluate and
document data quality (40 CFR 136.7). The laboratory must maintain
records to document the quality of data generated. Results of ongoing
performance tests are compared with established QC acceptance criteria
to determine if the results of analyses meet performance requirements
of this method. When results of spiked samples do not meet the QC
acceptance criteria in this method, a quality control check sample
(laboratory control sample; LCS) must be analyzed to confirm that the
measurements were performed in an in-control mode of operation. A
laboratory may develop its own performance criteria (as QC acceptance
criteria), provided such criteria are as or more restrictive than the
criteria in this method.
8.1.1 The laboratory must make an initial demonstration of
capability (DOC) to generate acceptable precision and recovery with
this method. This demonstration is detailed in Section 8.2.
8.1.2 In recognition of advances that are occurring in analytical
technology, and to overcome matrix interferences, the laboratory is
permitted certain options (Section 1.5 and 40 CFR 136.6(b)) to improve
separations or lower the costs of measurements. These options may
include an alternate purge-and-trap device, and changes in both column
and type of mass spectrometer (see 40 CFR 136.6(b)(4)(xvi)). Alternate
determinative techniques, such as substitution of spectroscopic or
immunoassay techniques, and changes that degrade method performance,
are not allowed. If an analytical technique other than GC/MS is used,
that technique must have a specificity equal to or greater than the
specificity of GC/MS for the analytes of interest. The laboratory is
also encouraged to participate in inter-comparison and performance
evaluation studies (see Section 8.9).
8.1.2.1 Each time a modification is made to this method, the
laboratory is required to repeat the procedure in Section 8.2. If the
detection limit of the method will be affected by the change, the
laboratory must demonstrate that the MDLs (40 CFR part 136, appendix B)
are lower than one-third the regulatory compliance limit, or at least
as low as the MDLs listed in this method, whichever are greater. If
calibration will be affected by the change, the instrument must be
recalibrated per Section 7. Once the modification is demonstrated to
produce results equivalent or superior to results produced by this
method, that modification may be used routinely thereafter, so long as
the other requirements in this method are met (e.g., matrix spike/
matrix spike duplicate recovery and relative percent difference).
8.1.2.1.1 If a modification is to be applied to a specific
discharge, the laboratory must prepare and analyze matrix spike/matrix
spike duplicate (MS/MSD) samples (Section 8.3) and LCS samples (Section
8.4). The laboratory must include internal standards and surrogates
(Section 8.7) in each of the samples. The MS/MSD and LCS samples must
be fortified with the analytes of interest (Section 1.3.). If the
modification is for nationwide use, MS/
[[Page 9033]]
MSD samples must be prepared from a minimum of nine different
discharges (See Section 8.1.2.1.2), and all QC acceptance criteria in
this method must be met. This evaluation only needs to be performed
once, other than for the routine QC required by this method (for
example it could be performed by the vendor of the alternate materials)
but any laboratory using that specific material must have the results
of the study available. This includes a full data package with the raw
data that will allow an independent reviewer to verify each
determination and calculation performed by the laboratory (see Section
8.1.2.2.5, items a-l).
8.1.2.1.2 Sample matrices on which MS/MSD tests must be performed
for nationwide use of an allowed modification:
(a) Effluent from a POTW
(b) ASTM D5905 Standard Specification for Substitute Wastewater
(c) Sewage sludge, if sewage sludge will be in the permit
(d) ASTM D1141 Standard Specification for Substitute Ocean Water,
if ocean water will be in the permit
(e) Untreated and treated wastewaters up to a total of nine matrix
types (see http:water.epa.gov/scitech/wastetech/guide/industry.cfm) for
a list of industrial categories with existing effluent guidelines).
At least one of the above wastewater matrix types must have at
least one of the following characteristics:
(i) Total suspended solids greater than 40 mg/L
(ii) Total dissolved solids greater than 100 mg/L
(iii) Oil and grease greater than 20 mg/L
(iv) NaCl greater than 120 mg/L
(v) CaCO3 greater than 140 mg/L
The interim acceptance criteria for MS, MSD recoveries that do not
have recovery limits specified in Table 7, and recoveries for
surrogates that do not have recovery limits specified in Table 7, must
be no wider than 60-140%, and the relative percent difference (RPD) of
the concentrations in the MS and MSD that do not have RPD limits
specified in Table 7 must be less than 30%. Alternatively, the
laboratory may use the laboratory's in-house limits if they are
tighter.
(f) A proficiency testing (PT) sample from a recognized provider,
in addition to tests of the nine matrices (Section 8.1.2.1.1).
8.1.2.2 The laboratory is required to maintain records of
modifications made to this method. These records include the following,
at a minimum:
8.1.2.2.1 The names, titles, street addresses, telephone numbers,
and email addresses of the analyst(s) that performed the analyses and
modification, and of the quality control officer that witnessed and
will verify the analyses and modifications.
8.1.2.2.2 A list of analytes, by name and CAS Registry Number.
8.1.2.2.3 A narrative stating reason(s) for the modifications.
8.1.2.2.4 Results from all quality control (QC) tests comparing the
modified method to this method, including:
(a) Calibration (Section 7).
(b) Calibration verification/LCS (Section 8.4).
(c) Initial demonstration of capability (Section 8.2).
(d) Analysis of blanks (Section 8.5).
(e) Matrix spike/matrix spike duplicate analysis (Section 8.3).
(f) Laboratory control sample analysis (Section 8.4).
8.1.2.2.5 Data that will allow an independent reviewer to validate
each determination by tracing the instrument output (peak height, area,
or other signal) to the final result. These data are to include:
(a) Sample numbers and other identifiers.
(b) Analysis dates and times.
(c) Analysis sequence/run chronology.
(d) Sample volume (Section 10).
(e) Sample dilution (Section 13.2).
(f) Instrument and operating conditions.
(g) Column (dimensions, material, etc).
(h) Operating conditions (temperature program, flow rate, etc).
(i) Detector (type, operating conditions, etc).
(j) Chromatograms, mass spectra, and other recordings of raw data.
(k) Quantitation reports, data system outputs, and other data to
link the raw data to the results reported.
(l) A written Standard Operating Procedure (SOP).
8.1.2.2.6 The individual laboratory wishing to use a given
modification must perform the start-up tests in Section 8.1.2 (e.g.,
DOC, MDL), with the modification as an integral part of this method
prior to applying the modification to specific discharges. Results of
the DOC must meet the QC acceptance criteria in Table 7 for the
analytes of interest (Section 1.3), and the MDLs must be equal to or
lower than the MDLs in Table3 for the analytes of interest
8.1.3 Before analyzing samples, the laboratory must analyze a blank
to demonstrate that interferences from the analytical system, labware,
and reagents are under control. Each time a batch of samples is
analyzed or reagents are changed, a blank must be analyzed as a
safeguard against laboratory contamination. Requirements for the blank
are given in Section 8.5.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of one sample, in duplicate, with the batch of samples run
during a given 12-hour shift (see the note at Section 8.4). The
laboratory must also spike and analyze, in duplicate, a minimum of 5%
of all samples from a given site or discharge to monitor and evaluate
method and laboratory performance on the sample matrix. The batch and
site/discharge samples may be the same. The procedure for spiking and
analysis is given in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
analysis of a quality control check sample (laboratory control sample,
LCS; on-going precision and recovery sample, OPR) that the measurement
system is in control. This procedure is given in Section 8.4.
8.1.6 The laboratory should maintain performance records to
document the quality of data that is generated. This procedure is given
in Section 8.8.
8.1.7 The large number of analytes tested in performance tests in
this method present a substantial probability that one or more will
fail acceptance criteria when many analytes are tested simultaneously,
and a re-test is allowed if this situation should occur. If, however,
continued re-testing results in further repeated failures, the
laboratory should document the failures (e.g., as qualifiers on
results) and either avoid reporting results for analytes that failed or
report the problem and failures with the data. Failure to report does
not relieve a discharger or permittee of reporting timely results.
Results for regulatory compliance must be accompanied by QC results
that meet all acceptance criteria.
8.2 Initial demonstration of capability (DOC)--To establish the
ability to generate acceptable recovery and precision, the laboratory
must perform the DOC in Sections 8.2.1 through 8.2.6 for the analytes
of interest. The laboratory must also establish MDLs for the analytes
of interest using the MDL procedure at 40 CFR part 136, appendix B. The
laboratory's MDLs must be equal to or lower than those listed in Table
1 for those analytes which list MDL values, or lower than one-third the
regulatory compliance limit, whichever is greater. For MDLs not listed
in Table 1, the laboratory must determine the MDLs using the MDL
procedure at 40 CFR part 136, appendix B under the same conditions
[[Page 9034]]
used to determine the MDLs for the analytes listed in Table 1. All
procedures used in the analysis must be included in the DOC.
8.2.1 For the DOC, a QC check sample concentrate containing each
analyte of interest (Section 1.3) is prepared in methanol. The QC check
sample concentrate must be prepared independently from those used for
calibration, but may be from the same source as the second-source
standard used for calibration verification/LCS (Sections 7.4 and 8.4).
The concentrate should produce concentrations of the analytes of
interest in water at the mid-point of the calibration range, and may be
at the same concentration as the LCS (Section 8.4).
Note: QC check sample concentrates are no longer available from
EPA.
8.2.2 Using a pipet or micro-syringe, prepare four LCSs by adding
an appropriate volume of the concentrate to each of four aliquots of
reagent water. The volume of reagent water must be the same as the
volume that will be used for the sample, blank (Section 8.5), and MS/
MSD (Section 8.3). A volume of 5 mL and a concentration of 20 [mu]g/L
were used to develop the QC acceptance criteria in Table 7. An
alternative volume and sample concentration may be used, provided that
all QC tests are performed and all QC acceptance criteria in this
method are met. Also add an aliquot of the surrogate spiking solution
(Section 6.7) and internal standard spiking solution (Section 7.3.1.3)
to the reagent-water aliquots.
8.2.3 Analyze the four LCSs according to the method beginning in
Section 10.
8.2.4 Calculate the average percent recovery (x) and the standard
deviation of the percent recovery (s) for each analyte using the four
results.
8.2.5 For each analyte, compare s and x with the corresponding
acceptance criteria for precision and recovery in Table 7. For analytes
in Tables 1 and 2 not listed in Table 7, DOC QC acceptance criteria
must be developed by the laboratory. EPA has provided guidance for
development of QC acceptance criteria (References 11 and 12). If s and
x for all analytes of interest meet the acceptance criteria, system
performance is acceptable and analysis of blanks and samples may begin.
If any individual s exceeds the precision limit or any individual x
falls outside the range for recovery, system performance is
unacceptable for that analyte.
Note: The large number of analytes in Tables 1 and 2 present a
substantial probability that one or more will fail at least one of
the acceptance criteria when many or all analytes are determined
simultaneously. Therefore, the analyst is permitted to conduct a
``re-test'' as described in Sec. 8.2.6.
8.2.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, repeat the test for only the analytes that
failed. If results for these analytes pass, system performance is
acceptable and analysis of samples and blanks may proceed. If one or
more of the analytes again fail, system performance is unacceptable for
the analytes that failed the acceptance criteria. Correct the problem
and repeat the test (Section 8.2). See Section 8.1.7 for disposition of
repeated failures.
Note: To maintain the validity of the test and re-test, system
maintenance and/or adjustment is not permitted between this pair of
tests.
8.3 Matrix spike and matrix spike duplicate (MS/MSD)--The
laboratory must, on an ongoing basis, spike at least 5% of the samples
from each sample site being monitored in duplicate to assess accuracy
(recovery and precision). The data user should identify the sample and
the analytes of interest (Section 1.3) to be spiked. If direction
cannot be obtained, the laboratory must spike at least one sample per
batch of samples analyzed on a given 12-hour shift with the analytes in
Table 1. Spiked sample results should be reported only to the data user
whose sample was spiked, or as requested or required by a regulatory/
control authority, or in a permit.
8.3.1 If, as in compliance monitoring, the concentration of a
specific analyte will be checked against a regulatory concentration
limit, the concentration of the spike should be at that limit;
otherwise, the concentration of the spike should be one to five times
higher than the background concentration determined in Section 8.3.2,
at or near the midpoint of the calibration range, or at the
concentration in the LCS (Section 8.4) whichever concentration would be
larger.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of the each analyte of interest. If necessary,
prepare a new check sample concentrate (Section 8.2.1) appropriate for
the background concentration. Spike and analyze two additional sample
aliquots, and determine the concentration after spiking (A1
and A2) of each analyte. Calculate the percent recoveries
(P1 and P2) as 100 (A1-B)/T and 100
(A2-B)/T, where T is the known true value of the spike. Also
calculate the relative percent difference (RPD) between the
concentrations (A1 and A2) as 200
[verbarlm]A1-A2 [verbarlm]/(A1 +
A2). If necessary, adjust the concentrations used to
calculate the RPD to account for differences in the volumes of the
spiked aliquots.
8.3.3 Compare the percent recoveries (P1 and
P2) and the RPD for each analyte in the MS/MSD aliquots with
the corresponding QC acceptance criteria in Table 7. A laboratory may
develop and apply QC acceptance criteria more restrictive than the
criteria in Table 6, if desired.
8.3.3.1 If any individual P falls outside the designated range for
recovery in either aliquot, or the RPD limit is exceeded, the result
for the analyte in the unspiked sample is suspect and may not be
reported or used for permitting or regulatory compliance purposes. See
Section 8.1.7 for disposition of failures.
8.3.3.2 The acceptance criteria in Table 7 were calculated to
include an allowance for error in measurement of both the background
and spike concentrations, assuming a spike to background ratio of 5:1.
This error will be accounted for to the extent that the spike to
background ratio approaches 5:1 (Reference 13). If spiking is performed
at a concentration lower than 20 [mu]g/L, the laboratory must use
either the QC acceptance criteria in Table 7, or optional QC acceptance
criteria calculated for the specific spike concentration. To use the
optional acceptance criteria: (1) Calculate recovery (X') using the
equation in Table 8, substituting the spike concentration (T) for C;
(2) Calculate overall precision (S') using the equation in Table 8,
substituting X' for x; (3) Calculate the range for recovery at the
spike concentration as (100 X'/T) 2.44(100 S'/T)%
(Reference 4). For analytes of interest in Tables 1 and 2 not listed in
Table 7, QC acceptance criteria must be developed by the laboratory.
EPA has provided guidance for development of QC acceptance criteria
(References 11 and 12).
8.3.4 After analysis of a minimum of 20 MS/MSD samples for each
target analyte and surrogate, the laboratory must calculate and apply
in-house QC limits for recovery and RPD of future MS/MSD samples
(Section 8.3). The QC limits for recovery are calculated as the mean
observed recovery 3 standard deviations, and the upper QC
limit for RPD is calculated as the mean RPD plus 3 standard deviations
of the RPDs. The in-house QC limits must be updated at least every two
years and re-established after any major change in the analytical
instrumentation or process. At least 80% of the analytes tested in the
MS/MSD must have in-house QC acceptance criteria that are tighter than
those in
[[Page 9035]]
Table 7. If an in-house QC limit for the RPD is greater than the limit
in Table 7, then the limit in Table 7 must be used. Similarly, if an
in-house lower limit for recovery is below the lower limit in Table 7,
then the lower limit in Table 7 must be used, and if an in-house upper
limit for recovery is above the upper limit in Table 7, then the upper
limit in Table 7 must be used. The laboratory must evaluate surrogate
recovery data in each sample against its in-house surrogate recovery
limits. The laboratory may use 60-140% as interim acceptance criteria
for surrogate recoveries until in-house limits are developed.
8.4 Calibration verification/laboratory control sample (LCS)--The
working calibration curve or RF must be verified at the beginning of
each 12-hour shift by the measurement of an LCS.
Note: The 12-hour shift begins after analysis of the blank that
follows the LCS and ends 12 hours later. The blank is outside of the
12-hour shift. The MS and MSD are treated as samples and are
analyzed within the 12-hour shift.
8.4.1 Prepare the LCS by adding QC check sample concentrate
(Section 8.2.1) to reagent water. Include all analytes of interest
(Section 1.3) in the LCS. The LCS may be the same sample prepared for
the DOC (Section 8.2.1). The volume of reagent water must be the same
as the volume used for the sample, blank (Section 8.5), and MS/MSD
(Section 8.3). Also add an aliquot of the surrogate solution (Section
6.7) and internal standard solution (Section 7.3.1.3). The
concentration of the analytes in reagent water should be the same as
the concentration in the DOC (Section 8.2.2).
8.4.2 Analyze the LCS prior to analysis of field samples in the
batch of samples analyzed during the 12-hour shift (see the Note at
Section 8.4). Determine the concentration (A) of each analyte.
Calculate the percent recovery (Q) as 100 (A/T) %, where T is the true
value of the concentration in the LCS.
8.4.3 Compare the percent recovery (Q) for each analyte with its
corresponding QC acceptance criterion in Table 7. For analytes of
interest in Tables 1 and 2 not listed in Table 7, use the QC acceptance
criteria developed for the MS/MSD (Section 8.3.3.2). If the recoveries
for all analytes of interest fall within their respective QC acceptance
criteria, analysis of blanks and field samples may proceed. If any
individual Q falls outside the range, proceed according to Section
8.4.4.
Note: The large number of analytes in Tables 1-2 present a
substantial probability that one or more will fail the acceptance
criteria when all analytes are tested simultaneously. Because a re-
test is allowed in event of failure (Sections 8.1.7 and 8.4.3), it
may be prudent to analyze two LCSs together and evaluate results of
the second analysis against the QC acceptance criteria only if an
analyte fails the first test.
8.4.4 Repeat the test only for those analytes that failed to meet
the acceptance criteria (Q). If these analytes now pass, system
performance is acceptable and analysis of blanks and samples may
proceed. Repeated failure, however, will confirm a general problem with
the measurement system. If this occurs, repeat the test using a fresh
LCS (Section 8.2.2) or an LCS prepared with a fresh QC check sample
concentrate (Section 8.2.1), or perform and document system repair.
Subsequent to repair, repeat the calibration verification/LCS test
(Section 8.4). If the acceptance criteria for Q cannot be met, re-
calibrate the instrument (Section 7). If failure of the LCS indicates a
systemic problem with samples analyzed during the 12-hour shift, re-
analyze the samples analyzed during that 12-hour shift. See Section
8.1.7 for disposition of repeated failures.
Note: To maintain the validity of the test and re-test, system
maintenance and/or adjustment is not permitted between this pair of
tests.
8.4.5 After analysis of 20 LCS samples, the laboratory must
calculate and apply in-house QC limits for recovery to future LCS
samples (Section 8.4). Limits for recovery in the LCS are calculated as
the mean recovery 3 standard deviations. A minimum of 80%
of the analytes tested for in the LCS must have QC acceptance criteria
tighter than those in Table 7. Many of the analytes and surrogates may
not contain recommended acceptance criteria. The laboratory should use
60-140% as interim acceptance criteria for recoveries of spiked
analytes and surrogates that do not have recovery limits specified in
Table 7, until in-house LCS and surrogate limits are developed. If an
in-house lower limit for recovery is lower than the lower limit in
Table 7, the lower limit in Table 7 must be used, and if an in-house
upper limit for recovery is higher than the upper limit in Table 7, the
upper limit in Table 7 must be used.
8.5 Blank--A blank must be analyzed at the beginning of each 12-
hour shift to demonstrate freedom from contamination. A blank must also
be analyzed after a sample containing a high concentration of an
analyte or potentially interfering compound to demonstrate freedom from
carry-over.
8.5.1 Spike the internal standards and surrogates into the blank.
Analyze the blank immediately after analysis of the LCS (Section 8.4)
and prior to analysis of the MS/MSD and samples to demonstrate freedom
from contamination.
8.5.2 If any analyte of interest is found in the blank: (1) at a
concentration greater than the MDL for the analyte, (2) at a
concentration greater than one-third the regulatory compliance limit,
or (3) at a concentration greater than one-tenth the concentration in a
sample analyzed during the 12-hour shift (Section 8.4), whichever is
greater; analysis of samples must be halted and samples affected by the
blank must be re-analyzed. Samples must be associated with an
uncontaminated blank before they may be reported or used for permitting
or regulatory compliance purposes.
8.6 Surrogate recoveries--Spike the surrogates into all samples,
blanks, LCSs, and MS/MSDs. Compare surrogate recoveries against the QC
acceptance criteria in Table 7. For surrogates in Table 5 without QC
acceptance criteria in Table 7, and for other surrogates that may be
used by the laboratory, limits must be developed by the laboratory. EPA
has provided guidance for development of QC acceptance criteria
(References 11 and 12). If any recovery fails its criteria, attempt to
find and correct the cause of the failure. Surrogate recoveries from
the blank and LCS may be used as pass/fail criteria by the laboratory
or as required by a regulatory authority, or may be used to diagnose
problems with the analytical system.
8.7 Internal standard responses.
8.7.1 Calibration verification/LCS--The responses (GC peak heights
or areas) of the internal standards in the calibration verification/LCS
must be within 50% to 200% (\1/2\ to 2x) of their respective responses
in the mid-point calibration standard. If they are not, repeat the LCS
test using a fresh QC check sample (Section 8.4.1) or perform and
document system repair. Subsequent to repair, repeat the calibration
verification/LCS test (Section 8.4). If the responses are still not
within 50% to 200%, re-calibrate the instrument (Section 7) and repeat
the calibration verification/LCS test.
8.7.2 Samples, blanks, and MS/MSDs--The responses (GC peak heights
or areas) of the internal standards in each sample, blank, and MS/MSD
must be within 50% to 200% (\1/2\ to 2x) of its respective response in
the most recent LCS. If, as a group, all internal standard are not
within this range, perform and document system repair, repeat the
calibration verification/LCS test
[[Page 9036]]
(Section 8.4), and re-analyze the affected samples. If a single
internal standard is not within the 50% to 200% range, use an alternate
internal standard for quantitation of the analyte referenced to the
affected internal standard.
8.8 As part of the QC program for the laboratory, control charts or
statements of accuracy for wastewater samples must be assessed and
records maintained periodically (see 40 CFR 136.7(c)(1)(viii)). After
analysis of five or more spiked wastewater samples as in Section 8.3,
calculate the average percent recovery (x) and the standard deviation
of the percent recovery (sp). Express the accuracy assessment as a
percent interval from x -2sp to x +2sp. For example, if x = 90% and sp
= 10%, the accuracy interval is expressed as 70-110%. Update the
accuracy assessment for each analyte on a regular basis (e.g., after
each 5-10 new accuracy measurements).
8.9 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and
the nature of the samples. Field duplicates may be analyzed to assess
the precision of environmental measurements. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Collect the sample as a grab sample in a glass container having
a total volume of at least 25 mL. Fill the sample bottle just to
overflowing in such a manner that no air bubbles pass through the
sample as the bottle is being filled. Seal the bottle so that no air
bubbles are entrapped in it. If needed, collect additional sample(s)
for the MS/MSD (Section 8.3).
9.2 Ice or refrigerate samples at <6 [deg]C from the time of
collection until analysis, but do not freeze. If residual chlorine is
present, add sodium thiosulfate preservative (10 mg/40 mL is sufficient
for up to 5 ppm Cl2) to the empty sample bottle just prior
to shipping to the sampling site. Any method suitable for field use may
be employed to test for residual chlorine (Reference 14). Field test
kits are also available for this purpose. If sodium thiosulfate
interferes in the determination of the analytes, an alternate
preservative (e.g., ascorbic acid or sodium sulfite) may be used. If
preservative has been added, shake the sample vigorously for one
minute. Maintain the hermetic seal on the sample bottle until time of
analysis.
9.3 If acrolein is to be determined, analyze the sample within 3
days. To extend the holding time to 14 days, acidify a separate sample
to pH 4-5 with HCl using the procedure in Section 9.7.
9.4 Experimental evidence indicates that some aromatic compounds,
notably benzene, toluene, and ethyl benzene are susceptible to rapid
biological degradation under certain environmental conditions
(Reference 3). Refrigeration alone may not be adequate to preserve
these compounds in wastewaters for more than seven days. To extend the
holding time for aromatic compounds to 14 days, acidify the sample to
approximately pH 2 using the procedure in Section 9.7.
9.5 If halocarbons are to be determined, either use the acidified
aromatics sample in Section 9.4 or acidify a separate sample to a pH of
about 2 using the procedure in Section 9.7. Aqueous samples should not
be preserved with acid if the ethers in Table 2, or the alcohols that
they would form upon hydrolysis, are of analytes of interest.
9.6 The ethers listed in Table 2 are prone to hydrolysis at pH 2
when a heated purge is used. Aqueous samples should not be acid
preserved if these ethers are of interest, or if the alcohols they
would form upon hydrolysis are of interest and the ethers are
anticipated to present.
9.7 Sample acidification--Collect about 500 mL of sample in a clean
container and adjust the pH of the sample to 4-5 for acrolein (Section
9.3), or to about 2 for the aromatic compounds (Section 9.4) by adding
1+1 HCl while swirling or stirring. Check the pH with narrow range pH
paper. Fill a sample container as described in Section 9.1.
Alternatively, fill a precleaned vial (Section 5.1.1) that contains
approximately 0.25 mL of 1+1 HCl with sample as in Section 9.1. If
preserved using this alternative procedure, the pH of the sample can be
verified to be <2 after some of the sample is removed for analysis.
Acidification will destroy 2-chloroethylvinyl ether; therefore,
determine 2-chloroethylvinyl ether from the unacidified sample.
9.8 All samples must be analyzed within 14 days of collection
(Reference 3), unless specified otherwise in Sections 9.3-9.7.
10. Sample Purging and Gas Chromatography
10.1 The footnote to Table 3 gives the suggested GC column and
operating conditions. Included in Table 3 are retention times and MDLs
that can be achieved under these conditions. Sections 10.2 through 10.7
suggest procedures that may be used with a manual purge-and-trap
system. Auto-samplers and other columns or chromatographic conditions
may be used if requirements in this method are met.
10.2 Attach the trap inlet to the purging device, and set the
purge-and-trap system to purge (Figure 3). Open the syringe valve
located on the purging device sample introduction needle.
10.3 Allow the sample to come to ambient temperature prior to
pouring an aliquot into the syringe. Remove the plunger from a syringe
and attach a closed syringe valve. Open the sample bottle (or standard)
and carefully pour the sample into the syringe barrel to just short of
overflowing. Replace the syringe plunger and compress the sample. Open
the syringe valve and vent any residual air while adjusting the sample
volume. Since this process of taking an aliquot destroys the validity
of the sample for future analysis, the analyst should fill a second
syringe at this time to protect against possible loss of data. Add the
surrogate spiking solution (Section 6.7) and internal standard spiking
solution (Section 7.3.1.3) through the valve bore, then close the
valve. The surrogate and internal standards may be mixed and added as a
single spiking solution. Autosamplers designed for purge-and-trap
analysis of volatiles also may be used.
10.4 Attach the syringe valve assembly to the syringe valve on the
purging device. Open the syringe valve and inject the sample into the
purging chamber.
10.5 Close both valves and purge the sample at a temperature, flow
rate, and duration sufficient to purge the less-volatile analytes onto
the trap, yet short enough to prevent blowing the more-volatile
analytes through the trap. The temperature, flow rate, and time should
be determined by test. The same purge temperature, flow rate, and purge
time must be used for all calibration, QC, and field samples.
10.6 After the purge, set the purge-and-trap system to the desorb
mode (Figure 4), and begin to temperature program the gas
chromatograph. Introduce the trapped materials to the GC column by
rapidly heating the trap to the desorb temperature while backflushing
the trap with carrier gas at the flow rate and for the time necessary
to desorb the analytes of interest. The optimum temperature, flow rate,
and time should be determined by test. The
[[Page 9037]]
same temperature, desorb time, and flow rate must be used for all
calibration, QC, and field samples. If heating of the trap does not
result in sharp peaks for the early eluting analytes, the GC column may
be used as a secondary trap by cooling to an ambient or subambient
temperature. To avoid carry-over and interferences, maintain the trap
at the desorb temperature and flow rate until the analytes, interfering
compounds, and excess water are desorbed. The optimum conditions should
be determined by test.
10.7 Start MS data acquisition at the start of the desorb cycle and
stop data collection when the analytes of interest, potentially
interfering compounds, and water have eluted (see the footnote to Table
3 for conditions).
10.8 Cool the trap to the purge temperature and return the trap to
the purge mode (Figure 3). When the trap is cool, the next sample can
be analyzed.
11. Performance Tests
11.1 At the beginning of each 12-hour shift during which analyses
are to be performed, GC/MS performance must be verified before blanks
or samples may be analyzed (Section 8.4). Use the instrument operating
conditions in the footnotes to Table 3 for these performance tests.
Alternate conditions may be used so as long as all QC requirements are
met.
11.2 BFB--Inject 50 ng of BFB solution directly on the column.
Alternatively, add BFB to reagent water or an aqueous standard such
that 50 ng or less of BFB will be introduced into the GC. Analyze
according to Section 10. Confirm that all criteria in Section 7.3.2.2
and Table 4 are met. If all criteria are not met, perform system
repair, retune the mass spectrometer, and repeat the test until all
criteria are met.
11.3 GC resolution--There must be a valley between 1,2-
dibromoethane and chlorobenzene, and the height of the valley must not
exceed 25 percent of the shorter of the two peaks. For an alternate GC
column, apply this valley height criterion to two representative GC
peaks separated by no more than 7 seconds.
11.4 Verify calibration with the LCS (Section 8.4) after the
criteria for BFB are met (Reference 15) and prior to analysis of a
blank or sample. After verification, analyze a blank (Section 8.5) to
demonstrate freedom from contamination and carry-over at the MDL.
12. Qualitative Identification
12.1 Target analytes are identified by comparison of results from
analysis of a sample or blank with data stored in the GC/MS data system
(Section 7.3.2.3). Identification of an analyte is confirmed per
Sections 12.1.1 through 12.1.4.
12.1.1 The signals for all characteristic m/z's stored in the data
system (Section 7.3.2.3) for each analyte of interest must be present
and must maximize within the same two consecutive scans.
12.1.2 Based on the relative retention time (RRT), the RRT for the
analyte must be within 0.06 of the RRT of the analyte in
the LCS run at the beginning of the shift (Section 8.4). Relative
retention time is used to establish the identification window because
it compensates for small changes in the GC temperature program whereas
the absolute retention time does not (see Section 7.3.1.2).
Note: RRT is a unitless quantity (see Sec. 20.2), although some
procedures refer to ``RRT units'' in providing the specification for
the agreement between the RRT values in the sample and the LCS or
other standard.
12.1.3 Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC
peak maximum, must agree within 50% to 200% (\1/2\ to 2 times) for all
m/z's in the reference mass spectrum stored in the data system (Section
7.3.2.3), or from a reference library. For example, if a peak has an
intensity of 20% relative to the base peak, the analyte is identified
if the intensity of the peak in the sample is in the range of 10% to
40% of the base peak.
12.1.4 The m/z's present in the acquired mass spectrum for the
sample that are not present in the reference mass spectrum must be
accounted for by contaminant or background m/z's. A reference library
may be helpful to identify and account for background or contaminant m/
z's. If the acquired mass spectrum is contaminated, or if
identification is ambiguous, an experienced spectrometrist (Section
1.6) must determine the presence or absence of the compound.
12.2 Structural isomers that have very similar mass spectra can be
identified only if the resolution between authentic isomers in a
standard mix is acceptable. Acceptable resolution is achieved if the
baseline to valley height between the isomers is less than 50% of the
height of the shorter of the two peaks. Otherwise, structural isomers
are identified as isomeric pairs.
13. Calculations
13.1 When an analyte has been identified, quantitation of that
analyte is based on the integrated abundance from the EICP of the
primary characteristic m/z in Table 5 or 6. Calculate the concentration
using the response factor (RF) determined in Section 7.3.3 and Equation
2. If a calibration curve was used, calculate the concentration using
the regression equation for the curve. If the concentration of an
analyte exceeds the calibration range, dilute the sample by the minimum
amount to bring the concentration into the calibration range, and re-
analyze. Determine a dilution factor (DF) from the amount of the
dilution. For example, if the extract is diluted by a factor of 2, DF =
2.
[GRAPHIC] [TIFF OMITTED] TP19FE15.013
Where:
Cs = Concentration of the analyte in the sample, and the
other terms are as defined in Section 7.3.3.
13.2 Reporting of results.
As noted in Section 1.4.1, EPA has promulgated this method at 40
CFR part 136 for use in wastewater compliance monitoring under the
National Pollutant Discharge Elimination System (NPDES). The data
reporting practices described here are focused on such monitoring needs
and may not be relevant to other uses of the method.
13.2.1 Report results for wastewater samples in [mu]g/L without
correction for recovery. (Other units may be used if required by in a
permit.) Report all QC data with the sample results.
13.2.2 Reporting level.
Unless otherwise specified in by a regulatory authority or in a
discharge permit, results for analytes that meet the identification
criteria are reported down to the concentration of the ML established
by the laboratory through calibration of the instrument (see Section
7.3.2 and the glossary for the derivation of the ML). EPA considers the
terms ``reporting limit,'' ``quantitation limit,'' and ``minimum
level'' to be synonymous.
13.2.2.1 Report a result for each analyte in each sample, blank, or
standard at or above the ML to 3 significant figures. Report a result
for each analyte found in each sample below the ML as ``12, are hazardous and must be
neutralized before being poured down a drain, or must be handled and
disposed of as hazardous waste.
16.3 Many analytes in this method decompose above 500 [deg]C. Low-
level waste such as absorbent paper, tissues, and plastic gloves may be
burned in an appropriate incinerator. Gross quantities of neat or
highly concentrated solutions of toxic or hazardous chemicals should be
packaged securely and disposed of through commercial or governmental
channels that are capable of handling these types of wastes.
16.4 For further information on waste management, consult The Waste
Management Manual for Laboratory Personnel and Less is Better-
Laboratory Chemical Management for Waste Reduction, available from the
American Chemical Society's Department of Government Relations and
Science Policy, 1155 16th Street NW., Washington, DC 20036, 202/872-
4477.
17. References
1. Bellar, T.A. and Lichtenberg, J.J. ``Determining Volatile
Organics at Microgram-per-Litre Levels by Gas Chromatography,''
Journal American Water Works Association, 66, 739 (1974).
2. ``Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants,'' U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio 45268, March 1977, Revised April 1977.
3. Bellar, T.A. and Lichtenberg, J.J. ``Semi-Automated Headspace
Analysis of Drinking Waters and Industrial Waters for Purgeable
Volatile Organic Compounds,'' Measurement of Organic Pollutants in
Water and Wastewater, C.E. Van Hall, editor, American Society for
Testing and Materials, Philadelphia, PA. Special Technical
Publication 686, 1978.
4. ``EPA Method Study 29 EPA Method 624-Purgeables,'' EPA 600/4-84-
054, National Technical Information Service, PB84-209915,
Springfield, Virginia 22161, June 1984.
5. 40 CFR part 136, appendix B.
6. ``Method Detection Limit for Methods 624 and 625,'' Olynyk, P.,
Budde, W.L., and Eichelberger, J.W. Unpublished report, May 14,
1980.
7. ``Carcinogens-Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
8. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR
part 1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
9. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 7th Edition,
2003.
10. 40 CFR 136.6(b)(5)(x).
11. 40 CFR 136.6(b)(2)(i).
12. Protocol for EPA Approval of New Methods for Organic and
Inorganic Analytes in Wastewater and Drinking Water (EPA-821-B-98-
003) March 1999
13. Provost, L.P. and Elder, R.S. ``Interpretation of Percent
Recovery Data,'' American Laboratory, 15, 58-63 (1983).
14. 40 CFR 136.3(a), Table IB, Chlorine--Total residual
15. Budde, W.L. and Eichelberger, J.W. ``Performance Tests for the
Evaluation of Computerized Gas Chromatography/Mass Spectrometry
Equipment and Laboratories,'' EPA-600/4-80-025, U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio 45268, April 1980.
16. ``Method Performance Data for Method 624,'' Memorandum from R.
Slater and T. Pressley, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
45268, January 17, 1984.
18. Tables
[[Page 9039]]
Table 1--Purgeables \1\
----------------------------------------------------------------------------------------------------------------
Analyte CAS Registry No. MDL ([mu]g/L) \2\ ML ([mu]g/L) \3\
----------------------------------------------------------------------------------------------------------------
Acrolein............................................... 107-02-8
Acrylonitrile.......................................... 107-13-1
Benzene................................................ 71-43-2 4.4 13.2
Bromodichloromethane................................... 75-27-4 2.2 6.6
Bromoform.............................................. 75-25-2 4.7 14.1
Bromomethane........................................... 74-83-9
Carbon tetrachloride................................... 56-23-5 2.8 8.4
Chlorobenzene.......................................... 108-90-7 6.0 18.0
Chloroethane........................................... 75-00-3
2-Chloroethylvinyl ether............................... 110-75-8
Chloroform............................................. 67-66-3 1.6 4.8
Chloromethane.......................................... 74-87-3
Dibromochloromethane................................... 124-48-1 3.1 9.3
1,2-Dichlorobenzene.................................... 95-50-1
1,3-Dichlorobenzene.................................... 541-73-1
1,4-Dichlorobenzene.................................... 106-46-7
1,1-Dichloroethane..................................... 75-34-3 4.7 14.1
1,2-Dichloroethane..................................... 107-06-2 2.8 8.4
1,1-Dichloroethene..................................... 75-35-4 2.8 8.4
trans-1,2-Dichloroethene............................... 156-60-5 1.6 4.8
1,2-Dichloropropane.................................... 78-87-5 6.0 18.0
cis-1,3-Dichloropropene................................ 10061-01-5 5.0 15.0
trans-1,3-Dichloropropene.............................. 10061-02-6
Ethyl benzene.......................................... 100-41-4 7.2 21.6
Methylene chloride..................................... 75-09-2 2.8 8.4
1,1,2,2-Tetrachloroethane.............................. 79-34-5 6.9 20.7
Tetrachloroethene...................................... 127-18-4 4.1 12.3
Toluene................................................ 108-88-3 6.0 18.0
1,1,1-Trichloroethane.................................. 71-55-6 3.8 11.4
1,1,2-Trichloroethane.................................. 79-00-5 5.0 15.0
Trichloroethene........................................ 79-01-6 1.9 5.7
Vinyl chloride......................................... 75-01-4
----------------------------------------------------------------------------------------------------------------
\1\ All the analytes in this table are Priority Pollutants (40 CFR part 423, appendix A)
\2\ MDL values from the 1984 promulgated version of Method 624
\3\ ML = Minimum Level--see Glossary for definition and derivation
Table 2--Additional Purgeables
------------------------------------------------------------------------
Analyte CAS Registry
------------------------------------------------------------------------
Acetone \1\............................................. 67-64-1
Acetonitrile \2\........................................ 75-05-8
Allyl alcohol \1\....................................... 107-18-6
Allyl chloride.......................................... 107-05-1
t-Amyl ethyl ether (TAEE)............................... 919-94-8
t-Amyl methyl ether (TAME).............................. 994-058
Benzyl chloride......................................... 100-44-7
Bromoacetone \2\........................................ 598-31-2
Bromobenzene............................................ 108-86-1
Bromochloromethane...................................... 74-97-5
1,3-Butadiene........................................... 106-99-0
n-Butanol \1\........................................... 71-36-3
2-Butanone (MEK) 1 2.................................... 78-93-3
t-Butyl alcohol (TBA)................................... 75-65-0
n-Butylbenzene.......................................... 104-51-8
sec-Butylbenzene........................................ 135-98-8
t-Butylbenzene.......................................... 98-06-6
t-Butyl ethyl ether (ETBE).............................. 637-92-3
Carbon disulfide........................................ 75-15-0
Chloral hydrate \2\..................................... 302-17-0
Chloroacetonitrile \1\.................................. 107-14-2
1-Chlorobutane.......................................... 109-69-3
Chlorodifluoromethane................................... 75-45-6
2-Chloroethanol \ 2\.................................... 107-07-3
bis (2-Chloroethyl) sulfide \ 2\........................ 505-60-2
1-Chlorohexanone........................................ 20261-68-1
Chloroprene (2-chloro-1,3-butadiene).................... 126-99-8
3-Chloropropene......................................... 107-05-1
3-Chloropropionitrile................................... 542-76-7
2-Chlorotoluene......................................... 95-49-8
4-Chlorotoluene......................................... 106-43-4
Crotonaldehyde 1 2...................................... 123-73-9
Cyclohexanone........................................... 108-94-1
1,2-Dibromo-3-chloropropane............................. 96-12-8
1,2-Dibromoethane....................................... 106-93-4
Dibromomethane.......................................... 74-95-3
cis-1,4-Dichloro-2-butene............................... 1476-11-5
trans-1,4-Dichloro-2-butene............................. 110-57-6
cis-1,2-Dichloroethene.................................. 156-59-2
Dichlorodifluoromethane................................. 75-71-8
1,3-Dichloropropane..................................... 142-28-9
2,2-Dichloropropane..................................... 590-20-7
1,3-Dichloro-2-propanol \2\............................. 96-23-1
1,1-Dichloropropene..................................... 563-58-6
cis-1,3-Dichloropropene................................. 10061-01-5
1:2,3:4-Diepoxybutane................................... 1464-53-5
Diethyl ether........................................... 60-29-7
Diisopropyl ether (DIPE)................................ 108-20-3
1,4-Dioxane \2\......................................... 123-91-1
Epichlorohydrin \2\..................................... 106-89-8
Ethanol \2\............................................. 64-17-5
Ethyl acetate \2\....................................... 141-78-6
Ethyl methacrylate...................................... 97-63-2
Ethylene oxide \2\...................................... 75-21-8
Hexachlorobutadiene..................................... 87-63-3
Hexachloroethane........................................ 67-72-1
2-Hexanone \2\.......................................... 591-78-6
Iodomethane............................................. 74-88-4
Isobutyl alcohol \1\.................................... 78-83-1
Isopropylbenzene........................................ 98-82-8
p-Isopropyltoluene...................................... 99-87-6
Methacrylonitrile \2\................................... 126-98-7
Methanol \2\............................................ 67-56-1
Malonitrile \2\......................................... 109-77-3
Methyl acetate.......................................... 79-20-9
Methyl acrylate......................................... 96-33-3
Methyl cyclohexane...................................... 108-87-2
Methyl iodide........................................... 74-88-4
Methyl methacrylate..................................... 78-83-1
4-Methyl-2-pentanone (MIBK) \2\......................... 108-10-1
Methyl-t-butyl ether (MTBE)............................. 1634-04-4
Naphthalene............................................. 91-20-3
Nitrobenzene............................................ 98-95-3
N-Nitroso-di-n-butylamine \2\........................... 924-16-3
2-Nitropropane.......................................... 79-46-9
Paraldehyde \2\......................................... 123-63-7
Pentachloroethane \2\................................... 76-01-7
Pentafluorobenzene...................................... 363-72-4
2-Pentanone \2\......................................... 107-19-7
2-Picoline \2\.......................................... 109-06-8
1-Propanol \1\.......................................... 71-23-8
2-Propanol \1\.......................................... 67-63-0
Propargyl alcohol \2\................................... 107-19-7
beta-Propiolactone \2\.................................. 57-58-8
Propionitrile (ethyl cyanide) \1\....................... 107-12-0
n-Propylamine........................................... 107-10-8
n-Propylbenzene......................................... 103-65-1
Pyridine \2\............................................ 110-86-1
[[Page 9040]]
Styrene................................................. 100-42-5
1,1,1,2-Tetrachloroethane............................... 630-20-6
Tetrahydrofuran......................................... 109-99-9
o-Toluidine \2\......................................... 95-53-4
1,2,3-Trichlorobenzene.................................. 87-61-6
Trichlorofluoromethane.................................. 75-69-4
1,2,3-Trichloropropane.................................. 96-18-4
1,2,3-Trimethylbenzene.................................. 526-73-8
1,2,4-Trimethylbenzene.................................. 95-63-6
1,3,5-Trimethylbenzene.................................. 108-67-8
Vinyl acetate........................................... 108-05-4
m-Xylene \3\............................................ 108-38-3
o-Xylene \3\............................................ 95-47-6
p-Xylene \3\............................................ 106-42-3
m+o- Xylene \3\......................................... 179601-22-0
m+p- Xylene \3\......................................... 179601-23-1
o+p- Xylene \3\......................................... 136777-61-2
------------------------------------------------------------------------
\1\ Determined at a purge temperature of 80 [deg]C.
\2\ May be detectable at a purge temperature of 80 [deg]C.
\3\ Determined in combination separated by GC column. Most GC columns
will resolve o-xylene from m+p-xylene. Report using the CAS number for
the individual xylene or the combination, as determined.
Table 3--Example Retention Times
------------------------------------------------------------------------
Retention
Analyte time (min)
------------------------------------------------------------------------
Chloromethane.............................................. 3.68
Vinyl chloride............................................. 3.92
Bromomethane............................................... 4.50
Chloroethane............................................... 4.65
Trichlorofluoromethane..................................... 5.25
Diethyl ether.............................................. 5.88
Acrolein................................................... 6.12
1,1-Dichloroethene......................................... 6.30
Acetone.................................................... 6.40
Iodomethane................................................ 6.58
Carbon disulfide........................................... 6.72
3-Chloropropene............................................ 6.98
Methylene chloride......................................... 7.22
Acrylonitrile.............................................. 7.63
trans-1,2-Dichloroethene................................... 7.73
1,1-Dichloroethane......................................... 8.45
Vinyl acetate.............................................. 8.55
Allyl alcohol.............................................. 8.58
2-Chloro-1,3-butadiene..................................... 8.65
Methyl ethyl ketone........................................ 9.50
cis-1,2-Dichloroethene..................................... 9.50
Ethyl cyanide.............................................. 9.57
Methacrylonitrile.......................................... 9.83
Chloroform................................................. 10.05
1,1,1-Trichloroethane...................................... 10.37
Carbon tetrachloride....................................... 10.70
Isobutanol................................................. 10.77
Benzene.................................................... 10.98
1,2-Dichloroethane......................................... 11.00
Crotonaldehyde............................................. 11.45
Trichloroethene............................................ 12.08
1,2-Dichloropropane........................................ 12.37
Methyl methacrylate........................................ 12.55
p-Dioxane.................................................. 12.63
Dibromomethane............................................. 12.65
Bromodichloromethane....................................... 12.95
Chloroacetonitrile......................................... 13.27
2-Chloroethylvinyl ether................................... 13.45
cis-1,3-Dichloropropene.................................... 13.65
4-Methyl-2-pentanone....................................... 13.83
Toluene.................................................... 14.18
trans-1,3-Dichloropropene.................................. 14.57
Ethyl methacrylate......................................... 14.70
1,1,2-Trichloroethane...................................... 14.93
1,3-Dichloropropane........................................ 15.18
Tetrachloroethene.......................................... 15.22
2-Hexanone................................................. 15.30
Dibromochloromethane....................................... 15.68
1,2-Dibromoethane.......................................... 15.90
Chlorobenzene.............................................. 16.78
Ethylbenzene............................................... 16.82
1,1,1,2-Tetrachloroethane.................................. 16.87
m+p-Xylene................................................. 17.08
o-Xylene................................................... 17.82
Bromoform.................................................. 18.27
Bromofluorobenzene......................................... 18.80
1,1,2,2-Tetrachloroethane.................................. 18.98
1,2,3-Trichloropropane..................................... 19.08
trans-1,4-Dichloro-2-butene................................ 19.12
------------------------------------------------------------------------
Column: 75 m x 0.53 mm ID x 3.0 [mu]m wide-bore DB-624.
Conditions: 40[deg]C for 4 min, 9[deg]C/min to 200[deg]C, 20[deg]C/min
(or higher) to 250[deg]C, hold for 20 min at 250[deg]C to remove
water.
Carrier gas flow rate: 6-7 mL/min at 40[deg]C.
Inlet split ratio: 3:1.
Interface split ratio: 7:2.
Table 4--BFB Key m/z Abundance Criteria \ 1\
------------------------------------------------------------------------
m/z Abundance criteria
------------------------------------------------------------------------
50........................................ 15-40% of m/z 95.
75........................................ 30-60% of m/z 95.
95........................................ Base Peak, 100% Relative
Abundance.
96........................................ 5-9% of m/z 95.
173....................................... <2% of m/z 174.
174....................................... >50% of m/z 95.
175....................................... 5-9% of m/z 174.
176....................................... >95% but <101% of m/z 174.
177....................................... 5-9% of m/z 176.
------------------------------------------------------------------------
\1\ Abundance criteria are for a quadrupole mass spectrometer; contact
the manufacturer for criteria for other types of mass spectrometers.
Table 5--Suggested Surrogate and Internal Standards
----------------------------------------------------------------------------------------------------------------
Retention time Secondary m/
Analyte (min) \1\ Primary m/z z's
----------------------------------------------------------------------------------------------------------------
Benzene-d6................................................... 10.95 84 ...........
4-Bromofluorobenzene......................................... 18.80 95 174, 176
Bromochloromethane........................................... 9.88 128 49, 130, 51
2-Bromo-1-chloropropane...................................... 14.80 77 79, 156
2-Butanone-d5................................................ 9.33 77 ...........
Chloroethane-d5.............................................. 4.63 71 ...........
Chloroform-\13\C............................................. 10.00 86 ...........
1,2-Dichlorobenzene-d4....................................... ................. 152 ...........
1,4-Dichlorobutane........................................... 18.57 55 90, 92
1,2-Dichloroethane-d4........................................ 10.88 102 ...........
1,1-Dichloroethene-d2........................................ 6.30 65 ...........
1,2-Dichloropropane-d6....................................... 12.27 67 ...........
trans-1,3-Dichloropropene-d4................................. 14.50 79 ...........
1,4-Difluorobenzene.......................................... ................. 114 63, 88
Ethylbenzene-d10............................................. 16.77 98 ...........
Fluorobenzene................................................ ................. 96 70
2-Hexanone-d5................................................ 15.30 63 ...........
Pentafluorobenzene........................................... ................. 168 ...........
1,1,2,2-Tetrachloroethane-d2................................. 18.93 84 ...........
Toluene-d8................................................... 14.13 100 ...........
Vinyl chloride-d3............................................ 3.87 65
----------------------------------------------------------------------------------------------------------------
\1\ For chromatographic conditions, see the footnote to Table 3.
[[Page 9041]]
Table 6--Characteristic m/z's for Purgeable Organics
------------------------------------------------------------------------
Analyte Primary m/z Secondary m/z's
------------------------------------------------------------------------
Chloromethane................... 50 52.
Bromomethane.................... 94 96.
Vinyl chloride.................. 62 64.
Chloroethane.................... 64 66.
Methylene chloride.............. 84 49, 51, and 86.
Trichlorofluoromethane.......... 101 103.
1,1-Dichloroethene.............. 96 61 and 98.
1,1-Dichloroethane.............. 63 65, 83, 85, 98, and
100.
trans-1,2-Dichloroethene........ 96 61 and 98.
Chloroform...................... 83 85.
1,2-Dichloroethane.............. 98 62, 64, and 100.
1,1,1-Trichloroethane........... 97 99, 117, and 119.
Carbon tetrachloride............ 117 119 and 121.
Bromodichloromethane............ 83 127, 85, and 129.
1,2-Dichloropropane............. 63 112, 65, and 114.
trans-1,3-Dichloropropene....... 75 77.
Trichloroethene................. 130 95, 97, and 132.
Benzene......................... 78 ...................
Dibromochloromethane............ 127 129, 208, and 206.
1,1,2-Trichloroethane........... 97 83, 85, 99, 132,
and 134.
cis-1,3-Dichloropropene......... 75 77.
2-Chloroethylvinyl ether........ 106 63 and 65.
Bromoform....................... 173 171, 175, 250, 252,
254, and 256.
1,1,2,2-Tetrachloroethane....... 168 83, 85, 131, 133,
and 166.
Tetrachloroethene............... 164 129, 131, and 166.
Toluene......................... 92 91.
Chlorobenzene................... 112 114.
Ethyl benzene................... 106 91.
1,3-Dichlorobenzene............. 146 148 and 111.
1,2-Dichlorobenzene............. 146 148 and 111.
1,4-Dichlorobenzene............. 146 148 and 111.
------------------------------------------------------------------------
Table 7--LCS (Q), DOC (S and X), and MS/MSD (P and RPD) Acceptance Criteria 1
--------------------------------------------------------------------------------------------------------------------------------------------------------
Range for X (%)
Analyte Range for Q (%) Limit for s (%) Range for P (%) Limit for RPD
--------------------------------------------------------------------------------------------------------------------------------------------------------
Benzene.................................................. 65-135 33 75-125 37-151 61
Benzene-d6............................................... ................. ................. ................. 70-130 .................
Bromodichloromethane..................................... 65-135 34 50-140 35-155 56
Bromoform................................................ 70-130 25 57-156 45-169 42
Bromomethane............................................. 15-185 90 D-206 D-242 61
2-Butanone-d5............................................ ................. ................. ................. 60-140 .................
Carbon tetrachloride..................................... 70-130 26 65-125 70-140 41
Chlorobenzene............................................ 65-135 29 82-137 37-160 53
Chloroethane............................................. 40-160 47 42-202 14-230 78
Chloroethane-d5.......................................... ................. ................. ................. 60-140 .................
2-Chloroethylvinyl ether................................. D-225 130 D-252 D-305 71
Chloroform............................................... 70-135 32 68-121 51-138 54
Chloroform-\13\C......................................... ................. ................. ................. 70-130 .................
Chloromethane............................................ D-205 472 D-230 D-273 60
Dibromochloromethane..................................... 70-135 30 69-133 53-149 50
1,2-Dichlorobenzene...................................... 65-135 31 59-174 18-190 57
1,2-Dichlorobenzene-d4................................... ................. ................. ................. 70-130 .................
1,3-Dichlorobenzene...................................... 70-130 24 75-144 59-156 43
1,4-Dichlorobenzene...................................... 65-135 31 59-174 18-190 57
1,1-Dichloroethane....................................... 70-130 24 71-143 59-155 40
1,2-Dichloroethane....................................... 70-130 29 72-137 49-155 49
1,2-Dichloroethane-d4.................................... ................. ................. ................. 70-130 .................
1,1-Dichloroethene....................................... 50-150 40 19-212 D-234 32
1,1-Dichloroethene-d2.................................... ................. ................. ................. 70-130 .................
trans-1,2-Dichloroethene................................. 70-130 27 68-143 54-156 45
1,2-Dichloropropane...................................... 35-165 69 19-181 D-210 55
1,2-Dichloropropane-d6................................... ................. ................. ................. 60-140 .................
cis-1,3-Dichloropropene.................................. 25-175 79 5-195 D-227 58
trans-1,3-Dichloropropene................................ 50-150 52 38-162 17-183 86
trans-1,3-Dichloropropene-d4............................. ................. ................. ................. 70-130 .................
Ethyl benzene............................................ 60-140 34 75-134 37-162 63
2-Hexanone-d5............................................ ................. ................. ................. 60-140 .................
Methylene chloride....................................... 60-140 192 D-205 D-221 28
1,1,2,2-Tetrachloroethane................................ 60-140 36 68-136 46-157 61
1,1,2,2-Tetrachloroethane-d2............................. ................. ................. ................. 70-130 .................
Tetrachloroethene........................................ 70-130 23 65-133 64-148 39
[[Page 9042]]
Toluene.................................................. 70-130 22 75-134 47-150 41
Toluene-d8............................................... ................. ................. ................. 70-130 .................
1,1,1-Trichloroethane.................................... 70-130 21 69-151 52-162 36
1,1,2-Trichloroethane.................................... 70-130 27 75-136 52-150 45
Trichloroethene.......................................... 65-135 29 75-138 70-157 48
Trichlorofluoromethane................................... 50-150 50 45-158 17-181 84
Vinyl chloride........................................... 5-195 100 D-218 D-251 66
Vinyl chloride-d3........................................ ................. ................. ................. 70-130 .................
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Criteria were calculated using an LCS concentration of 20 [mu]g/L
Q = Percent recovery in calibration verification/LCS (Section 8.4)
s = Standard deviation of percent recovery for four recovery measurements (Section 8.2.4)
X = Average percent recovery for four recovery measurements (Section 8.2.4)
P = Percent recovery for the MS or MSD (Section 8.3.3)
D = Detected; result must be greater than zero
Notes:
1. Criteria for pollutants are based upon the method performance data in Reference 4. Where necessary, limits for recovery have been broadened to assure
applicability to concentrations below those used to develop Table 7.
2. Criteria for surrogates are from EPA CLP SOM01.2D.
Table 8--Recovery and Precision as Functions of Concentration
----------------------------------------------------------------------------------------------------------------
Single analyst Overall precision, S'
Analyte Recovery, X' ([mu]g/L) precision, sr' ([mu]g/L) ([mu]g/L)
----------------------------------------------------------------------------------------------------------------
Benzene............................ 0.93C+2.00.............. 20.26 X-1.74............ 0.25 X-1.33
Bromodichloromethane............... 1.03C-1.58.............. 0.15 X+0.59............. 0.20 X+1.13
Bromoform.......................... 1.18C-2.35.............. 0.12 X+0.36............. 0.17 X+1.38
Bromomethane \a\................... 1.00C................... 0.43 X.................. 0.58 X
Carbon tetrachloride............... 1.10C-1.68.............. 0.12 X+0.25............. 0.11 X+0.37
Chlorobenzene...................... 0.98C+2.28.............. 0.16 X-0.09............. 0.26 X-1.92
Chloroethane....................... 1.18C+0.81.............. 0.14 X+2.78............. 0.29 X+1.75
2-Chloroethylvinyl ether \a\....... 1.00C................... 0.62 X.................. 0.84 X
Chloroform......................... 0.93C+0.33.............. 0.16 X+0.22............. 0.18 X+0.16
Chloromethane...................... 1.03C+0.81.............. 0.37 X+2.14............. 0.58 X+0.43
Dibromochloromethane............... 1.01C-0.03.............. 0.17 X-0.18............. 0.17 X+0.49
1,2-Dichlorobenzene \b\............ 0.94C+4.47.............. 0.22 X-1.45............. 0.30 X-1.20
1,3-Dichlorobenzene................ 1.06C+1.68.............. 0.14 X-0.48............. 0.18 X-0.82
1,4-Dichlorobenzene \b\............ 0.94C+4.47.............. 0.22 X-1.45............. 0.30 X-1.20
1,1-Dichloroethane................. 1.05C+0.36.............. 0.13 X-0.05............. 0.16 X+0.47
1,2-Dichloroethane................. 1.02C+0.45.............. 0.17 X-0.32............. 0.21 X-0.38
1,1-Dichloroethene................. 1.12C+0.61.............. 0.17 X+1.06............. 0.43 X-0.22
trans-1,2,-Dichloroethene.......... 1.05C+0.03.............. 0.14 X+0.09............. 0.19 X+0.17
1,2-Dichloropropane \a\............ 1.00C................... 0.33 X.................. 0.45 X
cis-1,3-Dichloropropene \a\........ 1.00C................... 0.38 X.................. 0.52 X
trans-1,3-Dichloropropene \a\...... 1.00C................... 0.25 X.................. 0.34 X
Ethyl benzene...................... 0.98C+2.48.............. 0.14 X+1.00............. 0.26 X-1.72
Methylene chloride................. 0.87C+1.88.............. 0.15 X+1.07............. 0.32 X+4.00
1,1,2,2-Tetrachloroethane.......... 0.93C+1.76.............. 0.16 X+0.69............. 0.20 X+0.41
Tetrachloroethene.................. 1.06C+0.60.............. 0.13 X-0.18............. 0.16 X-0.45
Toluene............................ 0.98C+2.03.............. 0.15 X-0.71............. 0.22 X-1.71
1,1,1-Trichloroethane.............. 1.06C+0.73.............. 0.12 X-0.15............. 0.21 X-0.39
1,1,2-Trichloroethane.............. 0.95C+1.71.............. 0.14 X+0.02............. 0.18 X+0.00
Trichloroethene.................... 1.04C+2.27.............. 0.13 X+0.36............. 0.12 X+0.59
Trichlorofluoromethane............. 0.99C+0.39.............. 0.33 X-1.48............. 0.34 X-0.39
Vinyl chloride..................... 1.00C................... 0.48 X.................. 0.65 X
----------------------------------------------------------------------------------------------------------------
X' = Expected recovery for one or more measurements of a sample containing a concentration of C, in [mu]g/L.
Sr' = Expected single analyst standard deviation of measurements at an average concentration found of X, in
[mu]g/L.
S' = Expected interlaboratory standard deviation of measurements at an average concentration found of X, in
[mu]g/L.
C = True value for the concentration, in [mu]g/L.
X = Average recovery found for measurements of samples containing a concentration of C, in [mu]g/L.
\a\ Estimates based upon the performance in a single laboratory (References 4 and 16).
\b\ Due to coelutions, performance statements for these isomers are based upon the sums of their concentrations.
[[Page 9043]]
19. Figures
BILLING CODE 6560-50-P
[GRAPHIC] [TIFF OMITTED] TP19FE15.014
BILLING CODE 6560-50-C
[[Page 9044]]
20. Glossary
These definitions and purposes are specific to this method, but
have been conformed to common usage to the extent possible.
20.1 Units of weight and measure and their abbreviations
[GRAPHIC] [TIFF OMITTED] TP19FE15.015
20.1.1 Symbols
[deg]C degrees Celsius
[mu]g microgram
[mu]L microliter
< less than
> greater than
% percent
20.1.2 Abbreviations (in alphabetical order)
cm centimeter
g gram
h hour
ID inside diameter
in. inch
L liter
M Molecular ion
m mass
mg milligram
min minute
mL milliliter
mm millimeter
ms millisecond
m/z mass-to-charge ratio
N normal; gram molecular weight of solute divided by hydrogen
equivalent of solute, per liter of solution
ng nanogram
pg picogram
ppb part-per-billion
ppm part-per-million
ppt part-per-trillion
psig pounds-per-square inch gauge
v/v volume per unit volume
w/v weight per unit volume
20.2 Definitions and acronyms (in alphabetical order)
Analyte--A compound tested for by this method. The analytes are
listed in Tables 1 and 2.
Analyte of interest--An analyte of interest is an analyte required
to be
[[Page 9045]]
determined by a regulatory/control authority or in a permit, or by a
client.
Analytical batch--The set of samples analyzed on a given instrument
during a 12-hour period that begins and ends with analysis of a
calibration verification/LCS. See Section 8.4.
Blank--An aliquot of reagent water that is treated exactly as a
sample including exposure to all glassware, equipment, solvents,
reagents, internal standards, and surrogates that are used with
samples. The blank is used to determine if analytes or interferences
are present in the laboratory environment, the reagents, or the
apparatus. See Section 8.5.
Calibration--The process of determining the relationship between
the output or response of a measuring instrument and the value of an
input standard. Historically, EPA has referred to a multi-point
calibration as the ``initial calibration,'' to differentiate it from a
single-point calibration verification.
Calibration standard--A solution prepared from stock solutions and/
or a secondary standards and containing the analytes of interest,
surrogates, and internal standards. The calibration standard is used to
calibrate the response of the GC/MS instrument against analyte
concentration.
Calibration verification standard--The laboratory control sample
(LCS) used to verify calibration. See Section 8.4.
Descriptor--In SIM, the beginning and ending retention times for
the RT window, the m/z's sampled in the RT window, and the dwell time
at each m/z.
Extracted ion current profile (EICP)--The line described by the
signal at a given m/z.
Field duplicates--Two samples collected at the same time and place
under identical conditions, and treated identically throughout field
and laboratory procedures. Results of analyses of field duplicates
provide an estimate of the precision associated with sample collection,
preservation, and storage, as well as with laboratory procedures.
Field blank--An aliquot of reagent water or other reference matrix
that is placed in a sample container in the field, and treated as a
sample in all respects, including exposure to sampling site conditions,
storage, preservation, and all analytical procedures. The purpose of
the field blank is to determine if the field or sample transporting
procedures and environments have contaminated the sample.
GC--Gas chromatograph or gas chromatography
Internal standard--A compound added to a sample in a known amount
and used as a reference for quantitation of the analytes of interest
and surrogates. Internal standards are listed in Table 5. Also see
Internal standard quantitation.
Internal standard quantitation--A means of determining the
concentration of an analyte of interest (Tables 1 and 2) by reference
to a compound added to a sample and not expected to be found in the
sample.
DOC--Initial demonstration of capability (DOC; Section 8.2); four
aliquots of reagent water spiked with the analytes of interest and
analyzed to establish the ability of the laboratory to generate
acceptable precision and recovery. A DOC is performed prior to the
first time this method is used and any time the method or
instrumentation is modified.
Laboratory control sample (LCS; laboratory fortified blank (LFB);
on-going precision and recovery sample; OPR)--An aliquot of reagent
water spiked with known quantities of the analytes of interest and
surrogates. The LCS is analyzed exactly like a sample. Its purpose is
to assure that the results produced by the laboratory remain within the
limits specified in this method for precision and recovery. In this
method, the LCS is synonymous with a calibration verification sample
(See Sections 7.4 and 8.4).
Laboratory fortified sample matrix--See Matrix spike.
Laboratory reagent blank--See Blank.
Matrix spike (MS) and matrix spike duplicate (MSD) (laboratory
fortified sample matrix and duplicate)--Two aliquots of an
environmental sample to which known quantities of the analytes of
interest and surrogates are added in the laboratory. The MS/MSD are
prepared and analyzed exactly like a field sample. Their purpose is to
quantify any additional bias and imprecision caused by the sample
matrix. The background concentrations of the analytes in the sample
matrix must be determined in a separate aliquot and the measured values
in the MS/MSD corrected for background concentrations.
May--This action, activity, or procedural step is neither required
nor prohibited.
May not--This action, activity, or procedural step is prohibited.
Method blank (laboratory reagent blank)--See Blank.
Method detection limit (MDL)--A detection limit determined by the
procedure at 40 CFR part 136, appendix B. The MDLs determined by EPA in
the original version of the method are listed in Table 1. As noted in
Sec. 1.4, use the MDLs in Table 1 in conjunction with current MDL data
from the laboratory actually analyzing samples to assess the
sensitivity of this procedure relative to project objectives and
regulatory requirements (where applicable).
Minimum level (ML)--The term ``minimum level'' refers to either the
sample concentration equivalent to the lowest calibration point in a
method or a multiple of the method detection limit (MDL), whichever is
higher. Minimum levels may be obtained in several ways: They may be
published in a method; they may be based on the lowest acceptable
calibration point used by a laboratory; or they may be calculated by
multiplying the MDL in a method, or the MDL determined by a laboratory,
by a factor of 3. For the purposes of NPDES compliance monitoring, EPA
considers the following terms to be synonymous: ``quantitation limit,''
``reporting limit,'' and ``minimum level.''
MS--Mass spectrometer or mass spectrometry.
Must--This action, activity, or procedural step is required.
m/z--The ratio of the mass of an ion (m) detected in the mass
spectrometer to the charge (z) of that ion.
Quality control sample (QCS)--A sample containing analytes of
interest at known concentrations. The QCS is obtained from a source
external to the laboratory or is prepared from standards obtained from
a different source than the calibration standards.
The purpose is to check laboratory performance using test materials
that have been prepared independent of the normal preparation process.
Reagent water--Water demonstrated to be free from the analytes of
interest and potentially interfering substances at the MDLs for the
analytes in this method.
Regulatory compliance limit (or regulatory concentration limit)--A
limit on the concentration or amount of a pollutant or contaminant
specified in a nationwide standard, in a permit, or otherwise
established by a regulatory/control authority.
Relative retention time (RRT)--The ratio of the retention time of
an analyte to the retention time of its associated internal standard.
RRT compensates for small changes in the GC temperature program that
can affect the absolute retention times of the analyte and internal
standard. RRT is a unitless quantity.
Relative standard deviation (RSD)--The standard deviation times 100
[[Page 9046]]
divided by the mean. Also termed ``coefficient of variation.''
RF--Response factor. See Section 7.3.3.
RSD--See relative standard deviation.
Safety Data Sheet (SDS)--Written information on a chemical's
toxicity, health hazards, physical properties, fire, and reactivity,
including storage, spill, and handling precautions that meet the
requirements of OSHA, 29 CFR 1910.1200(g) and appendix D to Sec.
1910.1200. United Nations Globally Harmonized System of Classification
and Labelling of Chemicals (GHS), third revised edition, United
Nations, 2009.
Selected Ion Monitoring (SIM)--An MS technique in which a few m/z's
are monitored. When used with gas chromatography, the m/z's monitored
are usually changed periodically throughout the chromatographic run to
correlate with the characteristic m/z's for the analytes, surrogates,
and internal standards as they elute from the chromatographic column.
The technique is often used to increase sensitivity and minimize
interferences.
Signal-to-noise ratio (S/N)--The height of the signal as measured
from the mean (average) of the noise to the peak maximum divided by the
width of the noise.
SIM--See Selection Ion Monitoring.
Should--This action, activity, or procedural step is suggested but
not required.
Stock solution--A solution containing an analyte that is prepared
using a reference material traceable to EPA, the National Institute of
Science and Technology (NIST), or a source that will attest to the
purity and authenticity of the reference material.
Surrogate--A compound unlikely to be found in a sample, and which
is spiked into sample in a known amount before purge-and-trap. The
surrogate is quantitated with the same procedures used to quantitate
the analytes of interest. The purpose of the surrogate is to monitor
method performance with each sample.
* * * * *
Method 625.1--Base/Neutrals and Acids by GC/MS
1. Scope and Application
1.1 This method is for determination of semivolatile organic
pollutants in industrial discharges and other environmental samples by
gas chromatography combined with mass spectrometry (GC/MS), as provided
under 40 CFR 136.1. This revision is based on a previous protocol
(Reference 1), on the basic revision promulgated October 26, 1984 (49
FR 43234), and on an interlaboratory method validation study (Reference
2). Although this method was validated through an interlaboratory study
conducted more than 29 years ago, the fundamental chemistry principles
used in this method remain sound and continue to apply.
1.2 The analytes that may be qualitatively and quantitatively
determined using this method and their CAS Registry numbers are listed
in Tables 1 and 2. The method may be extended to determine the analytes
listed in Table 3; however, extraction or gas chromatography of some of
these analytes may make quantitative determination difficult. For
examples, benzidine is subject to oxidative losses during solvent
concentration. Under the alkaline conditions of the extraction, alpha-
BHC, gamma-BHC, endosulfan I and II, and endrin are subject to
decomposition. Hexachlorocyclopentadiene is subject to thermal
decomposition in the inlet of the gas chromatograph, chemical reaction
in acetone solution, and photochemical decomposition. N-
nitrosodiphenylamine and other nitrosoamines may decompose in the gas
chromatographic inlet. EPA has provided other methods (e.g., Method
607--Nitrosamines) for determination of some of these analytes.
1.3 The large number of analytes in Tables 1-3 of this method makes
testing difficult if all analytes are determined simultaneously.
Therefore, it is necessary to determine and perform quality control
(QC) tests for the ``analytes of interest'' only. Analytes of interest
are those required to be determined by a regulatory/control authority
or in a permit, or by a client. If a list of analytes is not specified,
the analytes in Tables 1 and 2 must be determined, at a minimum, and QC
testing must be performed for these analytes. The analytes in Tables 1
and 2, and some of the analytes in Table 3 have been identified as
Toxic Pollutants (40 CFR 401.15), expanded to a list of Priority
Pollutants (40 CFR part 423, appendix A).
1.4 In this revision to Method 625, the pesticides and
polychlorinated biphenyls (PCBs) have been moved from Table 1 to Table
3 (Additional Analytes) to distinguish these analytes from the analytes
required in quality control tests (Tables 1 and 2). QC acceptance
criteria for pesticides and PCBs have been retained in Table 6 and may
continue to be applied if desired, or if requested or required by a
regulatory/control authority or in a permit. Method 608 should be used
for determination of pesticides and PCBs. Method 1668C may be useful
for determination of PCBs as individual chlorinated biphenyl congeners,
and Method 1699 may be useful for determination of pesticides. At the
time of writing of this revision, Methods 1668C and 1699 had not been
approved for use at 40 CFR part 136. The screening procedure for
2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) contained in the
version of Method 625 promulgated October 26, 1984 (49 FR 43234) has
been replaced with procedures for selected ion monitoring (SIM), and
2,3,7,8-TCDD may be determined using the SIM procedures. However, EPA
Method 613 or 1613B should be used for analyte-specific determination
of 2,3,7,8-TCDD because of the focus of these methods on this compound.
Methods 613 and 1613B are approved for use at 40 CFR part 136.
1.5 Method detection limits (MDLs; Reference 3) for the analytes in
Tables 1, 2, and 3 are listed in those tables. These MDLs were
determined in reagent water (Reference 4). Advances in analytical
technology, particularly the use of capillary (open-tubular) columns,
allowed laboratories to routinely achieve MDLs for the analytes in this
method that are 2-10 times lower than those in the version promulgated
in 1984 (40 FR 43234). The MDL for an analyte in a specific wastewater
may differ from those listed, depending upon the nature of
interferences in the sample matrix.
1.5.1 EPA has promulgated this method at 40 CFR part 136 for use in
wastewater compliance monitoring under the National Pollutant Discharge
Elimination System (NPDES). The data reporting practices described in
Section 15.2 are focused on such monitoring needs and may not be
relevant to other uses of the method.
1.5.2 This method includes ``reporting limits'' based on EPA's
``minimum level'' (ML) concept (see the glossary in Section 22). Tables
1, 2, and 3 contain MDL values and ML values for many of the analytes.
The MDL for an analyte in a specific wastewater may differ from those
listed in Tables 1, 2, and 3, depending upon the nature of
interferences in the sample matrix.
1.6 This method is performance-based. It may be modified to improve
performance (e.g., to overcome interferences or improve the accuracy of
results) provided all performance requirements are met.
1.6.1 Examples of allowed method modifications are described at 40
CFR 136.6. Other examples of allowed modifications specific to this
method are described in Section 8.1.2.
[[Page 9047]]
1.6.2 Any modification beyond those expressly permitted at 40 CFR
136.6 or in Section 8.1.2 of this method shall be considered a major
modification subject to application and approval of an alternate test
procedure under 40 CFR 136.4 and 136.5.
1.6.3 For regulatory compliance, any modification must be
demonstrated to produce results equivalent or superior to results
produced by this method when applied to relevant wastewaters (Section
8.3).
1.7 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph/mass
spectrometer and in the interpretation of mass spectra. Each laboratory
that uses this method must demonstrate the ability to generate
acceptable results using the procedure in Section 8.2.
1.8 Terms and units of measure used in this method are given in the
glossary at the end of the method.
2. Summary of Method
2.1 A measured volume of sample, sufficient to meet an MDL or
reporting limit, is serially extracted with methylene chloride at pH
11-13 and again at a pH less than 2 using a separatory funnel or
continuous liquid/liquid extractor.
2.2 The extract is concentrated to a volume necessary to meet the
required compliance or detection limit, and analyzed by GC/MS.
Qualitative identification of an analyte in the extract is performed
using the retention time and the relative abundance of two or more
characteristic masses (m/z's). Quantitative analysis is performed using
the internal standard technique with a single characteristic m/z.
3. Contamination and Interferences
3.1 Solvents, reagents, glassware, and other sample processing
labware may yield artifacts, elevated baselines, or matrix
interferences causing misinterpretation of chromatograms and mass
spectra. All materials used in the analysis must be demonstrated to be
free from contamination and interferences by analyzing blanks initially
and with each extraction batch (samples started through the extraction
process in a given 12-hour period, to a maximum of 20 samples--see
Glossary for detailed definition), as described in Section 8.5.
Specific selection of reagents and purification of solvents by
distillation in all-glass systems may be required. Where possible,
labware is cleaned by extraction or solvent rinse, or baking in a kiln
or oven.
3.2 Glassware must be scrupulously cleaned (Reference 5). Clean all
glassware as soon as possible after use by rinsing with the last
solvent used in it. Solvent rinsing should be followed by detergent
washing with hot water, and rinses with tap water and reagent water.
The glassware should then be drained dry, and heated at 400 [deg]C for
15-30 minutes. Some thermally stable materials, such as PCBs, may
require higher temperatures and longer baking times for removal.
Solvent rinses with pesticide quality acetone, hexane, or other
solvents may be substituted for heating. Volumetric labware should not
be heated above 90 [deg]C. After drying and cooling, glassware should
be sealed and stored in a clean environment to prevent any accumulation
of dust or other contaminants. Store inverted or capped with solvent-
rinsed or baked aluminum foil.
3.3 Matrix interferences may be caused by contaminants co-extracted
from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the industrial complex or municipality being sampled.
Interferences extracted from samples high in total organic carbon (TOC)
may result in elevated baselines, or by enhancing or suppressing a
signal at or near the retention time of an analyte of interest.
Analyses of the matrix spike and duplicate (Section 8.3) may be useful
in identifying matrix interferences, and gel permeation chromatography
(GPC; Section 11.1) and sulfur removal (Section 11.2) may aid in
eliminating these interferences. EPA has provided guidance that may aid
in overcoming matrix interferences (Reference 6).
3.4 In samples that contain an inordinate number of interferences,
the use of chemical ionization (CI) mass spectrometry may make
identification easier. Tables 4 and 5 give characteristic CI m/z's for
many of the analytes covered by this method. The use of CI mass
spectrometry to support electron ionization (EI) mass spectrometry is
encouraged, but not required.
4. Safety
4.1 Hazards associated with each reagent used in this method have
not been precisely defined; however, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to
these chemicals must be reduced to the lowest possible level by
whatever means available. The laboratory is responsible for maintaining
a current awareness file of OSHA regulations regarding the safe
handling of the chemicals specified in this method. A reference file of
safety data sheets (SDSs, OSHA, 29 CFR 1910.1200(g)) should also be
made available to all personnel involved in sample handling and
chemical analysis. Additional references to laboratory safety are
available and have been identified (References 7-9) for the information
of the analyst.
4.2 The following analytes covered by this method have been
tentatively classified as known or suspected human or mammalian
carcinogens: benzo(a)anthracene, benzidine, 3,3'-dichlorobenzidine,
benzo(a)pyrene, alpha-BHC, beta-BHC, delta-BHC, gamma-BHC, Dibenz(a,h)-
anthracene, N-nitrosodimethylamine, 4,4'-DDT, and PCBs. Other compounds
in Table 3 may also be toxic. Primary standards of toxic compounds
should be prepared in a chemical fume hood, and a NIOSH/MESA approved
toxic gas respirator should be worn when handling high concentrations
of these compounds.
4.3 This method allows the use of hydrogen as a carrier gas in
place of helium (Section 5.6.1.2). The laboratory should take the
necessary precautions in dealing with hydrogen, and should limit
hydrogen flow at the source to prevent buildup of an explosive mixture
of hydrogen in air.
5. Apparatus and Materials
Note: Brand names, suppliers, and part numbers are for
illustration purposes only. No endorsement is implied. Equivalent
performance may be achieved using equipment and materials other than
those specified here. Demonstrating that the equipment and supplies
used in the laboratory achieves the required performance is the
responsibility of the laboratory. Suppliers for equipment and
materials in this method may be found through an on-line search.
Please do not contact EPA for supplier information.
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle--amber glass bottle large enough to
contain the necessary sample volume, fitted with a fluoropolymer-lined
screw cap. Foil may be substituted for fluoropolymer if the sample is
not corrosive. If amber bottles are not available, protect samples from
light. Unless pre-cleaned, the bottle and cap liner must be washed,
rinsed with acetone or methylene chloride, and dried before use to
minimize contamination.
5.1.2 Automatic sampler (optional)--the sampler must incorporate a
pre-cleaned glass sample container. Samples must be kept refrigerated
at <6 [deg]C and protected from light during compositing. If the
sampler uses a peristaltic pump, a minimum length of compressible
silicone rubber tubing may be used. Before use,
[[Page 9048]]
however, the compressible tubing should be thoroughly rinsed with
methanol, followed by repeated rinsings with reagent water to minimize
the potential for contamination of the sample. An integrating flow
meter is required to collect flow-proportioned composites.
5.2 Glassware.
5.2.1 Separatory funnel--Size appropriate to hold sample volume and
extraction solvent volume, and equipped with fluoropolymer stopcock.
5.2.2 Drying column--Chromatographic column, approximately 400 mm
long by 19 mm ID, with coarse frit, or equivalent, sufficient to hold
15 g of anhydrous sodium sulfate.
5.2.3 Concentrator tube, Kuderna-Danish--10 mL, graduated (Kontes
570050-1025 or equivalent). Calibration must be checked at the volumes
employed in the test. A ground glass stopper is used to prevent
evaporation of extracts.
5.2.4 Evaporative flask, Kuderna-Danish--500 mL (Kontes 57001-0500
or equivalent). Attach to concentrator tube with springs.
Note: Use of a solvent recovery system with the K-D or other
solvent evaporation apparatus is strongly recommended.
5.2.5 Snyder column, Kuderna-Danish--Three ball macro (Kontes
503000-0121 or equivalent).
5.2.6 Snyder column, Kuderna-Danish--Two-ball micro (Kontes 569001-
0219 or equivalent).
5.2.7 Vials--10-15 mL, amber glass, with Teflon-lined screw cap.
5.2.8 Continuous liquid-liquid extractor--Equipped with
fluoropolymer or glass connecting joints and stopcocks requiring no
lubrication. (Hershberg-Wolf Extractor, Ace Glass Company, Vineland,
N.J., P/N 6848-20, or equivalent.)
5.2.9 In addition to the glassware listed above, the laboratory
should be equipped with all necessary pipets, volumetric flasks,
beakers, and other glassware listed in this method and necessary to
perform analyses successfully.
5.3 Boiling chips--Approximately 10/40 mesh, glass, silicon
carbide, or equivalent. Heat to 400 [deg]C for 30 minutes, or solvent
rinse or Soxhlet extract with methylene chloride.
5.4 Water bath--Heated, with concentric ring cover, capable of
temperature control (2 [deg]C). The bath should be used in
a hood.
5.5 Balances.
5.5.1 Analytical, capable of accurately weighing 0.1 mg.
5.5.2 Top loading, capable of accurately weighing 10 mg.
5.6 GC/MS system.
5.6.1 Gas chromatograph (GC)--An analytical system complete with a
temperature programmable gas chromatograph and all required
accessories, including syringes and analytical columns.
5.6.1.1 Injection port--Can be split, splitless, temperature
programmable split/splitless (PTV), solvent-purge, large-volume, on-
column, backflushed, or other. An autosampler is highly recommended
because it injects volumes more precisely than volumes injected
manually.
5.6.1.2 Carrier gas--Helium or hydrogen. Data in the tables in this
method were obtained using helium carrier gas. If hydrogen is used,
analytical conditions may need to be adjusted for optimum performance,
and calibration and all QC tests must be performed with hydrogen
carrier gas. See Section 4.3 for precautions regarding the use of
hydrogen as a carrier gas.
5.6.2 GC column--See the footnotes to Tables 4 and 5. Other columns
or column systems may be used provided all requirements in this method
are met.
5.6.3 Mass spectrometer--Capable of repetitively scanning from 35-
450 Daltons (amu) every two seconds or less, utilizing a 70 eV
(nominal) electron energy in the electron impact ionization mode, and
producing a mass spectrum which meets all the criteria in Table 9A or
9B when 50 ng or less of decafluorotriphenyl phosphine (DFTPP; CAS
5074-71-5; bis(pentafluorophenyl) phenyl phosphine) is injected into
the GC.
5.6.4 GC/MS interface--Any GC to MS interface that meets all
performance requirements in this method may be used.
5.6.5 Data system--A computer system must be interfaced to the mass
spectrometer that allows the continuous acquisition and storage of mass
spectra acquired throughout the chromatographic program. The computer
must have software that allows searching any GC/MS data file for
specific m/z's (masses) and plotting m/z abundances versus time or scan
number. This type of plot is defined as an extracted ion current
profile (EICP). Software must also be available that allows integrating
the abundance at any EICP between specified time or scan number limits.
5.7 Automated gel permeation chromatograph (GPC).
5.7.1 GPC column--150--700 mm long x 21-25 mm ID, packed with 70 g
of SX-3 Biobeads; Bio-Rad Labs, or equivalent
5.7.2 Pump, injection valve, UV detector, and other apparatus
necessary to meet the requirements in this method.
5.8 Nitrogen evaporation device--Equipped with a water bath than
can be maintained at 30-45 [deg]C; N-Evap, Organomation Associates, or
equivalent.
6. Reagents
6.1 Reagent water--Reagent water is defined as water in which the
analytes of interest and interfering compounds are not detected at the
MDLs of the analytes of interest.
6.2 Sodium hydroxide solution (10 N)--Dissolve 40 g of NaOH (ACS)
in reagent water and dilute to 100 mL.
6.3 Sodium thiosulfate--(ACS) granular.
6.4 Sulfuric acid (1+1)--Slowly add 50 mL of
H2SO4 (ACS, sp. gr. 1.84) to 50 mL of reagent
water.
6.5 Acetone, methanol, methylene chloride, 2-propanol--High purity
pesticide quality, or equivalent, demonstrated to be free of the
analytes of interest and interferences (Section 3). Purification of
solvents by distillation in all-glass systems may be required.
6.6 Sodium sulfate--(ACS) granular, anhydrous, rinsed or Soxhlet
extracted with methylene chloride (20 mL/g), baked at in a shallow tray
at 450 [deg]C for one hour minimum, cooled in a desiccator, and stored
in a pre-cleaned glass bottle with screw cap that prevents moisture
from entering.
6.7 Stock standard solutions (1.00 [mu]g/[mu]L)--Stock standard
solutions may be prepared from pure materials, or purchased as
certified solutions. Traceability must be to the National Institute of
Standards and Technology (NIST) or other national standard, when
available. Stock solution concentrations alternate to those below may
be used. Because of the toxicity of some of the compounds, primary
dilutions should be prepared in a hood, and a NIOSH/MESA approved toxic
gas respirator should be worn when high concentrations of neat
materials are handled. The following procedure may be used to prepare
standards from neat materials.
6.7.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in pesticide quality
methanol or other suitable solvent and dilute to volume in a 10 mL
volumetric flask. Larger volumes may be used at the convenience of the
laboratory. When compound purity is assayed to be 96% or greater, the
weight may be used without correction to calculate the concentration of
the stock standard. Commercially prepared stock standards
[[Page 9049]]
may be used at any concentration if they are certified by the
manufacturer or by an independent source.
6.7.2 Transfer the stock standard solutions to fluoropolymer-sealed
screw-cap bottles. Store at <6 [deg]C and protect from light. Stock
standard solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing
calibration standards from them.
6.7.3 Replace purchased certified stock standard solutions per the
expiration date. Replace stock standard solutions prepared by the
laboratory or mixed with purchased solutions after one year, or sooner
if comparison with QC check samples indicates a problem.
6.8 Surrogate standard spiking solution
6.8.1 Select a minimum of three surrogate compounds from Table 8
that most closely match the recovery of the analytes of interest. For
example, if all analytes tested are considered acids, use surrogates
that have similar chemical attributes. Other compounds may be used as
surrogates so long as they do not interfere in the analysis. The
deuterium and carbon-13 labeled compounds in Method 1625B are
particularly useful because Method 1625B contains QC acceptance
criteria for recovery of these compounds. If only one or two analytes
are determined, one or two surrogates may be used.
6.8.2 Prepare a solution containing each selected surrogate such
that the concentration in the sample would match the concentration in
the mid-point calibration standard. For example, if the midpoint of the
calibration is 100 [mu]g/L, prepare the spiking solution at a
concentration of 100 [mu]g/mL in methanol. Addition of 1.00 mL of this
solution to 1000 mL of sample will produce a concentration of 100
[mu]g/L of the surrogate. Alternate volumes and concentrations
appropriate to the response of the GC/MS instrument or for selective
ion monitoring (SIM) may be used, if desired.
6.8.3 Store the spiking solution at <= 6[deg]C in a fluoropolymer-
sealed glass container. The solution should be checked frequently for
stability. The solution must be replaced after one year, or sooner if
comparison with quality control check standards indicates a problem.
6.9 Internal standard spiking solution
6.9.1 Select three or more internal standards similar in
chromatographic behavior to the analytes of interest. Internal
standards are listed in Table 8. Suggested internal standards are: 1,4-
dichlorobenzene-d4; naphthalene-d8; acenaphthene-
d10; phenanthrene-d10; chrysene-d12;
and perylene-d12. The laboratory must demonstrate that
measurement of the internal standards is not affected by method or
matrix interferences (see also Section 7.3.4).
6.9.2 Prepare the internal standards at a concentration of 10 mg/mL
in methylene chloride or other suitable solvent. When 10 [mu]L of this
solution is spiked into a 1-mL extract, the concentration of the
internal standards will be 100 [mu]g/mL. A lower concentration
appropriate to the response of the GC/MS instrument or for SIM may be
used, if desired.
6.9.3 To assure accurate analyte identification, particularly when
SIM is used, it may be advantageous to include more internal standards
than those suggested in Section 6.9.1. An analyte will be located most
accurately if its retention time relative to an internal standard is in
the range of 0.8 to 1.2.
6.10 DFTPP standard--Prepare a solution of DFTPP in methanol or
other suitable solvent such that 50 ng or less will be injected (see
Section 13.2). An alternate concentration may be used to compensate for
specific injection volumes or to assure that the operating range of the
instrument is not exceeded, so long as the total injected is 50 ng or
less. Include benzidine and pentachlorophenol in this solution such
that <=100 ng of benzidine and <=50 ng of pentachlorophenol will be
injected.
6.11 Quality control check sample concentrate--See Section 8.2.1.
6.12 GPC calibration solution
6.12.1 Prepare a methylene chloride solution to contain corn oil,
bis(2-ethylhexyl) phthalate (BEHP), perylene, and sulfur at the
concentrations in Section 6.12.2, or at concentrations appropriate to
the response of the detector.
Note: Sulfur does not readily dissolve in methylene chloride,
but is soluble in warm corn oil. The following procedure is
suggested for preparation of the solution:
6.12.2 Weigh 8 mg sulfur and 2.5 g corn oil into a 100-mL
volumetric flask and warm to dissolve the sulfur. Separately weigh 100
mg BEHP and 2 mg perylene and add to flask. Bring to volume with
methylene chloride and mix thoroughly.
6.12.3 Store the solution in an amber glass bottle with a
fluoropolymer-lined screw cap at 0-6 [deg]C. Protect from light.
Refrigeration may cause the corn oil to precipitate. Before use, allow
the solution to stand at room temperature until the corn oil dissolves,
or warm slightly to aid in dissolution. Replace the solution every
year, or more frequently if the response of a component changes.
6.13 Sulfur removal--Copper foil or powder (bright, non-oxidized),
or tetrabutylammonium sulfite (TBA sulfite).
6.13.1 Copper foil, or powder--Fisher, Alfa Aesar 42455-18, 625
mesh, or equivalent. Cut copper foil into approximately 1-cm squares.
Copper must be activated on each day it will be used, as follows:
6.13.1.1 Place the quantity of copper needed for sulfur removal
(Section 11.2.1.3) in a ground-glass-stoppered Erlenmeyer flask or
bottle. Cover the foil or powder with methanol.
6.13.1.2 Add HCl dropwise (0.5-1.0 mL) while swirling, until the
copper brightens.
6.13.1.3 Pour off the methanol/HCl and rinse 3 times with reagent
water to remove all traces of acid, then 3 times with acetone, then 3
times with hexane.
6.13.1.4 For copper foil, cover with hexane after the final rinse.
Store in a stoppered flask under nitrogen until used. For the powder,
dry on a rotary evaporator or under a stream of nitrogen. Store in a
stoppered flask under nitrogen until used.
6.13.2 Tetrabutylammonium sodium sulfite (TBA sodium sulfite).
6.13.2.1 Tetrabutylammonium hydrogen sulfate,
[CH3(CH2)3]4NHSO4
.
6.13.2.2 Sodium sulfite, Na2SO3.
6.13.2.3 Dissolve approximately 3 g tetrabutylammonium hydrogen
sulfate in 100 mL of reagent water in an amber bottle with
fluoropolymer-lined screw cap. Extract with three 20-mL portions of
hexane and discard the hexane extracts.
6.13.2.4 Add 25 g sodium sulfite to produce a saturated solution.
Store at room temperature. Replace after 1 month.
7. Calibration
7.1 Establish operating conditions equivalent to those in the
footnote to Table 4 or 5 for the base/neutral or acid fraction,
respectively. If a combined base/neutral/acid fraction will be
analyzed, use the conditions in the footnote to Table 4. Alternative
temperature program and flow rate conditions may be used. It is
necessary to calibrate the GC/MS for the analytes of interest (Section
1.3) only.
7.2 Internal standard calibration
7.2.1 Prepare calibration standards for the analytes of interest
and surrogates at a minimum of five concentration levels by adding
appropriate volumes of one or more stock standards to volumetric
flasks. One of the calibration standards should be at a concentration
near the ML for the analyte in Table 1, 2, or 3. The ML value may be
rounded to a whole number that
[[Page 9050]]
is more convenient for preparing the standard, but must not exceed the
ML values listed in Table 1, 2, or 3 for those analytes which list ML
values. Alternatively, the laboratory may establish the ML for each
analyte based on the concentration of the lowest calibration standard
in a series of standards obtained from a commercial vendor, again,
provided that the ML values do not exceed the MLs in Tables 1, 2, or 3,
and provided that the resulting calibration meets the acceptance
criteria in Section 7.2.3, based on the RSD, RSE, or R\2\.
The other concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range
of the GC/MS system for full-scan and/or SIM operation, as appropriate.
A minimum of six concentration levels is required for a second order,
non-linear (e.g., quadratic; ax\2\ + bx + c) calibration. Calibrations
higher than second order are not allowed. To each calibration standard
or standard mixture, add a known constant volume of the internal
standard solution (Section 6.9), and dilute to volume with methylene
chloride.
Note: The large number of analytes in Tables 1 through 3 may not
be soluble or stable in a single solution; multiple solutions may be
required if a large number of analytes are to be determined
simultaneously.
7.2.1.1 Prior to analysis of the calibration standards, inject the
DFTPP standard (Section 6.10) and adjust the scan rate of the mass
spectrometer to produce a minimum of 5 mass spectra across the DFTPP GC
peak. Adjust instrument conditions until the DFTPP criteria in Table 9A
or 9B are met. Calculate peak tailing factors for benzidine and
pentachlorophenol. Calculation of the tailing factor is illustrated in
Figure 1. The tailing factor for benzidine and pentachlorophenol must
be <2; otherwise, adjust instrument conditions and either replace the
column or break off a short section of the front end of the column, and
repeat the test.
Note: The DFTPP spectrum may be evaluated by summing the
intensities of the m/z's across the GC peak, subtracting the
background at each m/z in a region of the chromatogram within 20
scans of but not including any part of, the DFTPP peak. The DFTPP
spectrum may also be evaluated by fitting a Gaussian to each m/z and
using the intensity at the maximum for each Gaussian or by
integrating the area at each m/z and using the integrated areas.
Other means may be used for evaluation of the DFTPP spectrum so long
as the spectrum is not distorted to meet the criteria in Table 9A or
9B.
7.2.1.2 Analyze the mid-point combined base/neutral and acid
calibration standard and enter or review the retention time, relative
retention time, mass spectrum, and quantitation m/z in the data system
for each analyte of interest, surrogate, and internal standard. If
additional analytes (Table 3) are to be quantified, include these
analytes in the standard. The mass spectrum for each analyte must be
comprised of a minimum of 2 m/z's (Tables 4 and 5); 3 to 5 m/z's assure
more reliable analyte identification. Suggested quantitation m/z's are
shown in Tables 4 and 5 as the primary m/z. If an interference occurs
at the primary m/z, use one of the secondary m/z's or an alternate m/z.
A single m/z only is required for quantitation.
7.2.1.3 For SIM operation, determine the analytes in each
descriptor, the quantitation and qualifier m/z's for each analyte (the
m/z's can be the same as for full-scan operation; Section 7.2.1.2), the
dwell time on each m/z for each analyte, and the beginning and ending
retention time for each descriptor. Analyze the verification standard
in scan mode to verify m/z's and establish the retention times for the
analytes. There must be a minimum of two m/z's for each analyte to
assure analyte identification. To maintain sensitivity and capture
enough scans (>=5) across each chromatographic peak, there should be no
more than 10 m/z's in a descriptor. For example, for a descriptor with
10 m/z's and a chromatographic peak width of 5 sec, a dwell time of 100
ms at each m/z would result in a scan time of 1 second and provide 5
scans across the GC peak. The quantitation m/z will usually be the most
intense peak in the mass spectrum. The quantitation m/z and dwell time
may be optimized for each analyte. However, if a GC peak spans two (or
more) descriptors, the dwell time and cycle time (scans/sec) should be
set to the same value in both segments in order to maintain equivalent
response. The acquisition table used for SIM must take into account the
mass defect (usually less than 0.2 Daltons) that can occur at each m/z
being monitored.
7.2.1.4 For combined scan and SIM operation, set up the scan
segments and descriptors to meet requirements in Sections 7.2.1.1-
7.2.1.3.
7.2.2 Analyze each calibration standard according to Section 12 and
tabulate the area at the quantitation m/z against concentration for
each analyte of interest, surrogate, and internal standard. If an
interference is encountered, use a secondary m/z (Table 4 or 5) for
quantitation. Calculate a response factor (RF) for each analyte of
interest at each concentration using Equation 1.
[GRAPHIC] [TIFF OMITTED] TP19FE15.016
Where:
As = Area of the characteristic m/z for the analyte of
interest or surrogate.
Ais = Area of the characteristic m/z for the internal
standard.
Cis = Concentration of the internal standard ([mu]g/mL).
Cs = Concentration of the analyte of interest or
surrogate ([mu]g/mL).
7.2.3 Calculate the mean (average) and relative standard deviation
(RSD) of the responses factors. If the RSD is less than 35%, the RF can
be assumed to be invariant and the average RF can be used for
calculations. Alternatively, the results can be used to fit a linear or
quadratic regression of response ratios, As/Ais, vs. concentration
ratios Cs/Cis. If used, the regression must be weighted inversely
proportional to concentration. The coefficient of determination (R\2\;
Reference 10) of the weighted regression must be greater than 0.920.
Alternatively, the relative standard error (Reference 11) may be used
as an acceptance criterion. As with the RSD, the RSE must be less than
35%. If an RSE less than 35% cannot be achieved for a quadratic
regression, system performance is unacceptable and the system must be
adjusted and re-calibrated.
Note: Using capillary columns and current instrumentation, it is
quite likely that a laboratory can calibrate the target analytes in
this method and achieve a linearity metric (either RSD or RSE) well
below 35%. Therefore, laboratories are permitted to use more
stringent acceptance criteria for calibration than described here,
for example, to harmonize their application of this method with
those from other sources.
7.3 Calibration verification--The RF or calibration curve must be
verified immediately after calibration and at the beginning of each 12-
hour shift, by analysis of a mid-point calibration standard (Section
7.2.1). The standard(s)
[[Page 9051]]
must be obtained from a second manufacturer or a manufacturer's batch
prepared independently from the batch used for calibration.
Traceability must be to a national standard, when available. The
concentration of the standard should be near the mid-point of the
calibration. Include the surrogates (Section 6.8) in this solution. It
is necessary to verify calibration for the analytes of interest
(Section 1.3) only.
Note: The 12-hour shift begins after the DFTPP (Section 13.1)
and DDT/endrin tests (if DDT and endrin are to be determined), and
after analysis of the calibration verification standard. The 12-hour
shift ends 12 hours later. The DFTPP and DDT/endrin tests are
outside of the 12-hour shift.
7.3.1 Analyze the calibration verification standard(s) beginning in
Section 12. Calculate the percent recovery of each analyte. Compare the
recoveries for the analytes of interest against the acceptance criteria
for recovery (Q) in Table 6, and the recoveries for the surrogates
against the acceptance criteria in Table 8. If recovery of the analytes
of interest and surrogates meet acceptance criteria, system performance
is acceptable and analysis of samples may continue. If any individual
recovery is outside its limit, system performance is unacceptable for
that analyte.
Note: The large number of analytes in Tables 6 and 8 present a
substantial probability that one or more will fail acceptance
criteria when all analytes are tested simultaneously.
7.3.2 When one or more analytes fail acceptance criteria, analyze a
second aliquot of the calibration verification standard and compare
only those analytes that failed the first test (Section 7.3.1) with
their respective acceptance criteria. If these analytes now pass,
system performance is acceptable and analysis of samples may continue.
A repeat failure of any analyte that failed the first test, however,
will confirm a general problem with the measurement system. If this
occurs, repair the system (Section 7.2.1.1) and repeat the test
(Section 7.3.1), or prepare a fresh calibration standard and repeat the
test. If calibration cannot be verified after maintenance or injection
of the fresh calibration standard, re-calibrate the instrument.
Note: If it is necessary to perform a repeat verification test
frequently; i.e., perform two tests in order to pass, it may be
prudent to perform two injections in succession and review the
results, rather than perform one injection, review the results, then
perform the second injection if results from the first injection
fail. To maintain the validity of the test and re-test, system
maintenance and/or adjustment is not permitted between the
injections.
7.3.3 Many of the analytes in Table 3 do not have QC acceptance
criteria in Table 6, and some of the surrogates in Table 8 do not have
acceptance criteria. If calibration is to be verified and other QC
tests are to be performed for these analytes, acceptance criteria must
be developed and applied. EPA has provided guidance for development of
QC acceptance criteria (References 12 and 13).
7.3.4 Internal standard responses--Verify that detector sensitivity
has not changed by comparing the response of each internal standard in
the calibration verification standard (Section 7.3) to the response of
the respective internal standard in the midpoint calibration standard
(Section 7.2.1). The peak areas or heights of the internal standards in
the calibration verification standard must be within 50% to 200% (\1/2\
to 2x) of their respective peak areas or heights in the mid-point
calibration standard. If not, repeat the calibration verification test
using a fresh calibration verification standard (7.3), or perform and
document system repair. Subsequent to repair, repeat the calibration
verification test (Section 7.3.1). If the responses are still not
within 50% to 200%, re-calibrate the instrument (Section 7.2.2) and
repeat the calibration verification test.
8. Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality assurance program. The minimum requirements of this
program consist of an initial demonstration of laboratory capability
and ongoing analysis of spiked samples and blanks to evaluate and
document data quality (40 CFR 136.7). The laboratory must maintain
records to document the quality of data generated. Results of ongoing
performance tests are compared with established QC acceptance criteria
to determine if the results of analyses meet performance requirements
of this method. When results of spiked samples do not meet the QC
acceptance criteria in this method, a quality control check sample
(laboratory control sample; LCS) must be analyzed to confirm that the
measurements were performed in an in-control mode of operation. A
laboratory may develop its own performance criteria (as QC acceptance
criteria), provided such criteria are as or more restrictive than the
criteria in this method.
8.1.1 The laboratory must make an initial demonstration of
capability (DOC) to generate acceptable precision and recovery with
this method. This demonstration is detailed in Section 8.2.
8.1.2 In recognition of advances that are occurring in analytical
technology, and to overcome matrix interferences, the laboratory is
permitted certain options (Section 1.6 and 40 CFR 136.6(b)) to improve
separations or lower the costs of measurements. These options may
include alternate extraction, concentration, and cleanup procedures
(e.g., solid-phase extraction; rotary-evaporator concentration; column
chromatography cleanup), changes in column and type of mass
spectrometer (40 CFR 136.6(b)(4)(xvi)). Alternate determinative
techniques, such as substitution of spectroscopic or immunoassay
techniques, and changes that degrade method performance, are not
allowed. If an analytical technique other than GC/MS is used, that
technique must have a specificity equal to or greater than the
specificity of GC/MS for the analytes of interest. The laboratory is
also encouraged to participate in inter-comparison and performance
evaluation studies (see Section 8.10).
8.1.2.1 Each time a modification is made to this method, the
laboratory is required to repeat the procedure in Section 8.2. If the
detection limit of the method will be affected by the change, the
laboratory must demonstrate that the MDLs (40 CFR part 136, appendix B)
are lower than one-third the regulatory compliance limit or the MDLs in
this method, whichever are greater. If calibration will be affected by
the change, the instrument must be recalibrated per Section 7. Once the
modification is demonstrated to produce results equivalent or superior
to results produced by this method, that modification may be used
routinely thereafter, so long as the other requirements in this method
are met (e.g., matrix spike/matrix spike duplicate recovery and
relative percent difference).
8.1.2.1.1 If SPE, or another allowed method modification, is to be
applied to a specific discharge, the laboratory must prepare and
analyze matrix spike/matrix spike duplicate (MS/MSD) samples (Section
8.3) and LCS samples (Section 8.4). The laboratory must include
surrogates (Section 8.7) in each of the samples. The MS/MSD and LCS
samples must be fortified with the analytes of interest (Section 1.3).
If the modification is for nationwide use, MS/MSD samples must be
prepared from a minimum of nine different discharges (See Section
8.1.2.1.2), and all QC acceptance criteria in this method must be met.
This evaluation only needs to be performed once other than for the
routine QC required by this method (for example it could be performed
by the
[[Page 9052]]
vendor of the SPE materials) but any laboratory using that specific SPE
material must have the results of the study available. This includes a
full data package with the raw data that will allow an independent
reviewer to verify each determination and calculation performed by the
laboratory (see Section 8.1.2.2.5, items a-q).
8.1.2.1.2 Sample matrices on which MS/MSD tests must be performed
for nationwide use of an allowed modification:
(a) Effluent from a POTW.
(b) ASTM D5905 Standard Specification for Substitute Wastewater.
(c) Sewage sludge, if sewage sludge will be in the permit.
(d) ASTM D1141 Standard Specification for Substitute Ocean Water,
if ocean water will be in the permit.
(e) Untreated and treated wastewaters up to a total of nine matrix
types (see http://water.epa.gov/scitech/wastetech/guide/industry.cfm)
for a list of industrial categories with existing effluent guidelines).
At least one of the above wastewater matrix types must have at
least one of the following characteristics:
(i) Total suspended solids greater than 40 mg/L.
(ii) Total dissolved solids greater than 100 mg/L.
(iii) Oil and grease greater than 20 mg/L.
(iv) NaCl greater than 120 mg/L.
(v) CaCO3 greater than 140 mg/L.
The interim acceptance criteria for MS, MSD recoveries that do not
have recovery limits specified in Table 6, and recoveries for
surrogates that do not have recovery limits specified in Table 8, must
be no wider than 60-140%, and the relative percent difference (RPD) of
the concentrations in the MS and MSD that do not have RPD limits
specified in Table 6 must be less than 30%. Alternatively, the
laboratory may use the laboratory's in-house limits if they are
tighter.
(f) A proficiency testing (PT) sample from a recognized provider,
in addition to tests of the nine matrices (Section 8.1.2.1.1).
8.1.2.2 The laboratory is required to maintain records of
modifications made to this method. These records include the following,
at a minimum:
8.1.2.2.1 The names, titles, street addresses, telephone numbers,
and email addresses of the analyst(s) that performed the analyses and
modification, and of the quality control officer that witnessed and
will verify the analyses and modifications.
8.1.2.2.2 A list of analytes, by name and CAS Registry Number.
8.1.2.2.3 A narrative stating reason(s) for the modifications.
8.1.2.2.4 Results from all quality control (QC) tests comparing the
modified method to this method, including:
(a) Calibration (Section 7).
(b) Calibration verification (Section 7).
(c) Initial demonstration of capability (Section 8.2).
(d) Analysis of blanks (Section 8.5).
(e) Matrix spike/matrix spike duplicate analysis (Section 8.3).
(f) Laboratory control sample analysis (Section 8.4).
8.1.2.2.5 Data that will allow an independent reviewer to validate
each determination by tracing the instrument output (peak height, area,
or other signal) to the final result. These data are to include:
(a) Sample numbers and other identifiers.
(b) Extraction dates.
(c) Analysis dates and times.
(d) Analysis sequence/run chronology.
(e) Sample weight or volume (Section 10).
(f) Extract volume prior to each cleanup step (Sections 10 and 11).
(g) Extract volume after each cleanup step (Section 11).
(h) Final extract volume prior to injection (Sections 10 and 12).
(i) Injection volume (Section 12.2.3).
(j) Sample or extract dilution (Section 12.2.3.2).
(k) Instrument and operating conditions.
(l) Column (dimensions, material, etc).
(m) Operating conditions (temperature program, flow rate, etc).
(n) Detector (type, operating conditions, etc).
(o) Chromatograms, mass spectra, and other recordings of raw data.
(p) Quantitation reports, data system outputs, and other data to
link the raw data to the results reported.
(q) A written Standard Operating Procedure (SOP).
8.1.2.2.6 Each individual laboratory wishing to use a given
modification must perform the start-up tests in Section 8.1.2 (e.g.,
DOC, MDL), with the modification as an integral part of this method
prior to applying the modification to specific discharges. Results of
the DOC must meet the QC acceptance criteria in Table 6 for the
analytes of interest (Section 1.3), and the MDLs must be equal to or
lower than the MDLs in Tables 4 and 5 for the analytes of interest.
8.1.3 Before analyzing samples, the laboratory must analyze a blank
to demonstrate that interferences from the analytical system, labware,
and reagents, are under control. Each time a batch of samples is
extracted or reagents are changed, a blank must be extracted and
analyzed as a safeguard against laboratory contamination. Requirements
for the blank are given in Section 8.5.
8.1.4 The laboratory must, on an ongoing basis, spike and analyze a
minimum of one sample, in duplicate, with the samples in an extraction
batch (Section 3.1). The laboratory must also spike and analyze, in
duplicate, a minimum of 5% of all samples from a given site or
discharge to monitor and evaluate method and laboratory performance on
the sample matrix. The batch and site/discharge samples may be the
same. The procedure for spiking and analysis is given in Section 8.3.
8.1.5 The laboratory must, on an ongoing basis, demonstrate through
analysis of a quality control check sample (laboratory control sample,
LCS; on-going precision and recovery sample, OPR) that the measurement
system is in control. This procedure is given in Section 8.4.
8.1.6 The laboratory should maintain performance records to
document the quality of data that is generated. This procedure is given
in Section 8.9.
8.1.7 The large number of analytes tested in performance tests in
this method present a substantial probability that one or more will
fail acceptance criteria when many analytes are tested simultaneously,
and a re-test is allowed if this situation should occur. If, however,
continued re-testing results in further repeated failures, the
laboratory should document the failures (e.g., as qualifiers on
results) and either avoid reporting results for analytes that failed or
report the problem and failures with the data. Failure to report does
not relieve a discharger or permittee of reporting timely results.
8.2 Initial demonstration of capability (DOC)--To establish the
ability to generate acceptable recovery and precision, the laboratory
must perform the DOC in Sections 8.2.1 through 8.2.6 for the analytes
of interest. The laboratory must also establish MDLs for the analytes
of interest using the MDL procedure at 40 CFR part 136, appendix B. The
laboratory's MDLs must be equal to or lower than those listed in Tables
1, 2, or 3 or lower than one third the regulatory compliance limit,
whichever is greater. For MDLs not listed in Tables 4 and 5, the
laboratory must determine the MDLs using the MDL procedure at 40 CFR
136, Appendix B under the same conditions used to determine the MDLs
for the analytes listed in Tables 1, 2, and 3. All
[[Page 9053]]
procedures used in the analysis, including cleanup procedures, must be
included in the DOC.
8.2.1 For the DOC, a QC check sample concentrate containing each
analyte of interest (Section 1.3) is prepared in a water-miscible
solvent. The QC check sample concentrate must be prepared independently
from those used for calibration, but may be from the same source as the
second-source standard used for calibration verification (Section 7.3).
The concentrate should produce concentrations of the analytes of
interest in water at the mid-point of the calibration range, and may be
at the same concentration as the LCS (Section 8.4). Multiple solutions
may be required.
Note: QC check sample concentrates are no longer available from
EPA.
8.2.2 Using a pipet or micro-syringe, prepare four LCSs by adding
an appropriate volume of the concentrate to each of four 1-L aliquots
of reagent water, and mix well. The volume of reagent water must be the
same as the volume that will be used for the sample, blank (Section
8.5), and MS/MSD (Section 8.3). A concentration of 100 [mu]g/L was used
to develop the QC acceptance criteria in Table 6. Also add an aliquot
of the surrogate spiking solution (Section 6.8). Also add an aliquot of
the surrogate spiking solution (Section 6.8) to the reagent-water
aliquots.
8.2.3 Extract and analyze the four LCSs according to the method
beginning in Section 10.
8.2.4 Calculate the average percent recovery (x) and the standard
deviation of the percent recovery(s) for each analyte using the four
results.
8.2.5 For each analyte, compare s and (x) with the corresponding
acceptance criteria for precision and recovery in Table 6. For analytes
in Table 3 not listed in Table 6, DOC QC acceptance criteria must be
developed by the laboratory. EPA has provided guidance for development
of QC acceptance criteria (References 12 and 13). If s and (x) for all
analytes of interest meet the acceptance criteria, system performance
is acceptable and analysis of blanks and samples may begin. If any
individual s exceeds the precision limit or any individual (x) falls
outside the range for recovery, system performance is unacceptable for
that analyte.
Note: The large number of analytes in Tables 1-3 present a
substantial probability that one or more will fail at least one of
the acceptance criteria when many or all analytes are determined
simultaneously. Therefore, the analyst is permitted to conduct a
``re-test'' as described in Sec. 8.2.6.
8.2.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, repeat the test for only the analytes that
failed. If results for these analytes pass, system performance is
acceptable and analysis of samples and blanks may proceed. If one or
more of the analytes again fail, system performance is unacceptable for
the analytes that failed the acceptance criteria. Correct the problem
and repeat the test (Section 8.2). See Section 8.1.7 for disposition of
repeated failures.
Note: To maintain the validity of the test and re-test, system
maintenance and/or adjustment is not permitted between this pair of
tests.
8.3 Matrix spike and matrix spike duplicate (MS/MSD)--The
laboratory must, on an ongoing basis, spike at least 5% of the samples
from each sample site being monitored in duplicate to assess accuracy
(recovery and precision). The data user should identify the sample and
the analytes of interest (Section 1.3) to be spiked. If direction
cannot be obtained, the laboratory must spike at least one sample per
extraction batch of up to 20 samples with the analytes in Tables 1 and
2. Spiked sample results should be reported only to the data user whose
sample was spiked, or as requested or required by a regulatory/control
authority.
8.3.1 If, as in compliance monitoring, the concentration of a
specific analyte will be checked against a regulatory concentration
limit, the concentration of the spike should be at that limit;
otherwise, the concentration of the spike should be one to five times
higher than the background concentration determined in Section 8.3.2,
at or near the midpoint of the calibration range, or at the
concentration in the LCS (Section 8.4) whichever concentration would be
larger.
8.3.2 Analyze one sample aliquot to determine the background
concentration (B) of the each analyte of interest. If necessary,
prepare a new check sample concentrate (Section 8.2.1) appropriate for
the background concentration. Spike and analyze two additional sample
aliquots, and determine the concentration after spiking (A1
and A2) of each analyte. Calculate the percent recoveries
(P1 and P2) as 100 (A1-B)/T and 100
(A2-B)/T, where T is the known true value of the spike. Also
calculate the relative percent difference (RPD) between the
concentrations (A1 and A2) as
200[verbarlm]A1-A2[verbarlm]/(A1 +
A2). If necessary, adjust the concentrations used to
calculate the RPD to account for differences in the volumes of the
spiked aliquots.
8.3.3 Compare the percent recoveries (P1 and
P2) and the RPD for each analyte in the MS/MSD aliquots with
the corresponding QC acceptance criteria in Table 6. A laboratory may
develop and apply QC acceptance criteria more restrictive than the
criteria in Table 6, if desired.
8.3.3.1 If any individual P falls outside the designated range for
recovery in either aliquot, or the RPD limit is exceeded, the result
for the analyte in the unspiked sample is suspect and may not be
reported or used for permitting or regulatory compliance purposes. See
Section 8.1.7 for disposition of failures.
8.3.3.2 The acceptance criteria in Table 6 were calculated to
include an allowance for error in measurement of both the background
and spike concentrations, assuming a spike to background ratio of 5:1.
This error will be accounted for to the extent that the spike to
background ratio approaches 5:1 (Reference 14). If spiking is performed
at a concentration lower than 100 [mu]g/L, the laboratory must use
either the QC acceptance criteria in Table 6, or optional QC acceptance
criteria calculated for the specific spike concentration. To use the
optional acceptance criteria: (1) Calculate recovery (X') using the
equation in Table 7, substituting the spike concentration (T) for C;
(2) Calculate overall precision (S') using the equation in Table 7,
substituting X' for x; (3) Calculate the range for recovery at the
spike concentration as (100 X'/T) 2.44(100 S'/T)%
(Reference 14). For analytes in Table 3 not listed in Table 6, QC
acceptance criteria must be developed by the laboratory. EPA has
provided guidance for development of QC acceptance criteria (References
12 and 13).
8.3.4 After analysis of a minimum of 20 MS/MSD samples for each
target analyte and surrogate, the laboratory must calculate and apply
in-house QC limits for recovery and RPD of future MS/MSD samples
(Section 8.3). The QC limits for recovery are calculated as the mean
observed recovery 3 standard deviations, and the upper QC
limit for RPD is calculated as the mean RPD plus 3 standard deviations
of the RPDs. The in-house QC limits must be updated at least every two
years and re-established after any major change in the analytical
instrumentation or process. At least 80% of the analytes tested in the
MS/MSD must have in-house QC acceptance criteria that are tighter than
those in Table 6. If an in-house QC limit for the RPD is greater than
the limit in Table 6,
[[Page 9054]]
then the limit in Table 6 must be used. Similarly, if an in-house lower
limit for recovery is below the lower limit in Table 6, then the lower
limit in Table 6 must be used, and if an in-house upper limit for
recovery is above the upper limit in Table 6, then the upper limit in
Table 6 must be used. The laboratory must evaluate surrogate recovery
data in each sample against its in-house surrogate recovery limits. The
laboratory may use 60-140% as interim acceptance criteria for surrogate
recoveries until in-house limits are developed.
8.4 Laboratory control sample (LCS)--A QC check sample (laboratory
control sample, LCS; on-going precision and recovery sample, OPR)
containing each analyte of interest (Section 1.3) and surrogate must be
prepared and analyzed with each extraction batch of up to 20 samples to
demonstrate acceptable recovery of the analytes of interest from a
clean sample matrix.
8.4.1 Prepare the LCS by adding QC check sample concentrate
(Section 8.2.1) to reagent water. Include all analytes of interest
(Section 1.3) in the LCS. The LCS may be the same sample prepared for
the DOC (Section 8.2.1). The volume of reagent water must be the same
as the volume used for the sample, blank (Section 8.5), and MS/MSD
(Section 8.3). Also add an aliquot of the surrogate spiking solution
(Section 6.8). The concentration of the analytes in reagent water
should be the same as the concentration in the DOC (Section 8.2.2).
8.4.2 Analyze the LCS prior to analysis of field samples in the
extraction batch. Determine the concentration (A) of each analyte.
Calculate the percent recovery (PS) as 100 (A/T)%, where T is the true
value of the concentration in the LCS.
8.4.3 Compare the percent recovery (PS) for each analyte with its
corresponding QC acceptance criterion in Table 6. For analytes of
interest in Table 3 not listed in Table 6, use the QC acceptance
criteria developed for the MS/MSD (Section 8.3.3.2). If the recoveries
for all analytes of interest fall within their respective QC acceptance
criteria, analysis of blanks and field samples may proceed. If any
individual PS falls outside the range, proceed according to Section
8.4.4.
Note: The large number of analytes in Tables 1-3 present a
substantial probability that one or more will fail the acceptance
criteria when all analytes are tested simultaneously. Because a re-
test is allowed in event of failure (Sections 8.1.7 and 8.4.3), it
may be prudent to extract and analyze two LCSs together and evaluate
results of the second analysis against the QC acceptance criteria
only if an analyte fails the first test.
8.4.4 Repeat the test only for those analytes that failed to meet
the acceptance criteria (PS). If these analytes now pass, system
performance is acceptable and analysis of blanks and samples may
proceed. Repeated failure, however, will confirm a general problem with
the measurement system. If this occurs, repeat the test using a fresh
LCS (Section 8.2.2) or an LCS prepared with a fresh QC check sample
concentrate (Section 8.2.1), or perform and document system repair.
Subsequent to repair, repeat the LCS test (Section 8.4). If failure of
the LCS indicates a systemic problem with samples in the batch, re-
extract and re-analyze the samples in the batch. See Section 8.1.7 for
disposition of repeated failures.
Note: To maintain the validity of the test and re-test, system
maintenance and/or adjustment is not permitted between the pair of
tests.
8.4.5 After analysis of 20 LCS samples, the laboratory must
calculate and apply in-house QC limits for recovery to future LCS
samples (Section 8.4). Limits for recovery in the LCS are calculated as
the mean recovery 3 standard deviations. A minimum of 80%
of the analytes tested for in the LCS must have QC acceptance criteria
tighter than those in Table 6. Many of the analytes and surrogates may
not contain recommended acceptance criteria. The laboratory should use
60-140% as interim acceptance criteria for recoveries of spiked
analytes and surrogates that do not have recovery limits specified in
Table 8, until in-house LCS and surrogate limits are developed. If an
in-house lower limit for recovery is lower than the lower limit in
Table 6, the lower limit in Table 6 must be used, and if an in-house
upper limit for recovery is higher than the upper limit in Table 6, the
upper limit in Table 6 must be used.
8.5 Blank--A blank must be extracted and analyzed with each
extraction batch to demonstrate that the reagents and equipment used
for preparation and analysis are free from contamination.
8.5.1 Spike the surrogates into the blank. Extract and concentrate
the blank using the same procedures and reagents used for the samples,
LCS, and MS/MSD in the batch. Analyze the blank immediately after
analysis of the LCS (Section 8.4) and prior to analysis of the MS/MSD
and samples to demonstrate freedom from contamination.
8.5.2 If any analyte of interest is found in the blank: 1) At a
concentration greater than the MDL for the analyte, 2) at a
concentration greater than one-third the regulatory compliance limit,
or 3) at a concentration greater than one-tenth the concentration in a
sample in the extraction batch, whichever is greater, analysis of
samples must be halted and samples affected by the blank must be re-
extracted and the extracts re-analyzed. Samples must be associated with
an uncontaminated blank before they may be reported or used for
permitting or regulatory compliance purposes.
8.6 Internal standards responses.
8.6.1 Calibration verification--The responses (GC peak heights or
areas) of the internal standards in the calibration verification must
be within 50% to 200% (\1/2\ to 2x) of their respective responses in
the mid-point calibration standard. If they are not, repeat the
calibration verification (Section 7.4) test or perform and document
system repair. Subsequent to repair, repeat the calibration
verification. If the responses are still not within 50% to 200%, re-
calibrate the instrument (Section 7) and repeat the calibration
verification/LCS test.
8.6.2 Samples, blanks, LCSs, and MS/MSDs--The responses (GC peak
heights or areas) of the internal standards in each sample, blank, and
MS/MSD must be within 50% to 200% (\1/2\ to 2x) of its respective
response in the most recent LCS. If, as a group, all internal standards
are not within this range, perform and document system repair, repeat
the calibration verification/LCS test (Section 8.4), and re-analyze the
affected samples. If a single internal standard is not within the 50%
to 200% range, use an alternate internal standard for quantitation of
the analyte referenced to the affected internal standard.
8.7 Surrogate recoveries--Spike the surrogates into all samples,
blanks, LCSs, and MS/MSDs. Compare surrogate recoveries against the QC
acceptance criteria in Table 8 and/or those developed in Section 7.3.3.
If any recovery fails its criteria, attempt to find and correct the
cause of the failure. Surrogate recoveries from the blank and LCS may
be used as pass/fail criteria by the laboratory or as required by a
regulatory authority, or may be used to diagnose problems with the
analytical system.
8.8 DDT and endrin decomposition (breakdown)--If DDT and/or endrin
are to be analyzed using this method, a DDT/endrin decomposition test
must be performed to reliably quantify these two pesticides. The DDT/
endrin decomposition test to be used is in EPA Method 608A or 1656.
[[Page 9055]]
8.9 As part of the QC program for the laboratory, control charts or
statements of accuracy for wastewater samples must be assessed and
records maintained (40 CFR 136.7(c)(1)(viii)). After analysis of five
or more spiked wastewater samples as in Section 8.3, calculate the
average percent recovery (x) and the standard deviation of the percent
recovery (sp). Express the accuracy assessment as a percent interval
from x -2sp to x +2sp. For example, if x = 90% and sp = 10%, the
accuracy interval is expressed as 70-110%. Update the accuracy
assessment for each analyte on a regular basis (e.g., after each 5-10
new accuracy measurements).
8.10 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices
that are most productive depend upon the needs of the laboratory and
the nature of the samples. Field duplicates may be analyzed to assess
the precision of environmental measurements. Whenever possible, the
laboratory should analyze standard reference materials and participate
in relevant performance evaluation studies.
9. Sample Collection, Preservation, and Handling
9.1 Collect samples as grab samples in glass bottles or in
refrigerated bottles using automatic sampling equipment. Collect 1-L of
ambient waters, effluents, and other aqueous samples. If the
sensitivity of the analytical system is sufficient, a smaller volume
(e.g., 250 mL), but no less than 100 mL, may be used. Conventional
sampling practices (Reference 15) should be followed, except that the
bottle must not be pre-rinsed with sample before collection. Automatic
sampling equipment must be as free as possible of polyvinyl chloride or
other tubing or other potential sources of contamination. If needed,
collect additional sample(s) for the MS/MSD (Section 8.3).
9.2 Ice or refrigerate samples at <=6 [deg]C from the time of
collection until extraction, but do not freeze. If residual chlorine is
present, add 80 mg of sodium thiosulfate per liter of sample and mix
well. Any method suitable for field use may be employed to test for
residual chlorine (Reference 16). Do not add excess sodium thiosulfate.
If sodium thiosulfate interferes in the determination of the analytes,
an alternate preservative (e.g., ascorbic acid or sodium sulfite) may
be used.
9.3 All samples must be extracted within 7 days of collection and
sample extracts must be analyzed within 40 days of extraction.
10. Extraction
10.1 This section contains procedures for separatory funnel liquid-
liquid extraction (SFLLE) and continuous liquid-liquid extraction
(CLLE). SFLLE is faster, but may not be as effective as CLLE for
recovery of polar analytes such as phenol. SFLLE is labor intensive and
may result in formation of emulsions that are difficult to break. CLLE
is less labor intensive, avoids emulsion formation, but requires more
time (18-24 hours) and more hood space, and may require more solvent.
The procedures assume base-neutral extraction followed by acid
extraction. For some matrices and analytes of interest, improved
results may be obtained by acid-neutral extraction followed by base
extraction. A single acid or base extraction may also be performed. If
an extraction scheme alternate to base-neutral followed by acid
extraction is used, all QC tests must be performed and all QC
acceptance criteria must be met with that extraction scheme as an
integral part of this method.
10.2 Separatory funnel liquid-liquid extraction (SFLLE) and extract
concentration
10.2.1 The SFLLE procedure below assumes a sample volume of 1 L.
When a different sample volume is extracted, adjust the volume of
methylene chloride accordingly.
10.2.2 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into the
separatory funnel. Pipet the surrogate standard spiking solution
(Section 6.8) into the separatory funnel. If the sample will be used
for the LCS or MS or MSD, pipet the appropriate check sample
concentrate (Section 8.2.1 or 8.3.2) into the separatory funnel. Mix
well. Check the pH of the sample with wide-range pH paper and adjust to
pH 11-13 with sodium hydroxide solution.
10.2.3 Add 60 mL of methylene chloride to the sample bottle, seal,
and shake for approximately 30 seconds to rinse the inner surface.
Transfer the solvent to the separatory funnel and extract the sample by
shaking the funnel for two minutes with periodic venting to release
excess pressure. Allow the organic layer to separate from the water
phase for a minimum of 10 minutes. If the emulsion interface between
layers is more than one-third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample, but may
include stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical methods. Collect the methylene
chloride extract in a flask. If the emulsion cannot be broken (recovery
of <80% of the methylene chloride), transfer the sample, solvent, and
emulsion into a continuous extractor and proceed as described in
Section 10.3.
10.2.4 Add a second 60-mL volume of methylene chloride to the
sample bottle and repeat the extraction procedure a second time,
combining the extracts in the Erlenmeyer flask. Perform a third
extraction in the same manner.
10.2.5 Adjust the pH of the aqueous phase to less than 2 using
sulfuric acid. Serially extract the acidified aqueous phase three times
with 60 mL aliquots of methylene chloride. Collect and combine the
extracts in a flask in the same manner as the base/neutral extracts.
Note: Base/neutral and acid extracts may be combined for
concentration and analysis provided all QC tests are performed and
all QC acceptance criteria met for the analytes of interest with the
combined extract as an integral part of this method, and provided
that the analytes of interest are as reliably identified and
quantified as when the extracts are analyzed separately. If doubt
exists as to whether identification and quantitation will be
affected by use of a combined extract, the fractions must be
analyzed separately.
10.2.6 For each fraction or the combined fractions, assemble a
Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator
tube to a 500-mL evaporative flask. Other concentration devices or
techniques may be used in place of the K-D concentrator so long as the
requirements in Section 8.2 are met.
10.2.7 For each fraction or the combined fractions, pour the
extract through a solvent-rinsed drying column containing about 10 cm
of anhydrous sodium sulfate, and collect the extract in the K-D
concentrator. Rinse the Erlenmeyer flask and column with 20-30 mL of
methylene chloride to complete the quantitative transfer.
10.2.8 Add one or two clean boiling chips and attach a three-ball
Snyder column to the evaporative flask for each fraction (Section
10.2.7). Pre-wet the Snyder column by adding about 1 mL of methylene
chloride to the top. Place the K-D apparatus on a hot water bath (60-65
[deg]C) so that the concentrator tube is partially immersed in the hot
water, and the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 15-20 minutes.
At the proper rate of
[[Page 9056]]
distillation, the balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent
volume of liquid reaches 1 mL or other determined amount, remove the K-
D apparatus from the water bath and allow to drain and cool for at
least 10 minutes. Remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1-2 mL of methylene
chloride. A 5-mL syringe is recommended for this operation. If the
sample will be cleaned up, reserve the K-D apparatus for concentration
of the cleaned up extract. Adjust the volume to 5 mL with methylene
chloride and proceed to Section 11 for cleanup; otherwise, further
concentrate the extract for GC/MS analysis per Section 10.2.9 or
10.2.10.
10.2.9 Micro Kuderna-Danish concentration--add another one or two
clean boiling chips to the concentrator tube for each fraction and
attach a two-ball micro-Snyder column. Pre-wet the Snyder column by
adding about 0.5 mL of methylene chloride to the top. Place the K-D
apparatus on a hot water bath (60-65 [deg]C) so that the concentrator
tube is partially immersed in hot water. Adjust the vertical position
of the apparatus and the water temperature as required to complete the
concentration in 5-10 minutes. At the proper rate of distillation the
balls of the column will actively chatter but the chambers will not
flood with condensed solvent. When the apparent volume of liquid
reaches about 1 mL or other determined amount, remove the K-D apparatus
from the water bath and allow it to drain and cool for at least 10
minutes. Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with approximately 0.2 mL of or
methylene chloride. Adjust the final volume to 1.0 mL or a volume
appropriate to the sensitivity desired (e.g., to meet lower MDLs or for
selected ion monitoring). Record the volume, stopper the concentrator
tube and store refrigerated if further processing will not be performed
immediately. If the extracts will be stored longer than two days, they
should be transferred to fluoropolymer-lined screw-cap vials and
labeled base/neutral or acid fraction as appropriate. Mark the level of
the extract on the vial so that solvent loss can be detected.
10.2.10 Nitrogen evaporation and solvent exchange--Extracts may be
concentrated for analysis using nitrogen evaporation in place of micro
K-D concentration (Section 10.2.9). Extracts that have been cleaned up
using sulfur removal (Section 12.2) and are ready for analysis are
exchanged into methylene chloride.
10.2.10.1 Transfer the vial containing the sample extract to the
nitrogen evaporation (blowdown) device (Section 5.8). Lower the vial
into the water bath and begin concentrating. If the more volatile
analytes (Section 1.2) are to be concentrated, use room temperature for
concentration; otherwise, a slightly elevated (e.g., 30-45 [deg]C) may
be used. During the solvent evaporation process, keep the solvent level
below the water level of the bath and do not allow the extract to
become dry. Adjust the flow of nitrogen so that the surface of the
solvent is just visibly disturbed. A large vortex in the solvent may
cause analyte loss.
10.2.10.2 Extracts to be solvent exchanged--When the volume of the
liquid is approximately 200 [mu]L, add 2 to 3 mL of methylene chloride
and continue concentrating to approximately 100 [mu]L. Repeat the
addition of solvent and concentrate once more. Adjust the final extract
volume to be consistent with the volume extracted and the sensitivity
desired.
10.2.10.3 For extracts that have been cleaned up by GPC and that
are to be concentrated to a nominal volume of 1 mL, adjust the final
volume to compensate the GPC loss. For a 50% GPC loss, concentrate the
extract to 1/2000 of the volume extracted. For example, if the volume
extracted is 950 mL, adjust the final volume to 0.48 mL. For extracts
that have not been cleaned up by GPC and are to be concentrated to a
nominal volume of 1.0 mL, adjust the final extract volume to 1/1000 of
the volume extracted. For example, if the volume extracted is 950 mL,
adjust the final extract volume to 0.95 mL.
Note: The difference in the volume fraction for an extract
cleaned up by GPC accounts for the loss in GPC cleanup. Also, by
preserving the ratio between the volume extracted and the final
extract volume, the concentrations and detection limits do not need
to be adjusted for differences in the volume extracted and the
extract volume.
10.2.11 Transfer the concentrated extract to a vial with
fluoropolymer-lined cap. Seal the vial and label with the sample
number. Store in the dark at room temperature until ready for GC
analysis. If GC analysis will not be performed on the same day, store
the vial in the dark at <=6 [deg]C. Analyze the extract by GC/MS per
the procedure in Section 12.
10.2.12 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the liquid to an
appropriately sized graduated cylinder. For sample volumes on the order
of 1000 mL, record the sample volume to the nearest 10 mL; for sample
volumes on the order of 100 mL, record the volume to the nearest 1 mL.
Sample volumes may also be determined by weighing the container before
and after filling to the mark with water.
10.3 Continuous liquid/liquid extraction (CLLE).
Note: With CLLE, phenol, 2,4-dimethyl phenol, and some other
analytes may be preferentially extracted into the base-neutral
fraction. Determine an analyte in the fraction in which it is
identified and quantified most reliably. Also, the short-chain
phthalate esters (e.g., dimethyl phthalate, diethyl phthalate) and
some other compounds may hydrolyze during prolonged exposure to
basic conditions required for continuous extraction, resulting in
low recovery of these analytes. When these analytes are of interest,
their recovery may be improved by performing the acid extraction
first.
10.3.1 Use CLLE when experience with a sample from a given source
indicates an emulsion problem, or when an emulsion is encountered
during SFLLE. CLLE may be used for all samples, if desired.
10.3.2 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Check the pH of the sample with
wide-range pH paper and adjust to pH 11-13 with sodium hydroxide
solution. Transfer the sample to the continuous extractor. Pipet
surrogate standard spiking solution (Section 6.8) into the sample. If
the sample will be used for the LCS or MS or MSD, pipet the appropriate
check sample concentrate (Section 8.2.1 or 8.3.2) into the extractor.
Mix well. Add 60 mL of methylene chloride to the sample bottle, seal,
and shake for 30 seconds to rinse the inner surface. Transfer the
solvent to the extractor.
10.3.3 Repeat the sample bottle rinse with an additional 50-100 mL
portion of methylene chloride and add the rinse to the extractor.
10.3.4 Add a suitable volume of methylene chloride to the
distilling flask (generally 200-500 mL), add sufficient reagent water
to ensure proper operation, and extract for 18-24 hours. A shorter or
longer extraction time may be used if all QC acceptance criteria are
met. Test and, if necessary, adjust the pH of the water during the
second or third hour of the extraction. After extraction, allow the
apparatus to cool, then detach the distilling flask. Dry, concentrate,
and seal the extract per Sections 10.2.6 through 10.2.11. See the note
at Section 10.2.5 regarding combining extracts of the base/neutral and
acid fractions.
10.3.5 Charge the distilling flask with methylene chloride and
attach it to the continuous extractor. Carefully,
[[Page 9057]]
while stirring, adjust the pH of the aqueous phase to less than 2 using
sulfuric acid. Extract for 18-24 hours. A shorter or longer extraction
time may be used if all QC acceptance criteria are met. Test and, if
necessary, adjust the pH of the water during the second or third hour
of the extraction. After extraction, allow the apparatus to cool, then
detach the distilling flask. Dry, concentrate, and seal the extract per
Sections 10.2.6 through 10.2.11. Determine the sample volume per
Section 10.2.12.
11. Extract Cleanup
Note: Cleanup may not be necessary for relatively clean samples
(e.g., treated effluents, groundwater, drinking water). If
particular circumstances require the use of a cleanup procedure, the
laboratory may use any or all of the procedures below or any other
appropriate procedure. Before using a cleanup procedure, the
laboratory must demonstrate that the requirements of Section 8.1.2
can be met using the cleanup procedure as an integral part of this
method.
11.1 Gel permeation chromatography (GPC).
11.1.1 Calibration.
11.1.1.1 Load the calibration solution (Section 6.12) into the
sample loop.
11.1.1.2 Inject the calibration solution and record the signal from
the detector. The elution pattern will be corn oil, bis(2-ethylhexyl)
phthalate, pentachlorophenol, perylene, and sulfur.
11.1.1.3 Set the ``dump time'' to allow >85% removal of the corn
oil and >85% collection of the phthalate.
11.1.1.4 Set the ``collect time'' to the peak minimum between
perylene and sulfur.
11.1.1.5 Verify calibration with the calibration solution after
every 20 or fewer extracts. Calibration is verified if the recovery of
the pentachlorophenol is greater than 85%. If calibration is not
verified, recalibrate using the calibration solution, and re-extract
and clean up the preceding extracts using the calibrated GPC system.
11.1.2 Extract cleanup--GPC requires that the column not be
overloaded. The column specified in this method is designed to handle a
maximum of 0.5 g of high molecular weight material in a 5-mL extract.
If the extract is known or expected to contain more than 0.5 g, the
extract is split into fractions for GPC and the fractions are combined
after elution from the column. The solids content of the extract may be
obtained gravimetrically by evaporating the solvent from a 50-[mu]L
aliquot.
11.1.2.1 Filter the extract or load through the filter holder to
remove particulates. Load the extract into the sample loop. The maximum
capacity of the column is 0.5-1.0 g. If necessary, split the extract
into multiple aliquots to prevent column overload.
11.1.2.2 Elute the extract using the calibration data determined in
Section 11.1.1. Collect the eluate in the K-D apparatus reserved in
Section 10.2.8.
11.1.3 Concentrate the cleaned up extract per Sections 10.2.8 and
10.2.9 or 10.2.10.
11.1.4 Rinse the sample loading tube thoroughly with methylene
chloride between extracts to prepare for the next sample.
11.1.5 If a particularly dirty extract is encountered, run a
methylene chloride blank through the system to check for carry-over.
11.2 Sulfur removal.
Note: Separate procedures using copper or TBA sulfite are
provided in this section for sulfur removal. They may be used
separately or in combination, if desired.
11.2.1 Removal with copper (Reference 17).
Note: If (1) an additional compound (Table 3) is to be
determined; (2) sulfur is to be removed; (3) copper will be used for
sulfur removal; and (4) a sulfur matrix is known or suspected to be
present, the laboratory must demonstrate that the additional
compound can be successfully extracted and treated with copper in
the sulfur matrix. Some of the additional compounds (Table 3) are
known not to be amenable to sulfur removal with copper (e.g.
Atrazine and Diazinon).
11.2.1.1 Quantitatively transfer the extract from Section 10.2.8 to
a 40- to 50-mL flask or bottle. If there is evidence of water in the
concentrator tube after the transfer, rinse the tube with small
portions of hexane:acetone (40:60) and add to the flask or bottle. Mark
and set aside the concentrator tube for use in re-concentrating the
extract.
11.2.1.2 Add 10-20 g of granular anhydrous sodium sulfate to the
flask. Swirl to dry the extract.
11.2.1.3 Add activated copper (Section 6.13.1.4) and allow to stand
for 30-60 minutes, swirling occasionally. If the copper does not remain
bright, add more and swirl occasionally for another 30-60 minutes.
11.2.1.4 After drying and sulfur removal, quantitatively transfer
the extract to a nitrogen-evaporation vial or tube and proceed to
Section 10.2.10 for nitrogen evaporation and solvent exchange, taking
care to leave the sodium sulfate and copper in the flask.
11.2.2 Removal with TBA sulfite.
11.2.2.1 Using small volumes of hexane, quantitatively transfer the
extract to a 40- to 50-mL centrifuge tube with fluoropolymer-lined
screw cap.
11.2.2.2 Add 1-2 mL of TBA sulfite reagent (Section 6.13.2.4), 2-3
mL of 2-propanol, and approximately 0.7 g of sodium sulfite (Section
6.13.2.2) crystals to the tube. Cap and shake for 1-2 minutes. If the
sample is colorless or if the initial color is unchanged, and if clear
crystals (precipitated sodium sulfite) are observed, sufficient sodium
sulfite is present. If the precipitated sodium sulfite disappears, add
more crystalline sodium sulfite in approximately 0.5 g portions until a
solid residue remains after repeated shaking.
11.2.2.3 Add 5-10 mL of reagent water and shake for 1-2 minutes.
Centrifuge to settle the solids.
11.2.2.4 Quantitatively transfer the hexane (top) layer through a
small funnel containing a few grams of granular anhydrous sodium
sulfate to a nitrogen-evaporation vial or tube and proceed to Section
10.2.10 for nitrogen evaporation and solvent exchange.
12. Gas Chromatography/Mass Spectrometry
12.1 Establish the operating conditions in Table 4 or 5 for
analysis of a base/neutral or acid extract, respectively. For analysis
of a combined extract (Section 10.2.5, note), use the operating
conditions in Table 4. Included in these tables are retention times and
MDLs that can be achieved under these conditions. Examples of the
separations achieved are shown in Figure 2 for the combined extract.
Alternative columns or chromatographic conditions may be used if the
requirements of Section 8.2 are met. Verify system performance per
Section 13.
12.2 Analysis of a standard or extract.
12.2.1 Bring the standard or concentrated extract (Section 10.2.9
or 10.2.11) to room temperature and verify that any precipitate has
redissolved. Verify the level on the extract and bring to the mark with
solvent if required.
12.2.2 Add the internal standard solution (Section 6.9) to the
extract. Mix thoroughly.
12.2.3 Inject an appropriate volume of the sample extract or
standard solution using split, splitless, solvent purge, large-volume,
or on-column injection. If the sample is injected manually the solvent-
flush technique should be used. The injection volume depends upon the
technique used and the ability to meet MDLs or reporting limits for
regulatory compliance. Injected volumes must be the same for standards
and sample extracts. Record the volume injected to two significant
figures.
[[Page 9058]]
12.2.3.1 Start the GC column oven program upon injection. Start MS
data collection after the solvent peak elutes. Stop data collection
after benzo(ghi)perylene elutes for the base/neutral or combined
fractions, or after pentachlorophenol elutes for the acid fraction.
Return the column to the initial temperature for analysis of the next
standard solution or extract.
12.2.3.2 If the concentration of any analyte of interest exceeds
the calibration range, either extract and analyze a smaller sample
volume, or dilute and analyze the diluted extract after bringing the
concentrations of the internal standards to the levels in the undiluted
extract.
12.2.4 Perform all qualitative and quantitative measurements as
described in Sections 14 and 15. When standards and extracts are not
being used for analyses, store them refrigerated at <=6 [deg]C
protected from light in screw-cap vials equipped with un-pierced
fluoropolymer-lined septa.
13. Performance tests
13.1 At the beginning of each 12-hour shift during which standards
or extracts will be analyzed, perform the tests in Sections 13.2-13.7
to verify system performance. If DDT and/or endrin are to be
determined, perform the decomposition test in Section 13.8. If an
extract is concentrated for greater sensitivity (e.g., by SIM), all
tests must be performed at levels consistent with the reduced extract
volume.
13.2 DFTPP--Inject the DFTPP standard (Section 6.10) and verify
that the criteria for DFTPP in Section 7.2.1.1 and Table 9A (Reference
18) for a quadrupole MS, or Table 9B (Reference 19) for a time-of-
flight MS, are met. It is not necessary to meet DFTPP criteria for SIM
operation.
13.3 GC resolution--There must be a valley between
benzo(b)fluoranthene and benzo(k)fluoranthene at m/z 252, and the
height of the valley must not exceed 25 percent of the shorter of the
two peaks.
13.4 Calibration verification--Verify calibration per Sections 7.3
and Table 6.
13.5 Peak tailing--Verify the tailing factor specifications are met
per Section 7.2.1.1.
13.6 Laboratory control sample and blank--Analyze the extracts of
the LCS and blank at the beginning of analyses of samples in the
extraction batch (Section 3.1). The LCS must meet the requirements in
Section 8.4, and the blank must meet the requirements in Section 8.5
before sample extracts may be analyzed.
13.7 Matrix spike/matrix spike duplicate--Analyze the background
sample for the MS/MSD and the MS and MSD after the blank (Section
8.3.2). Results for the MS/MSD must meet the requirements in Section
8.3 before a result for an analyte in any unspiked sample in the batch
may be reported or used for permitting or regulatory compliance
purposes.
13.8 DDT/endrin decomposition test--If DDT and/or endrin analytes
of interest, the DDT/endrin test (Section 8.8) must be performed and
the QC acceptance criteria must be met before analyzing samples for DDT
and/or endrin.
14. Qualitative Identification
14.1 Identification is accomplished by comparison of data from
analysis of a sample or blank with data stored in the GC/MS data system
(Sections 5.6.5 and 7.2.1.2, and Tables 4 and 5). Identification of an
analyte is confirmed per Sections 14.1.1 through 14.1.4.
14.1.1 The signals for all characteristic m/z's stored in the data
system for each analyte of interest must be present and must maximize
within the same two consecutive scans.
14.1.2 Based on the relative retention time (RRT), the RRT for the
analyte must be within 0.06 of the RRT of the analyte in
the calibration verification run at the beginning of the shift (Section
7.3 or 13.4). Relative retention time is used to establish the
identification window because it compensates for small changes in the
GC temperature program whereas the absolute retention time does not
(see Section 6.9.3).
Note: RRT is a unitless quantity (see Sec. 20.2), although some
procedures refer to ``RRT units'' in providing the specification for
the agreement between the RRT values in the sample and the
calibration verification or other standard.
14.1.3 Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC
peak maximum, must agree within 50% to 200% (\1/2\ to 2 times) for all
m/z's in the reference mass spectrum stored in the data system (Section
7.2.1.2), or from a reference library. For example, if a peak has an
intensity of 20% relative to the base peak, the analyte is identified
if the intensity of the peak in the sample is in the range of 10% to
40% of the base peak.
14.1.4 The m/z's present in the acquired mass spectrum for the
sample that are not present in the reference mass spectrum must be
accounted for by contaminant or background m/z's. A reference library
may be helpful to identify and account for background or contaminant m/
z's. If the acquired mass spectrum is contaminated, or if
identification is ambiguous, an experienced spectrometrist (Section
1.7) must determine the presence or absence of the compound.
14.2 Structural isomers that have very similar mass spectra can be
identified only if the resolution between authentic isomers in a
standard mix is acceptable. Acceptable resolution is achieved if the
baseline to valley height between the isomers is less than 50% of the
height of the shorter of the two peaks. Otherwise, structural isomers
are identified as isomeric pairs.
15. Calculations
15.1 When an analyte has been identified, quantitation of that
analyte is based on the integrated abundance from the EICP of the
primary characteristic m/z in Table 4 or 5. Calculate the concentration
in the extract using the response factor (RF) determined in Section
7.2.2 and Equation 2. If the concentration of an analyte exceeds the
calibration range, dilute the extract by the minimum amount to bring
the concentration into the calibration range, and re-analyze the
extract. Determine a dilution factor (DF) from the amount of the
dilution. For example, if the extract is diluted by a factor of 2, DF =
2.
[GRAPHIC] [TIFF OMITTED] TP19FE15.017
Where:
Cex = Concentration of the analyte in the extract, in
[micro]g/mL, and the other terms are as defined in Equation 1.
Calculate the concentration of the analyte in the sample using the
concentration in the extract, the extract volume, the sample volume,
and the dilution factor, per Equation 3:
[[Page 9059]]
[GRAPHIC] [TIFF OMITTED] TP19FE15.018
Where:
Cs = Concentration of the analyte in the sample
Cex = Concentration of the analyte in the extract, in
[mu]g/mL
Vex = Volume of extract (mL)
Vs = Volume of sample (L)
DF = Dilution factor
15.2 Reporting of results
As noted in Section 1.4.1, EPA has promulgated this method at 40
CFR part 136 for use in wastewater compliance monitoring under the
National Pollutant Discharge Elimination System (NPDES). The data
reporting practices described here are focused on such monitoring needs
and may not be relevant to other uses of the method.
15.2.1 Report results for wastewater samples in [mu]g/L without
correction for recovery. (Other units may be used if required by in a
permit.) Report all QC data with the sample results.
15.2.2 Reporting level
Unless otherwise specified in by a regulatory authority or in a
discharge permit, results for analytes that meet the identification
criteria are reported down to the concentration of the ML established
by the laboratory through calibration of the instrument (see Section
7.3.2 and the glossary for the derivation of the ML). EPA considers the
terms ``reporting limit,'' ``quantitation limit,'' and ``minimum
level'' to be synonymous.
15.2.2.1 Report a result for each analyte in each sample, blank, or
standard at or above the ML to 3 significant figures. Report a result
for each analyte found in each sample below the ML as ``ML,'' or as
required by the regulatory authority or permit. Results are reported
without blank subtraction unless requested or required by a regulatory
authority or in a permit. In this case, both the sample result and the
blank results must be reported together.
15.2.2.2 In addition to reporting results for samples and blanks
separately, the concentration of each analyte in a blank associated
with the sample may be subtracted from the result for that sample, but
only if requested or required by a regulatory authority or in a permit.
In this case, both the sample result and the blank results must be
reported together.
15.2.2.3 Report a result for an analyte found in a sample or
extract that has been diluted at the least dilute level at which the
area at the quantitation m/z is within the calibration range (i.e.,
above the ML for the analyte) and the MS/MSD recovery and RPD are
within their respective QC acceptance criteria (Table 6). This may
require reporting results for some analytes from different analyses.
15.2.3 Results from tests performed with an analytical system that
is not in control (i.e., that does not meet acceptance criteria for all
of QC tests in this method) must not be reported or otherwise used for
permitting or regulatory compliance purposes, but do not relieve a
discharger or permittee of reporting timely results. If the holding
time would be exceeded for a re-analysis of the sample, the regulatory/
control authority should be consulted for disposition.
16. Method Performance
16.1 The basic version of this method was tested by 15 laboratories
using reagent water, drinking water, surface water, and industrial
wastewaters spiked at six concentrations over the range 5-1300 [mu]g/L
(Reference 2). Single operator precision, overall precision, and method
accuracy were found to be directly related to the concentration of the
analyte and essentially independent of the sample matrix. Linear
equations to describe these relationships are presented in Table 7.
16.2 As noted in Sec. 1.1, this method was validated through an
interlaboratory study conducted more than 29 years ago. However, the
fundamental chemistry principles used in this method remain sound and
continue to apply.
16.3 A chromatogram of the combined acid/base/neutral calibration
standard is shown in Figure 2.
17. Pollution Prevention
17.1 Pollution prevention encompasses any technique that reduces or
eliminates the quantity or toxicity of waste at the point of
generation. Many opportunities for pollution prevention exist in
laboratory operations. EPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention as
the management option of first choice. Whenever feasible, the
laboratory should use pollution prevention techniques to address waste
generation. When wastes cannot be reduced at the source, the Agency
recommends recycling as the next best option.
17.2 The analytes in this method are used in extremely small
amounts and pose little threat to the environment when managed
properly. Standards should be prepared in volumes consistent with
laboratory use to minimize the disposal of excess volumes of expired
standards. This method utilizes significant quantities of methylene
chloride. Laboratories are encouraged to recover and recycle this and
other solvents during extract concentration.
17.3 For information about pollution prevention that may be applied
to laboratories and research institutions, consult Less is Better:
Laboratory Chemical Management for Waste Reduction, available from the
American Chemical Society's Department of Governmental Relations and
Science Policy, 1155 16th Street NW., Washington, DC 20036, 202/872-
4477.
18. Waste Management
18.1 The laboratory is responsible for complying with all Federal,
State, and local regulations governing waste management, particularly
the hazardous waste identification rules and land disposal
restrictions, and to protect the air, water, and land by minimizing and
controlling all releases from fume hoods and bench operations.
Compliance is also required with any sewage discharge permits and
regulations. An overview of requirements can be found in Environmental
Management Guide for Small Laboratories (EPA 233-B-98-001).
18.2 Samples at pH <2, or pH >12 are hazardous and must be
neutralized before being poured down a drain, or must be handled and
disposed of as hazardous waste.
18.3 Many analytes in this method decompose above 500 [deg]C. Low-
level waste such as absorbent paper, tissues, and plastic gloves may be
burned in an appropriate incinerator. Gross quantities of neat or
highly concentrated solutions of toxic or hazardous chemicals should be
packaged securely and disposed of through commercial or governmental
channels that are capable of handling these types of wastes.
18.4 For further information on waste management, consult The Waste
Management Manual for Laboratory Personnel and Less is Better-
Laboratory Chemical Management for Waste Reduction, available from the
American Chemical Society's Department of Government Relations and
Science Policy, 1155 16th Street NW., Washington, DC 20036, 202/872-
4477.
[[Page 9060]]
19. References
1. ``Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants,'' U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio 45268, March 1977, Revised April 1977.
2. ``EPA Method Study 30, Method 625, Base/Neutrals, Acids, and
Pesticides,'' EPA 600/4-84-053, National Technical Information Service,
PB84-206572, Springfield, Virginia 22161, June 1984.
3. 40 CFR part 136, appendix B.
4. Olynyk, P., Budde, W.L. and Eichelberger, J.W. ``Method Detection
Limit for Methods 624 and 625,'' Unpublished report, May 14, 1980.
5. Annual Book of ASTM Standards, Volume 11.02, D3694-96, ``Standard
Practices for Preparation of Sample Containers and for Preservation of
Organic Constituents,'' American Society for Testing and Materials,
Philadelphia.
6. Solutions to Analytical Chemistry Problems with Clean Water Act
Methods, EPA 821-R-07-002, March 2007.
7. ``Carcinogens-Working With Carcinogens,'' Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
8. ``OSHA Safety and Health Standards, General Industry,'' (29 CFR part
1910), Occupational Safety and Health Administration, OSHA 2206
(Revised, January 1976).
9. ``Safety in Academic Chemistry Laboratories,'' American Chemical
Society Publication, Committee on Chemical Safety, 7th Edition, 2003.
10. http://en.wikipedia.org/wiki/Coefficient_of_determination (accessed
on 09/10/2013).
11. 40 CFR 136.6(b)(4)(x).
12. 40 CFR 136.6(b)(2)(i).
13. Protocol for EPA Approval of New Methods for Organic and Inorganic
Analytes in Wastewater and Drinking Water (EPA-821-B-98-003) March
1999.
14. Provost, L.P. and Elder, R.S. ``Interpretation of Percent Recovery
Data,'' American Laboratory, 15, 58-63 (1983). (The value 2.44 used in
the equation in Section 8.3.3 is two times the value 1.22 derived in
this report.)
15. ASTM Annual Book of Standards, Part 31, D3370-76. ``Standard
Practices for Sampling Water,'' American Society for Testing and
Materials, Philadelphia.
16. 40 CFR 136.3(a), Table IB, Chlorine--Total Residual.
17. ``Manual of Analytical Methods for the Analysis of Pesticides in
Human and Environmental Samples,'' EPA-600/8-80-038, U.S. Environmental
Protection Agency, Health Effects Research Laboratory, Research
Triangle Park, North Carolina.
18. Eichelberger, J.W., Harris, L.E., and Budde, W.L. ``Reference
Compound to Calibrate Ion Abundance Measurement in Gas Chromatography-
Mass Spectrometry,'' Analytical Chemistry, 47, 995 (1975).
19. Letter of approval of acceptance criteria for DFTPP for time-of-
flight mass spectrometers from William A. Telliard and Herb Brass of
EPA to Jack Cochran of LECO Corporation, February 9, 2005.
20. Tables.
Table 1--Non Pesticide/PCB Base/Neutral Extractables \1\
----------------------------------------------------------------------------------------------------------------
Analyte CAS Registry MDL \4\ ML \5\
----------------------------------------------------------------------------------------------------------------
Acenaphthene.................................................... 83-32-9 1.9 5.7
Acenaphthylene.................................................. 208-96-8 3.5 10.5
Anthracene...................................................... 120-12-7 1.9 5.7
Benzidine \2\................................................... 92-87-5 44 132
Benzo(a)anthracene.............................................. 56-55-3 7.8 23.4
Benzo(a)pyrene.................................................. 50-32-8 2.5 7.5
Benzo(b)fluoranthene............................................ 205-99-2 4.8 14.4
Benzo(k)fluoranthene............................................ 207-08-9 2.5 7.5
Benzo(ghi)perylene.............................................. 191-24-2 4.1 12.3
Benzyl butyl phthalate.......................................... 85-68-7 2.5 7.5
bis(2-Chloroethoxy)methane...................................... 111-91-1 5.3 15.9
bis(2-Ethylhexyl)phthalate...................................... 117-81-7 2.5 7.5
bis(2-Chloroisopropyl) ether (2,2'-Oxybis(1-chloropropane))..... 108-60-1 5.7 17.1
4-Bromophenyl phenyl ether...................................... 101-55-3 1.9 5.7
2-Chloronaphthalene............................................. 91-58-7 1.9 5.7
4-Chlorophenyl phenyl ether..................................... 7005-72-3 4.2 12.6
Chrysene........................................................ 218-01-9 2.5 7.5
Dibenz(a,h)anthracene........................................... 53-70-3 2.5 7.5
Di-n-butylphthalate............................................. 84-74-2 2.5 7.5
3,3'-Dichlorobenzidine.......................................... 91-94-1 16.5 49.5
Diethyl phthalate............................................... 84-66-2 1.9 5.7
Dimethyl phthalate.............................................. 131-11-3 1.6 4.8
2,4-Dinitrotoluene.............................................. 121-14-2 5.7 17.1
2,6-Dinitrotoluene.............................................. 606-20-2 1.9 5.7
Di-n-octylphthalate............................................. 117-84-0 2.5 7.5
Fluoranthene.................................................... 206-44-0 2.2 6.6
Fluorene........................................................ 86-73-7 1.9 5.7
Hexachlorobenzene............................................... 118-74-1 1.9 5.7
Hexachlorobutadiene............................................. 87-68-3 0.9 2.7
Hexachloroethane................................................ 67-72-1 1.6 4.8
Indeno(1,2,3-cd)pyrene.......................................... 193-39-5 3.7 11.1
Isophorone...................................................... 78-59-1 2.2 6.6
Naphthalene..................................................... 91-20-3 1.6 4.8
Nitrobenzene.................................................... 98-95-3 1.9 5.7
N-Nitrosodi-n-propylamine \3\................................... 621-64-7 -- --
Phenanthrene.................................................... 85-01-8 5.4 16.2
Pyrene.......................................................... 129-00-0 1.9 5.7
1,2,4-Trichlorobenzene.......................................... 120-82-1 1.9 5.7
----------------------------------------------------------------------------------------------------------------
\1\ All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A).
[[Page 9061]]
\2\ Included for tailing factor testing.
\3\ See Section 1.2.
\4\ MDL values from the 1984 promulgated version of Method 624.
\5\ ML = Minimum Level--see Glossary for definition and derivation.
Table 2--Acid Extractables \1\
----------------------------------------------------------------------------------------------------------------
Analyte CAS Registry MDL \3\ ML \4\
----------------------------------------------------------------------------------------------------------------
4-Chloro-3-methylphenol......................................... 59-50-7 3.0 9.0
2-Chlorophenol.................................................. 95-57-8 3.3 9.9
2,4-Dichlorophenol.............................................. 120-83-2 2.7 8.1
2,4-Dimethylphenol.............................................. 105-67-9 2.7 8.1
2,4-Dinitrophenol............................................... 51-28-5 42 126
2-Methyl-4,6-dinitrophenol...................................... 534-52-1 24 72
2-Nitrophenol................................................... 88-75-5 3.6 10.8
4-Nitrophenol................................................... 100-02-7 2.4 7.2
Pentachlorophenol \2\........................................... 87-86-5 3.6 10.8
Phenol.......................................................... 108-95-2 1.5 4.5
2,4,6-Trichlorophenol........................................... 88-06-2 2.7 8.1
----------------------------------------------------------------------------------------------------------------
\1\ All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A).
\2\ See Section 1.2; included for tailing factor testing.
\3\ MDL values from the 1984 promulgated version of Method 624.
\4\ ML = Minimum Level--see Glossary for definition and derivation.
Table 3--Additional Extractable Analytes \1\ \2\
----------------------------------------------------------------------------------------------------------------
Analyte CAS Registry MDL \6\ ML \7\
----------------------------------------------------------------------------------------------------------------
Acetophenone.................................................... 98-86-2
2-Acetylaminofluorene........................................... 53-96-3
1-Acetyl-2-thiourea............................................. 591-08-2
Alachlor........................................................ 15972-60-8
Aldrin \3\...................................................... 309-00-2 1.9 5.7
Ametryn......................................................... 834-12-8
2-Aminoanthraquinone............................................ 117-79-3
Aminoazobenzene................................................. 60-09-3
4-Aminobiphenyl................................................. 92-67-1
3-Amino-9-ethylcarbazole........................................ 132-32-1
Anilazine....................................................... 101-05-3
Aniline......................................................... 62-53-3
o-Anisidine..................................................... 90-04-0
Aramite......................................................... 140-57-8
Atraton......................................................... 1610-17-9
Atrazine........................................................ 1912-24-9
Azinphos-methyl................................................. 86-50-0
Barban.......................................................... 101-27-9
Benzanthrone.................................................... 82-05-3
Benzenethiol.................................................... 108-98-5
Benzidine \3\ \4\............................................... 92-87-5 44 132
Benzoic acid.................................................... 65-85-0
2,3-Benzofluorene............................................... 243-17-4
p-Benzoquinone.................................................. 106-51-4
Benzyl alcohol.................................................. 100-51-6
alpha-BHC \3\ \4\............................................... 319-84-6
beta-BHC \3\.................................................... 319-85-7 3.1 9.3
gamma-BHC (Lindane) 3 4......................................... 58-89-8 4.2 12.6
delta-BHC \3\................................................... 319-86-8
Biphenyl........................................................ 92-52-4
Bromacil........................................................ 314-40-9
2-Bromochlorobenzene............................................ 694-80-4
3-Bromochlorobenzene............................................ 108-39-2
Bromoxynil...................................................... 1689-84-5
Butachlor....................................................... 2318-4669
Butylate........................................................ 2008-41-5
n-C10 (n-decane)................................................ 124-18-5
n-C12 (n-undecane).............................................. 112-40-2
n-C14 (n-tetradecane)........................................... 629-59-4
n-C16 (n-hexadecane)............................................ 544-76-3
n-C18 (n-octadecane)............................................ 593-45-3
n-C20 (n-eicosane).............................................. 112-95-8
n-C22 (n-docosane).............................................. 629-97-0
n-C24 (n-tetracosane)........................................... 646-31-1
n-C26 (n-hexacosane)............................................ 630-01-3
n-C28 (n-octacosane)............................................ 630-02-4
n-C30 (n-triacontane)........................................... 638-68-6
[[Page 9062]]
Captafol........................................................ 2425-06-1
Captan.......................................................... 133-06-2
Carbaryl........................................................ 63-25-2
Carbazole....................................................... 86-74-8
Carbofuran...................................................... 1563-66-2
Carboxin........................................................ 5234-68-4
Carbophenothion................................................. 786-19-6
Chlordane\3\ \5\................................................ 57-74-9
bis(2-Chloroethyl) ether \3\ \4\................................ 111-44-4 5.7 17.1
Chloroneb....................................................... 2675-77-6
4-Chloroaniline................................................. 106-47-8
Chlorobenzilate................................................. 510-15-6
Chlorfenvinphos................................................. 470-90-6
4-Chloro-2-methylaniline........................................ 95-69-2
3-(Chloromethyl)pyridine hydrochloride.......................... 6959-48-4
4-Chloro-2-nitroaniline......................................... 89-63-4
Chlorpropham.................................................... 101-21-3
Chlorothalonil.................................................. 1897-45-6
1-Chloronaphthalene............................................. 90-13-1
3-Chloronitribenzene............................................ 121-73-3
4-Chloro-1,2-phenylenediamine................................... 95-83-0
4-Chloro-1,3-phenylenediamine................................... 5131-60-2
2-Chlorobiphenyl................................................ 2051-60-7
Chlorpyrifos.................................................... 2921-88-2
Coumaphos....................................................... 56-72-4
m+p-Cresol...................................................... 65794-96-9
o-Cresol........................................................ 95-48-7
p-Cresidine..................................................... 120-71-8
Crotoxyphos..................................................... 7700-17-6
2-Cyclohexyl-4,6-dinitro-phenol................................. 131-89-5
Cyanazine....................................................... 21725-46-2
Cycloate........................................................ 1134-23-2
p-Cymene........................................................ 99-87-6
Dacthal (DCPA).................................................. 1861-32-1
4,4'-DDD \3\.................................................... 72-54-8 2.8 8.4
4,4'-DDE \3\.................................................... 72-55-9 5.6 16.8
4,4'-DDT \3\.................................................... 50-29-3 4.7 14.1
Demeton-O....................................................... 298-03-3
Demeton-S....................................................... 126-75-0
Diallate (cis or trans)......................................... 2303-16-4
2,4-Diaminotoluene.............................................. 95-80-7
Diazinon........................................................ 333-41-5
Dibenz(a,j)acridine............................................. 224-42-0
Dibenzofuran.................................................... 132-64-9
Dibenzo(a,e)pyrene.............................................. 192-65-4
Dibenzothiophene................................................ 132-65-0
1,2-Dibromo-3-chloropropane..................................... 96-12-8
3,5-Dibromo-4-hydroxybenzonitrile............................... 1689-84-5
2,6-Di-tert-butyl-p-benzoquinone................................ 719-22-2
Dichlone........................................................ 117-80-6
2,3-Dichloroaniline............................................. 608-27-5
2,3-Dichlorobiphenyl............................................ 16605-91-7
2,6-Dichloro-4-nitroaniline..................................... 99-30-9
2,3-Dichloronitrobenzene........................................ 3209-22-1
1,3-Dichloro-2-propanol......................................... 96-23-1
2,6-Dichlorophenol.............................................. 120-83-2
Dichlorvos...................................................... 62-73-7
Dicrotophos..................................................... 141-66-2
Dieldrin \3\.................................................... 60-57-1 2.5 7.5
1,2:3,4-Diepoxybutane........................................... 1464-53-5
Di(2-ethylhexyl) adipate........................................ 103-23-1
Diethylstilbestrol.............................................. 56-53-1
Diethyl sulfate................................................. 64-67-5
Dilantin (5,5-Diphenylhydantoin)................................ 57-41-0
Dimethoate...................................................... 60-51-5
3,3'-Dimethoxybenzidine......................................... 119-90-4
Dimethylaminoazobenzene......................................... 60-11-7
7,12-Dimethylbenz(a)anthracene.................................. 57-97-6
3,3'-Dimethylbenzidine.......................................... 119-93-7
N,N-Dimethylformamide........................................... 68-12-2
3,6-Dimethylphenathrene......................................... 1576-67-6
alpha, alpha-Dimethylphenethylamine............................. 122-09-8
[[Page 9063]]
Dimethyl sulfone................................................ 67-71-0
1,2-Dinitrobenzene.............................................. 528-29-0
1,3-Dinitrobenzene.............................................. 99-65-0
1,4-Dinitrobenzene.............................................. 100-25-4
Dinocap......................................................... 39300-45-3
Dinoseb......................................................... 88-85-7
Diphenylamine................................................... 122-39-4
Diphenyl ether.................................................. 101-84-8
1,2-Diphenylhydrazine........................................... 122-66-7
Diphenamid...................................................... 957-51-7
Diphenyldisulfide............................................... 882-33-7
Disulfoton...................................................... 298-04-4
Disulfoton sulfoxide............................................ 2497-07-6
Disulfoton sulfone.............................................. 2497-06-5
Endosulfan I \3\ \4\............................................ 959-98-8
Endosulfan II \3\ \4\........................................... 33213-65-9
Endosulfan sulfate \3\.......................................... 1031-07-8 5.6 16.8
Endrin \3\ \4\.................................................. 72-20-8
Endrin aldehyde \3\ \4\......................................... 7421-93-4
Endrin ketone \3\ \4\........................................... 53494-70-5
EPN............................................................. 2104-64-5
EPTC............................................................ 759-94-4
Ethion.......................................................... 563-12-2
Ethoprop........................................................ 13194-48-4
Ethyl carbamate................................................. 51-79-6
Ethyl methanesulfonate.......................................... 65-50-0
Ethylenethiourea................................................ 96-45-7
Etridiazole..................................................... 2593-15-9
Ethynylestradiol-3-methyl ether................................. 72-33-3
Famphur......................................................... 52-85-7
Fenamiphos...................................................... 22224-92-6
Fenarimol....................................................... 60168-88-9
Fensulfothion................................................... 115-90-2
Fenthion........................................................ 55-38-9
Fluchloralin.................................................... 33245-39-5
Fluridone....................................................... 59756-60-4
Heptachlor \3\.................................................. 76-44-8 1.9 5.7
Heptachlor epoxide \3\.......................................... 1024-57-3 2.2 6.6
2,2',3,3',4,4',6-Heptachlorobiphenyl............................ 52663-71-5
2,2',4,4',5',6-Hexachlorobiphenyl............................... 60145-22-4
Hexachlorocyclopentadiene \3\ \4\............................... 77-47-4
Hexachlorophene................................................. 70-30-4
Hexachloropropene............................................... 1888-71-7
Hexamethylphosphoramide......................................... 680-31-9
Hexanoic acid................................................... 142-62-1
Hexazinone...................................................... 51235-04-2
Hydroquinone.................................................... 123-31-9
Isodrin......................................................... 465-73-6
2-Isopropylnapthalene........................................... 2027-17-0
Isosafrole...................................................... 120-58-1
Kepone.......................................................... 143-50-0
Leptophos....................................................... 21609-90-5
Longifolene..................................................... 475-20-7
Malachite green................................................. 569-64-2
Malathion....................................................... 121-75-5
Maleic anhydride................................................ 108-31-6
Merphos......................................................... 150-50-5
Mestranol....................................................... 72-33-3
Methapyrilene................................................... 91-80-5
Methoxychlor.................................................... 72-43-5
2-Methylbenzothioazole.......................................... 120-75-2
3-Methylcholanthrene............................................ 56-49-5
4,4'-Methylenebis(2-chloroaniline).............................. 101-14-4
4,4'-Methylenebis(N,N-dimethylaniline).......................... 101-61-1
4,5-Methylenephenanthrene....................................... 203-64-5
1-Methylfluorene................................................ 1730-37-6
Methyl methanesulfonate......................................... 66-27-3
2-Methylnaphthalene............................................. 91-57-6
Methylparaoxon.................................................. 950-35-6
Methyl parathion................................................ 298-00-0
1-Methylphenanthrene............................................ 832-69-9
2-(Methylthio)benzothiazole..................................... 615-22-5
[[Page 9064]]
Metolachlor..................................................... 5218-45-2
Metribuzin...................................................... 21087-64-9
Mevinphos....................................................... 7786-34-7
Mexacarbate..................................................... 315-18-4
MGK 264......................................................... 113-48-4
Mirex........................................................... 2385-85-5
Molinate........................................................ 2212-67-1
Monocrotophos................................................... 6923-22-4
Naled........................................................... 300-76-5
Napropamide..................................................... 15299-99-7
1,4-Naphthoquinone.............................................. 130-15-4
1-Naphthylamine................................................. 134-32-7
2-Naphthylamine................................................. 91-59-8
1,5-Naphthalenediamine.......................................... 2243-62-1
Nicotine........................................................ 54-11-5
5-Nitroacenaphthene............................................. 602-87-9
2-Nitroaniline.................................................. 88-74-4
3-Nitroaniline.................................................. 99-09-2
4-Nitroaniline.................................................. 100-01-6
5-Nitro-o-anisidine............................................. 99-59-2
4-Nitrobiphenyl................................................. 92-93-3
Nitrofen........................................................ 1836-75-5
5-Nitro-o-toluidine............................................. 99-55-8
Nitroquinoline-1-oxide.......................................... 56-57-5
N-Nitrosodi-n-butylamine \4\.................................... 924-16-3
N-Nitrosodiethylamine \4\....................................... 55-18-5
N-Nitrosodimethylamine \3\ \4\.................................. 62-75-9
N-Nitrosodiphenylamine \3\ \4\.................................. 86-30-6
N-Nitrosomethylethylamine \4\................................... 10595-95-6
N-Nitrosomethylphenylamine \4\.................................. 614-00-6
N-Nitrosomorpholine \4\......................................... 59-89-2
N-Nitrosopiperidine \4\......................................... 100-75-5
N-Nitrosopyrrolidine \4\........................................ 930-55-2
trans-Nonachlor................................................. 39765-80-5
Norflurazon..................................................... 27314-13-2
2,2',3,3',4,5',6,6'-Octachlorobiphenyl.......................... 40186-71-8
Octamethyl pyrophosphoramide.................................... 152-16-9
4,4'-Oxydianiline............................................... 101-80-4
Parathion....................................................... 56-38-2
PCB-1016 \3\ \5\................................................ 12674-11-2
PCB-1221 \3\ \5\................................................ 11104-28-2 30 90
PCB-1232 \3\ \5\................................................ 11141-16-5
PCB-1242 \3\ \5\................................................ 53469-21-9
PCB-1248 \3\ \5\................................................ 12672-29-6
PCB-1254 \3\ \5\................................................ 11097-69-1 36 108
PCB-1260 \3\ \5\................................................ 11098-82-5
PCB-1268 \3\ \5\................................................ 11100-14-4
Pebulate........................................................ 1114-71-2
Pentachlorobenzene.............................................. 608-93-5
Pentachloronitrobenzene......................................... 82-68-8
2,2',3,4',6-Pentachlorobiphenyl................................. 68194-05-8
Pentachloroethane............................................... 76-01-7
Pentamethylbenzene.............................................. 700-12-9
Perylene........................................................ 198-55-0
Phenacetin...................................................... 62-44-2
cis-Permethrin.................................................. 61949-76-6
trans-Permethrin................................................ 61949-77-7
Phenobarbital................................................... 50-06-6
Phenothiazene................................................... 92-84-2
1,4-Phenylenediamine............................................ 624-18-0
1-Phenylnaphthalene............................................. 605-02-7
2-Phenylnaphthalene............................................. 612-94-2
Phorate......................................................... 298-02-2
Phosalone....................................................... 2310-18-0
Phosmet......................................................... 732-11-6
Phosphamidon.................................................... 13171-21-6
Phthalic anhydride.............................................. 85-44-9
alpha-Picoline (2-Methylpyridine)............................... 109-06-8
Piperonyl sulfoxide............................................. 120-62-7
Prometon........................................................ 1610-18-0
Prometryn....................................................... 7287-19-6
Pronamide....................................................... 23950-58-5
[[Page 9065]]
Propachlor...................................................... 1918-16-7
Propazine....................................................... 139-40-2
Propylthiouracil................................................ 51-52-5
Pyridine........................................................ 110-86-1
Resorcinol (1,3-Benzenediol).................................... 108-46-3
Safrole......................................................... 94-59-7
Simazine........................................................ 122-34-9
Simetryn........................................................ 1014-70-6
Squalene........................................................ 7683-64-9
Stirofos........................................................ 22248-79-9
Strychnine...................................................... 57-24-9
Styrene......................................................... 100-42-5
Sulfallate...................................................... 95-06-7
Tebuthiuron..................................................... 34014-18-1
Terbacil........................................................ 5902-51-2
Terbufos........................................................ 13071-79-9
Terbutryn....................................................... 886-50-0
alpha-Terpineol................................................. 98-55-5
1,2,4,5-Tetrachlorobenzene...................................... 95-94-3
2,2',4,4'-Tetrachlorobiphenyl................................... 2437-79-8
2,3,7,8-Tetrachlorodibenzo-p-dioxin............................. 1746-01-6
2,3,4,6-Tetrachlorophenol....................................... 58-90-2
Tetrachlorvinphos............................................... 22248-79-9
Tetraethyl dithiopyrophosphate.................................. 3689-24-5
Tetraethyl pyrophosphate........................................ 107-49-3
Thianaphthene (2,3-Benzothiophene).............................. 95-15-8
Thioacetamide................................................... 62-55-5
Thionazin....................................................... 297-97-2
Thiophenol (Benzenethiol)....................................... 108-98-5
Thioxanthone.................................................... 492-22-8
Toluene-1,3-diisocyanate........................................ 26471-62-5
Toluene-2,4-diisocyanate........................................ 584-84-9
o-Toluidine..................................................... 95-53-4
Toxaphene \3\ \5\............................................... 8001-35-2
Triadimefon..................................................... 43121-43-3
1,2,3-Trichlorobenzene.......................................... 87-61-6
2,4,5-Trichlorobiphenyl......................................... 15862-07-4
2,3,6-Trichlorophenol........................................... 933-75-5
2,4,5-Trichlorophenol........................................... 95-95-4
Tricyclazole.................................................... 41814-78-2
Trifluralin..................................................... 1582-09-8
1,2,3-Trimethoxybenzene......................................... 634-36-6
2,4,5-Trimethylaniline.......................................... 137-17-7
Trimethyl phosphate............................................. 512-56-1
Triphenylene.................................................... 217-59-4
Tripropyleneglycolmethyl ether.................................. 20324-33-8
1,3,5-Trinitrobenzene........................................... 99-35-4
Tris(2,3-dibromopropyl) phosphate............................... 126-72-7
Tri-p-tolyl phosphate........................................... 78-32-0
O,O,O-Triethyl phosphorothioate................................. 126-68-1
Trithiane....................................................... 291-29-4
Vernolate....................................................... 1929-77-7
----------------------------------------------------------------------------------------------------------------
\1\ Compounds that have been demonstrated amenable to extraction and gas chromatography.
\2\ Determine each analyte in the fraction that gives the most accurate result.
\3\ Priority Pollutant (40 CFR part 423, appendix A).
\4\ See Section 1.2.
\5\ These compounds are mixtures of various isomers.
\6\ MDL values from the 1984 promulgated version of Method 624.
\7\ ML = Minimum Level--see Glossary for definition and derivation.
Table 4--Chromatographic Conditions and Characteristic m/z's for Base/Neutral Extractables
--------------------------------------------------------------------------------------------------------------------------------------------------------
Characteristic m/z's
Retention -----------------------------------------------------------------------------
Analyte time (sec) Electron impact ionization Chemical ionization
\1\ -----------------------------------------------------------------------------
Primary Second Second Methane Methane Methane
--------------------------------------------------------------------------------------------------------------------------------------------------------
N-Nitrosodimethylamine....................................... 385 42 74 44
bis(2-Chloroethyl) ether..................................... 704 93 63 95 63 107 109
bis(2-Chloroisopropyl) ether................................. 799 45 77 79 77 135 137
Hexachloroethane............................................. 823 117 201 199 199 201 203
[[Page 9066]]
N-Nitrosodi-n-propylamine.................................... 830 130 42 101
Nitrobenzene................................................. 849 77 123 65 124 152 164
Isophorone................................................... 889 82 95 138 139 167 178
bis(2-Chloroethoxy) methane.................................. 939 93 95 123 65 107 137
1,2,4-Trichlorobenzene....................................... 958 180 182 145 181 183 209
Naphthalene.................................................. 967 128 129 127 129 157 169
Hexachlorobutadiene.......................................... 1006 225 223 227 223 225 227
Hexachlorocyclopentadiene.................................... 1142 237 235 272 235 237 239
2-Chloronaphthalene.......................................... 1200 162 164 127 163 191 203
Acenaphthylene............................................... 1247 152 151 153 152 153 181
Dimethyl phthalate........................................... 1273 163 194 164 151 163 164
2,6-Dinitrotoluene........................................... 1300 165 89 121 183 211 223
Acenaphthene................................................. 1304 154 153 152 154 155 183
2,4-Dinitrotoluene........................................... 1364 165 63 182 183 211 223
Fluorene..................................................... 1401 166 165 167 166 167 195
4-Chlorophenyl phenyl ether.................................. 1409 204 206 141
Diethyl phthalate............................................ 1414 149 177 150 177 223 251
N-Nitrosodiphenylamine....................................... 1464 169 168 167 169 170 198
4-Bromophenyl phenyl ether................................... 1498 248 250 141 249 251 277
alpha-BHC.................................................... 1514 183 181 109
Hexachlorobenzene............................................ 1522 284 142 249 284 286 288
beta-BHC..................................................... 1544 183 181 109
gamma-BHC.................................................... 1557 181 183 109
Phenanthrene................................................. 1583 178 179 176 178 179 207
Anthracene................................................... 1592 178 179 176 178 179 207
delta-BHC.................................................... 1599 183 109 181
Heptachlor................................................... 1683 100 272 274
Di-n-butyl phthalate......................................... 1723 149 150 104 149 205 279
Aldrin....................................................... 1753 66 263 220
Fluoranthene................................................. 1817 202 101 100 203 231 243
Heptachlor epoxide........................................... 1820 353 355 351
gamma-Chlordane.............................................. 1834 373 375 377
Pyrene....................................................... 1852 202 101 100 203 231 243
Benzidine \2\................................................ 1853 184 92 185 185 213 225
alpha-Chlordane.............................................. 1854 373 375 377
Endosulfan I................................................. 1855 237 339 341
4,4'-DDE..................................................... 1892 246 248 176
Dieldrin..................................................... 1907 79 263 279
Endrin....................................................... 1935 81 263 82
Endosulfan II................................................ 2014 237 339 341
4,4'-DDD..................................................... 2019 235 237 165
Endrin aldehyde.............................................. 2031 67 345 250
Butyl benzyl phthalate....................................... 2060 149 91 206 149 299 327
Endosulfan sulfate........................................... 2068 272 387 422
4,4'-DDT..................................................... 2073 235 237 165
Chrysene..................................................... 2083 228 226 229 228 229 257
3,3'-Dichlorobenzidine....................................... 2086 252 254 126
Benzo(a)anthracene........................................... 2090 228 229 226 228 229 257
bis(2-Ethylhexyl) phthalate.................................. 2124 149 167 279 149
Di-n-octyl phthalate......................................... 2240 149 43 57
Benzo(b)fluoranthene......................................... 2286 252 253 125 252 253 281
Benzo(k)fluoranthene......................................... 2293 252 253 125 252 253 281
Benzo(a)pyrene............................................... 2350 252 253 125 252 253 281
Indeno(1,2,3-cd) pyrene...................................... 2650 276 138 277 276 277 305
Dibenz(a,h)anthracene........................................ 2660 278 139 279 278 279 307
Benzo(ghi)perylene........................................... 2750 276 138 277 276 277 305
Toxaphene.................................................... ........... 159 231 233
PCB 1016..................................................... ........... 224 260 294
PCB 1221..................................................... ........... 190 224 260
PCB 1232..................................................... ........... 190 224 260
PCB 1242..................................................... ........... 224 260 294
PCB 1248..................................................... ........... 294 330 262
PCB 1254..................................................... ........... 294 330 362
PCB 1260..................................................... ........... 330 362 394
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Column: 30 m x 0.25 mm ID; 94% methyl, 5% phenyl, 1% vinyl bonded phase fused silica capillary.
Conditions: 5 min at 30 [deg]C; 30-280 at 8 [deg]C per min; isothermal at 280 [deg]C until benzo(ghi)perylene elutes.
Gas velocity: 30 cm/sec at 30 [deg]C (at constant pressure).
\2\ See Section 1.2; included for tailing factor testing.
[[Page 9067]]
Table 5--Chromatographic Conditions and Characteristic m/z's for Acid Extractables
--------------------------------------------------------------------------------------------------------------------------------------------------------
Characteristic m/z's
Retention -----------------------------------------------------------------------------
Analyte time (sec) Electron impact ionization Chemical ionization
\1\ -----------------------------------------------------------------------------
Primary Second Second Methane Methane Methane
--------------------------------------------------------------------------------------------------------------------------------------------------------
2-Chlorophenol............................................... 705 128 64 130 129 131 157
Phenol....................................................... 700 94 65 66 95 123 135
2-Nitrophenol................................................ 900 139 65 109 140 168 122
2,4-Dimethylphenol........................................... 924 122 107 121 123 151 163
2,4-Dichlorophenol........................................... 947 162 164 98 163 165 167
4-Chloro-3-methylphenol...................................... 1091 142 107 144 143 171 183
2,4,6-Trichlorophenol........................................ 1165 196 198 200 197 199 201
2,4-Dinitrophenol............................................ 1325 184 63 154 185 213 225
4-Nitrophenol................................................ 1354 65 139 109 140 168 122
2-Methyl-4,6-dinitrophenol................................... 1435 198 182 77 199 227 239
Pentachlorophenol............................................ 1561 266 264 268 267 265 269
--------------------------------------------------------------------------------------------------------------------------------------------------------
Column: 30 m x 0.25 mm ID; 94% methyl, 5% phenyl, 1% vinyl bonded phase fused silica capillary.
Conditions: 5 min at 30 [deg]C; 30-250 at 8 [deg]C per min; isothermal at 280 [deg]C until pentachlorophenol elutes.
Gas velocity: 30 cm/sec at 30 [deg]C (at constant pressure).
Table 6--QC Acceptance Criteria--Method 625 \1\
----------------------------------------------------------------------------------------------------------------
Range for X Range for
Analyte Range for Q Limit for s (%) \3\ P, Ps (%) Limit for
(%) \2\ (%) \3\ \3\ RPD (%)
----------------------------------------------------------------------------------------------------------------
Acenaphthene................................... 70-130 29 60-132 47-145 48
Acenaphthylene................................. 60-130 45 54-126 33-145 74
Aldrin......................................... 7-152 39 7-152 D-166 81
Anthracene..................................... 58-130 40 43-120 27-133 66
Benzo(a)anthracene............................. 42-133 32 42-133 33-143 53
Benzo(b)fluoranthene........................... 42-140 43 42-140 24-159 71
Benzo(k)fluoranthene........................... 25-146 38 25-146 11-162 63
Benzo(a)pyrene................................. 32-148 43 32-148 17-163 72
Benzo(ghi)perylene............................. 13-195 61 D-195 D-219 97
Benzyl butyl phthalate......................... 43-140 36 D-140 D-152 60
beta-BHC....................................... 42-131 37 42-131 24-149 61
delta-BHC...................................... D-130 77 D-120 D-120 129
bis(2-Chloroethyl)ether........................ 52-130 65 43-126 12-158 108
bis(2-Chloroethoxy)methane..................... 52-164 32 49-165 33-184 54
bis(2-Chloroisopropyl) ether................... 63-139 46 63-139 36-166 76
bis(2-Ethylhexyl) phthalate.................... 43-137 50 29-137 8-158 82
4-Bromophenyl phenyl ether..................... 70-130 26 65-120 53-127 43
2-Chloronaphthalene............................ 70-130 15 65-120 60-120 24
4-Chlorophenyl phenyl ether.................... 57-145 36 38-145 25-158 61
Chrysene....................................... 44-140 53 44-140 17-168 87
4,4'-DDD....................................... D-135 56 D-135 D-145 93
4,4'-DDE....................................... 19-130 46 19-120 4-136 77
4,4'-DDT....................................... D-171 81 D-171 D-203 135
Dibenz(a,h)anthracene.......................... 13-200 75 D-200 D-227 126
Di-n-butyl phthalate........................... 52-130 28 8-120 1-120 47
3,3'-Dichlorobenzidine......................... 18-213 65 8-213 D-262 108
Dieldrin....................................... 70-130 38 44-119 29-136 62
Diethyl phthalate.............................. 47-130 60 D-120 D-120 100
Dimethyl phthalate............................. 50-130 110 D-120 D-120 183
2,4-Dinitrotoluene............................. 53-130 25 48-127 39-139 42
2,6-Dinitrotoluene............................. 68-137 29 68-137 50-158 48
Di-n-octyl phthalate........................... 21-132 42 19-132 4-146 69
Endosulfan sulfate............................. D-130 42 D-120 D-120 70
Endrin aldehyde................................ D-189 45 D-189 D-209 75
Fluoranthene................................... 47-130 40 43-121 26-137 66
Fluorene....................................... 70-130 23 70-120 59-121 38
Heptachlor..................................... D-172 44 D-172 D-192 74
Heptachlor epoxide............................. 70-130 61 71-120 26-155 101
Hexachlorobenzene.............................. 38-142 33 8-142 D-152 55
Hexachlorobutadiene............................ 68-130 38 38-120 24-120 62
Hexachloroethane............................... 55-130 32 55-120 40-120 52
Indeno(1,2,3-cd)pyrene......................... 13-151 60 D-151 D-171 99
Isophorone..................................... 52-180 56 47-180 21-196 93
Naphthalene.................................... 70-130 39 36-120 21-133 65
Nitrobenzene................................... 54-158 37 54-158 35-180 62
N-Nitrosodi-n-propylamine...................... 59-170 52 14-198 D-230 87
PCB-1260....................................... 19-130 77 19-130 D-164 128
[[Page 9068]]
Phenanthrene................................... 67-130 24 65-120 54-120 39
Pyrene......................................... 70-130 30 70-120 52-120 49
1,2,4-Trichlorobenzene......................... 61-130 30 57-130 44-142 50
4-Chloro-3-methylphenol........................ 68-130 44 41-128 22-147 73
2-Chlorophenol................................. 55-130 37 36-120 23-134 61
2,4-Dichlorophenol............................. 64-130 30 53-122 39-135 50
2,4-Dimethylphenol............................. 58-130 35 42-120 32-120 58
2,4-Dinitrophenol.............................. 39-173 79 D-173 D-191 132
2-Methyl-4,6-dinitrophenol..................... 56-130 122 53-130 D-181 203
2-Nitrophenol.................................. 61-163 33 45-167 29-182 55
4-Nitrophenol.................................. 35-130 79 13-129 D-132 131
Pentachlorophenol.............................. 42-152 52 38-152 14-176 86
Phenol......................................... 48-130 39 17-120 5-120 64
2,4,6-Trichlorophenol.......................... 69-130 35 52-129 37-144 58
----------------------------------------------------------------------------------------------------------------
\1\ Acceptance criteria are based upon method performance data in Table 7 and from EPA Method 1625. Where
necessary, limits for recovery have been broadened to assure applicability to concentrations below those used
to develop Table 7.
\2\ Test concentration = 100 [mu]g/mL.
\3\ Test concentration = 100 [mu]g/L.
Q = Calibration verification (Sections 7.3.1 and 13.4).
s = Standard deviation for four recovery measurements in the DOC test (Section 8.2.4).
X = Average recovery for four recovery measurements in the DOC test (Section 8.2.4).
P, Ps = MS/MSD recovery (Section 8.3.2, Section 8.4.2).
RPD = MS/MSD relative percent difference (RPD; Section 8.3.3).
D = Detected; result must be greater than zero.
Table 7--Precision and Recovery as Functions of Concentration--Method 625 \ 1\
----------------------------------------------------------------------------------------------------------------
Single analyst
Analyte Recovery, X' ([mu]g/L) precision, sr' ([mu]g/ Overall precision, S'
L) ([mu]g/L)
----------------------------------------------------------------------------------------------------------------
Acenaphthene....................... 0.96C+0.19.............. 0.15 x -0.12............ 0.21 x -0.67
Acenaphthylene..................... 0.89C+0.74.............. 0.24 x -1.06............ 0.26 x -0.54
Aldrin............................. 0.78C+1.66.............. 0.27 x -1.28............ 0.43 x +1.13
Anthracene......................... 0.80C+0.68.............. 0.21 x -0.32............ 0.27 x -0.64
Benzo(a)anthracene................. 0.88C-0.60.............. 0.15 x +0.93............ 0.26 x -0.28
Benzo(b)fluoranthene............... 0.93C-1.80.............. 0.22 x +0.43............ 0.29 x +0.96
Benzo(k)fluoranthene............... 0.87C-1.56.............. 0.19 x +1.03............ 0.35 x +0.40
Benzo(a)pyrene..................... 0.90C-0.13.............. 0.22 x +0.48............ 0.32 x +1.35
Benzo(ghi)perylene................. 0.98C-0.86.............. 0.29 x +2.40............ 0.51 x -0.44
Benzyl butyl phthalate............. 0.66C-1.68.............. 0.18 x +0.94............ 0.53 x +0.92
beta-BHC........................... 0.87C-0.94.............. 0.20 x -0.58............ 0.30 x -1.94
delta-BHC.......................... 0.29C-1.09.............. 0.34 x +0.86............ 0.93 x -0.17
bis(2-Chloroethyl)ether............ 0.86C-1.54.............. 0.35 x -0.99............ 0.35 x +0.10
bis(2-Chloroethoxy)methane......... 1.12C-5.04.............. 0.16 x +1.34............ 0.26 x +2.01
bis(2-Chloroisopropyl)ether........ 1.03C-2.31.............. 0.24 x +0.28............ 0.25 x +1.04
bis(2-Ethylhexyl)phthalate......... 0.84C-1.18.............. 0.26 x +0.73............ 0.36 x +0.67
4-Bromophenyl phenyl ether......... 0.91C-1.34.............. 0.13 x +0.66............ 0.16 x +0.66
2-Chloronaphthalene................ 0.89C+0.01.............. 0.07 x +0.52............ 0.13 x +0.34
4-Chlorophenyl phenyl ether........ 0.91C+0.53.............. 0.20 x -0.94............ 0.30 x -0.46
Chrysene........................... 0.93C-1.00.............. 0.28 x +0.13............ 0.33 x -0.09
4,4'-DDD........................... 0.56C-0.40.............. 0.29 x -0.32............ 0.66 x -0.96
4,4'-DDE........................... 0.70C-0.54.............. 0.26 x -1.17............ 0.39 x -1.04
4,4'-DDT........................... 0.79C-3.28.............. 0.42 x +0.19............ 0.65 x -0.58
Dibenz(a,h)anthracene.............. 0.88C+4.72.............. 0.30 x +8.51............ 0.59 x +0.25
Di-n-butyl phthalate............... 0.59C+0.71.............. 0.13 x +1.16............ 0.39 x +0.60
3,3'-Dichlorobenzidine............. 1.23C-12.65............. 0.28 x +7.33............ 0.47 x +3.45
Dieldrin........................... 0.82C-0.16.............. 0.20 x -0.16............ 0.26 x -0.07
Diethyl phthalate.................. 0.43C+1.00.............. 0.28 x +1.44............ 0.52 x +0.22
Dimethyl phthalate................. 0.20C+1.03.............. 0.54 x +0.19............ 1.05 x -0.92
2,4-Dinitrotoluene................. 0.92C-4.81.............. 0.12 x +1.06............ 0.21 x +1.50
2,6-Dinitrotoluene................. 1.06C-3.60.............. 0.14 x +1.26............ 0.19 x +0.35
Di-n-octyl phthalate............... 0.76C-0.79.............. 0.21 x +1.19............ 0.37 x +1.19
Endosulfan sulfate................. 0.39C+0.41.............. 0.12 x +2.47............ 0.63 x -1.03
Endrin aldehyde.................... 0.76C-3.86.............. 0.18 x +3.91............ 0.73 x -0.62
Fluoranthene....................... 0.81C+1.10.............. 0.22 x +0.73............ 0.28 x -0.60
Fluorene........................... 0.90C-0.00.............. 0.12 x +0.26............ 0.13 x +0.61
Heptachlor......................... 0.87C-2.97.............. 0.24 x -0.56............ 0.50 x -0.23
Heptachlor epoxide................. 0.92C-1.87.............. 0.33 x -0.46............ 0.28 x +0.64
Hexachlorobenzene.................. 0.74C+0.66.............. 0.18 x -0.10............ 0.43 x -0.52
[[Page 9069]]
Hexachlorobutadiene................ 0.71C-1.01.............. 0.19 x +0.92............ 0.26 x +0.49
Hexachloroethane................... 0.73C-0.83.............. 0.17 x +0.67............ 0.17 x +0.80
Indeno(1,2,3-cd)pyrene............. 0.78C-3.10.............. 0.29 x +1.46............ 0.50 x +0.44
Isophorone......................... 1.12C+1.41.............. 0.27 x +0.77............ 0.33 x +0.26
Naphthalene........................ 0.76C+1.58.............. 0.21 x -0.41............ 0.30 x -0.68
Nitrobenzene....................... 1.09C-3.05.............. 0.19 x +0.92............ 0.27 x +0.21
N-Nitrosodi-n-propylamine.......... 1.12C-6.22.............. 0.27 x +0.68............ 0.44 x +0.47
PCB-1260........................... 0.81C-10.86............. 0.35 x +3.61............ 0.43 x +1.82
Phenanthrene....................... 0.87C-0.06.............. 0.12 x +0.57............ 0.15 x +0.25
Pyrene............................. 0.84C-0.16.............. 0.16 x +0.06............ 0.15 x +0.31
1,2,4-Trichlorobenzene............. 0.94C-0.79.............. 0.15 x +0.85............ 0.21 x +0.39
4-Chloro-3-methylphenol............ 0.84C+0.35.............. 0.23 x +0.75............ 0.29 x +1.31
2-Chlorophenol..................... 0.78C+0.29.............. 0.18 x +1.46............ 0.28 x 0.97
2,4-Dichlorophenol................. 0.87C+0.13.............. 0.15 x +1.25............ 0.21 x +1.28
2,4-Dimethylphenol................. 0.71C+4.41.............. 0.16 x +1.21............ 0.22 x +1.31
2,4-Dinitrophenol.................. 0.81C-18.04............. 0.38 x +2.36............ 0.42 x +26.29
2-Methyl-4,6-Dinitrophenol......... 1.04C-28.04............. 0.05 x +42.29........... 0.26 x +23.10
2-Nitrophenol...................... 1.07C-1.15.............. 0.16 x +1.94............ 0.27 x +2.60
4-Nitrophenol...................... 0.61C-1.22.............. 0.38 x +2.57............ 0.44 x +3.24
Pentachlorophenol.................. 0.93C+1.99.............. 0.24 x +3.03............ 0.30 x +4.33
Phenol............................. 0.43C+1.26.............. 0.26 x +0.73............ 0.35 x +0.58
2,4,6-Trichlorophenol.............. 0.91C-0.18.............. 0.16 x +2.22............ 0.22 x +1.81
----------------------------------------------------------------------------------------------------------------
\1\ Regressions based on data from Reference 2
X' = Expected recovery for one or more measurements of a sample containing a concentration of C, in [mu]g/L.
sr' = Expected single analyst standard deviation of measurements at an average concentration found of x, in
[mu]g/L.
S' = Expected interlaboratory standard deviation of measurements at an average concentration found of x, in
[mu]g/L.
C = True value for the concentration, in [mu]g/L.
x = Average recovery found for measurements of samples containing a concentration of C, in [mu]g/L.
Table 8--Suggested Internal and Surrogate Standards
------------------------------------------------------------------------
Range for surrogate recovery (%)
\1\
Base/neutral fraction ---------------------------------
Calibration Recovery from
verification samples
------------------------------------------------------------------------
Acenaphthalene-d8..................... 66-152 33-168
Acenaphthene-d10...................... 71-141 30-180
Aniline-d5.
Anthracene-d10........................ 58-171 23-142
Benzo(a)anthracene-d12................ 28-357 22-329
Benzo(a)pyrene-d12.................... 32-194 32-194
4-Chloroaniline-d4.................... 1-145 1-145
bis(2-Chloroethyl) ether-d8........... 52-194 25-222
Chrysene-d12.......................... 23-290 23-290
Decafluorobiphenyl.
4,4'-Dibromobiphenyl.
4,4'-Dibromooctafluorobiphenyl.
1,4-Dichlorobenzene-d4................ 65-153 11-245
2,2'-Difluorobiphenyl.
Dimethyl phthalate-d6................. 47-211 1-500
Fluoranthene-d10...................... 47-215 30-187
Fluorene-d10.......................... 61-164 38-172
4-Fluoroaniline.
1-Fluoronaphthalene.
2-Fluoronaphthalene.
2-Methylnaphthalene-d10............... 50-150 50-150
Naphthalene-d8........................ 71-141 22-192
Nitrobenzene-d5....................... 46-219 15-314
2,3,4,5,6-Pentafluorobiphenyl.
Perylene-d12.
Phenanthrene-d10...................... 67-149 34-168
Pyrene-d10............................ 48-210 28-196
Pyridine-d5.
------------------------------------------------------------------------
Acid fraction
------------------------------------------------------------------------
2-Chlorophenol-d4..................... 55-180 33-180
2,4-Dichlorophenol-d3................. 64-157 34-182
4,6-Dinitro-2-methylphenol-d2......... 56-177 22-307
[[Page 9070]]
2-Fluorophenol.
4-Methylphenol-d8..................... 25-111 25-111
2-Nitrophenol-d4...................... 61-163 37-163
4-Nitrophenol-d4...................... 35-287 6-500
Pentafluorophenol.
2-Perfluoromethylphenol.
Phenol-d5............................. 48-208 8-424
------------------------------------------------------------------------
\1\ Recovery from samples is the wider of the criteria in the CLP SOW
for organics or in Method 1625.
Table 9A--DFTPP Key m/z's and Abundance Criteria for Quadrupole
Instruments \1\
------------------------------------------------------------------------
m/z Abundance criteria
------------------------------------------------------------------------
51 30-60 percent of m/z 198.
68 Less than 2 percent of m/z 69.
70 Less than 2 percent of m/z 69.
127 40-60 percent of base peak m/z 198.
197 Less than 1 percent of m/z 198.
198 Base peak, 100 percent relative abundance.
199 5-9 percent of m/z 198.
275 10-30 percent of m/z 198.
365 Greater than 1 percent of m/z 198.
441 Present but less than m/z 443.
442 40-100 percent of m/z 198.
443 17-23 percent of m/z 442.
------------------------------------------------------------------------
\1\ Criteria in these tables are for quadrupole and time-of-flight
instruments. Alternative tuning criteria may be used for other
instruments, provided method performance is not adversely affected.
Table 9B--DFTPP Key m/z's and Abundance Criteria for Time-of-flight
Instruments \1\
------------------------------------------------------------------------
m/z Abundance criteria
------------------------------------------------------------------------
51 10-85 percent of the base peak.
68 Less than 2 percent of m/z 69.
70 Less than 2 percent of m/z 69.
127 10-80 percent of the base peak.
197 Less than 2 percent of Mass 198.
198 Base peak, or greater than 50% of m/z 442.
199 5-9 percent of m/z 198.
275 10-60 percent of the base peak.
365 Greater than 0.5 percent of m/z 198.
441 Less than 150 percent of m/z 443.
442 Base peak or greater than 30 percent of m/z 198.
443 15-24 percent of m/z 442.
------------------------------------------------------------------------
\1\ Criteria in these tables are for quadrupole and time-of-flight
instruments. Alternative tuning criteria may be used for other
instruments, provided method performance is not adversely affected.
21. Figures
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[GRAPHIC] [TIFF OMITTED] TP19FE15.019
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[GRAPHIC] [TIFF OMITTED] TP19FE15.020
BILLING CODE 6560-50-C
22. Glossary
These definitions and purposes are specific to this method but have
been conformed to common usage to the extent possible.
22.1 Units of weight and measure and their abbreviations
22.1.1 Symbols
[ordm]C degrees Celsius
[micro]g microgram
[micro]L microliter
< less than
> greater than
<= less than or equal to
% percent
22.1.2 Abbreviations (in alphabetical order)
cm centimeter
g gram
h hour
ID inside diameter
in. inch
L liter
M Molecular ion
m mass or meter
mg milligram
min minute
mL milliliter
mm millimeter
ms millisecond
m/z mass-to-charge ratio
N normal; gram molecular weight of solute divided by hydrogen
equivalent of solute, per liter of solution
ng nanogram
pg picogram
ppb part-per-billion
ppm part-per-million
ppt part-per-trillion
psig pounds-per-square inch gauge
22.2 Definitions and acronyms (in alphabetical order)
Analyte--A compound or mixture of compounds (e.g., PCBs) tested for
by this method. The analytes are listed in Tables 1-3.
Batch--See Extraction
Blank--An aliquot of reagent water that is treated exactly as a
sample including exposure to all glassware, equipment, solvents,
reagents, internal standards, and surrogates that are used with
samples. The blank is used to determine if analytes or interferences
are present in the laboratory environment, the reagents, or the
apparatus.
Calibration--The process of determining the relationship between
the output or response of a measuring instrument and the value of an
input standard. Historically, EPA has referred to a multi-point
calibration as the ``initial calibration,'' to differentiate it from a
single-point calibration verification.
Calibration standard--A solution prepared from stock solutions and/
or a secondary standards and containing the analytes of interest,
surrogates, and internal standards. The calibration standard is used to
calibrate the response of the GC/MS instrument against analyte
concentration.
Calibration verification standard--The mid-point calibration
standard used to verify calibration. See Sections 7.3 and 13.4.
Descriptor--In SIM, the beginning and ending retention times for
the RT window, the m/z's sampled in the RT window, and the dwell time
at each m/z.
Extracted ion current profile (EICP)--The line described by the
signal at a given m/z.
Extraction Batch--A set of up to 20 field samples (not including QC
samples) started through the extraction process on a given 12-hour
shift (Section 3.1). Each extraction batch must be accompanied by a
blank (Section 8.5), a laboratory control
[[Page 9073]]
sample (LCS, Section 8.4), and a matrix spike and duplicate (MS/MSD;
Section 8.3), resulting in a minimum of five analyses (1 sample, 1
blank, 1 LCS, 1 MS, and 1 MSD) and a maximum of 24 analyses (20 field
samples, 1 blank, 1 LCS, 1 MS, and 1 MSD) for the batch. If greater
than 20 samples are to be extracted in a 12-hour shift, the samples
must be separated into extraction batches of 20 or fewer samples.
Field Duplicates--Two samples collected at the same time and place
under identical conditions, and treated identically throughout field
and laboratory procedures. Results of analyses the field duplicates
provide an estimate of the precision associated with sample collection,
preservation, and storage, as well as with laboratory procedures.
Field blank--An aliquot of reagent water or other reference matrix
that is placed in a sample container in the field, and treated as a
sample in all respects, including exposure to sampling site conditions,
storage, preservation, and all analytical procedures. The purpose of
the field blank is to determine if the field or sample transporting
procedures and environments have contaminated the sample.
GC--Gas chromatograph or gas chromatography
Internal standard--A compound added to an extract or standard
solution in a known amount and used as a reference for quantitation of
the analytes of interest and surrogates. In this method the internal
standards are stable isotopically labeled analogs of selected method
analytes (Table 8). Also see Internal standard quantitation.
Internal standard quantitation--A means of determining the
concentration of an analyte of interest (Tables 1-3) by reference to a
compound not expected to be found in a sample.
DOC--Initial demonstration of capability (Section 8.2); four
aliquots of reagent water spiked with the analytes of interest and
analyzed to establish the ability of the laboratory to generate
acceptable precision and recovery. A DOC is performed prior to the
first time this method is used and any time the method or
instrumentation is modified.
Laboratory Control Sample (LCS; laboratory fortified blank; Section
8.4)--An aliquot of reagent water spiked with known quantities of the
analytes of interest and surrogates. The LCS is analyzed exactly like a
sample. Its purpose is to assure that the results produced by the
laboratory remain within the limits specified in this method for
precision and recovery.
Laboratory fortified sample matrix--See Matrix spike
Laboratory reagent blank--A blank run on laboratory reagents; e.g.,
methylene chloride (Section 11.1.5).
Matrix spike (MS) and matrix spike duplicate (MSD) (laboratory
fortified sample matrix and duplicate)--Two aliquots of an
environmental sample to which known quantities of the analytes of
interest and surrogates are added in the laboratory. The MS/MSD are
prepared and analyzed exactly like a field sample. Their purpose is to
quantify any additional bias and imprecision caused by the sample
matrix. The background concentrations of the analytes in the sample
matrix must be determined in a separate aliquot and the measured values
in the MS/MSD corrected for background concentrations.
May--This action, activity, or procedural step is neither required
nor prohibited.
May not--This action, activity, or procedural step is prohibited.
Method blank--See blank.
Method detection limit (MDL)--A detection limit determined by the
procedure at 40 CFR 136, Appendix B. The MDLs determined by EPA in the
original version of the method are listed in Tables 1, 2 and 3. As
noted in Sec. 1.5, use the MDLs in Tables 1, 2, and 3 in conjunction
with current MDL data from the laboratory actually analyzing samples to
assess the sensitivity of this procedure relative to project objectives
and regulatory requirements (where applicable).
Minimum level (ML)--The term ``minimum level'' refers to either the
sample concentration equivalent to the lowest calibration point in a
method or a multiple of the method detection limit (MDL), whichever is
higher. Minimum levels may be obtained in several ways: They may be
published in a method; they may be based on the lowest acceptable
calibration point used by a laboratory; or they may be calculated by
multiplying the MDL in a method, or the MDL determined by a laboratory,
by a factor of 3. For the purposes of NPDES compliance monitoring, EPA
considers the following terms to be synonymous: ``quantitation limit,''
``reporting limit,'' and ``minimum level.''
MS--Mass spectrometer or mass spectrometry, or matrix spike (a QC
sample type).
MSD--Matrix spike duplicate (a QC sample type).
Must--This action, activity, or procedural step is required.
m/z--The ratio of the mass of an ion (m) detected in the mass
spectrometer to the charge (z) of that ion.
Preparation blank--See blank.
Quality control check sample (QCS)--See Laboratory Control Sample.
Reagent water--Water demonstrated to be free from the analytes of
interest and potentially interfering substances at the MDLs for the
analytes in this method.
Regulatory compliance limit (or regulatory concentration limit)--A
limit on the concentration or amount of a pollutant or contaminant
specified in a nationwide standard, in a permit, or otherwise
established by a regulatory/control authority.
Relative retention time (RRT)--The ratio of the retention time of
an analyte to the retention time of its associated internal standard.
RRT compensates for small changes in the GC temperature program that
can affect the absolute retention times of the analyte and internal
standard. RRT is a unitless quantity.
Relative standard deviation (RSD)--The standard deviation times 100
divided by the mean. Also termed ``coefficient of variation.''
RF--Response factor. See Section 7.2.2.
RSD--See relative standard deviation.
Safety Data Sheet (SDS)--Written information on a chemical's
toxicity, health hazards, physical properties, fire, and reactivity,
including storage, spill, and handling precautions that meet the
requirements of OSHA, 29 CFR 1910.1200(g) and appendix D to Sec.
1910.1200. United Nations Globally Harmonized System of Classification
and Labelling of Chemicals (GHS), third revised edition, United
Nations, 2009.
Selected Ion Monitoring (SIM)--An MS technique in which a few m/z's
are monitored. When used with gas chromatography, the m/z's monitored
are usually changed periodically throughout the chromatographic run, to
correlate with the characteristic m/z's of the analytes, surrogates,
and internal standards as they elute from the chromatographic column.
The technique is often used to increase sensitivity and minimize
interferences.
Signal-to-noise ratio (S/N)--The height of the signal as measured
from the mean (average) of the noise to the peak maximum divided by the
width of the noise.
Should--This action, activity, or procedural step is suggested but
not required.
SPE--Solid-phase extraction; an extraction technique in which an
analyte is extracted from an aqueous solution by passage over or
through a material capable of reversibly adsorbing the analyte. Also
termed liquid-solid extraction.
[[Page 9074]]
Stock solution--A solution containing an analyte that is prepared
using a reference material traceable to EPA, the National Institute of
Science and Technology (NIST), or a source that will attest to the
purity, authenticity, and concentration of the standard.
Surrogate--A compound unlikely to be found in a sample, and which
is spiked into sample in a known amount before extraction or other
processing, and is quantitated with the same procedures used to
quantify other sample components. The purpose of the surrogate is to
monitor method performance with each sample.
* * * * *
0
9. Revise Appendix B to part 136 to read as follows:
Appendix B to Part 136--Definition and Procedure for the Determination
of the Method Detection Limit--Revision 2
Definition
The method detection limit (MDL) is defined as the minimum
measured concentration of a substance that can be reported with 99%
confidence that the measured concentration is distinguishable from
method blank results.
Scope and Application
The MDL procedure is designed to be a straightforward technique
for estimation of the detection limit for a broad variety of
physical and chemical methods. The procedure requires a complete,
specific, and well defined analytical method. It is essential that
all sample processing steps used by the laboratory be included in
the determination of the method detection limit.
Procedure
(1) Estimate the Initial MDL using one of the following:
(a) The mean plus three times the standard deviation of a set of
method blanks.
(b) The concentration value that corresponds to an instrument
signal/noise in the range of 3 to 5.
(c) The concentration equivalent of three times the standard
deviation of replicate instrumental measurements of spiked blanks.
(d) That region of the standard curve where there is a
significant change in sensitivity, i.e., a break in the slope of the
standard curve.
(e) Instrumental limitations.
(f) Previously determined MDL.
It is recognized that the experience of the analyst is important
to this process. However, the analyst should include some or all of
the above considerations in the initial estimate of the MDL.
(2) Determine the Initial MDL
(a) Select a spiking level, typically 2-10 times the estimated
MDL in section 1. Spiking levels in excess of 10 times the estimated
detection limit may be required for analytes with very poor recovery
(e.g., an analyte with 10% recovery, spiked at 100 micrograms/L,
mean recovery, 10 micrograms/L; MDL may calculate at 3 micrograms/L.
So, in this case the spiking level is 33xMDL, but spiking lower may
result in no recovery at all).
(b) Process a minimum of 7 spiked blank samples and 7 method
blank samples through all steps of the method, including any sample
preservation. Both preparation and analysis of these samples must
include at least three batches on three separate calendar dates.
Existing data may be used if compliant with the requirements for at
least 3 batches and generated within the last 2 years.
(i) If there are multiple instruments that will be assigned the
same MDL, then the samples must be distributed across all of the
instruments.
(ii) A minimum of two spiked samples and two method blank
samples prepared and analyzed on different calendar dates is
required for each instrument.
(c) Evaluate the spiking level: If any result for any individual
analyte from the spiked blank samples does not meet the method
qualitative identification criteria or does not provide a numerical
result greater than zero then repeat the spikes at a higher
concentration. Qualitative identification criteria are a set of
rules or guidelines for establishing the identification or presence
of an analyte using a measurement system. Qualitative identification
does not ensure that quantitative results for the analyte can be
obtained.
(d) Make all computations according to the defined method with
final results in the method reporting units.
(i) Calculate the sample standard deviation (S) of the replicate
spiked blank measurements and the sample standard deviation of the
replicate method blank measurements from all instruments.
(ii) Compute the MDLs (MDL based on spiked blanks) as
follows:
MDLS = t(n-1, 1-[vprop]=0.99) SS
Where:
MDLs = the method detection limit based on spiked blanks
t(n-1, 1-[alpha]=0.99) = the Student's t-value
appropriate for a the single tailed 99th percentile t statistic and
a standard deviation estimate with n-1 degrees of freedom. See Table
1.
Ss = sample standard deviation of the replicate spiked
blank sample analyses.
(iii) Compute the MDLb (MDL based on method blanks) as
follows:
(A) If none of the method blanks give numerical results for an
individual analyte, the MDLb does not apply. A numerical
result includes both positive and negative results, including results
below the current MDL, but not results of ND (not detected) commonly
observed when a peak is not present in chromatographic analysis.
(B) If some (but not all) of the method blanks for an individual
analyte give numerical results, set the MDLb equal to the
highest method blank result. If more than 100 method blanks are
available, set MDLb to the level that is no less than the
99th percentile of the blank results. For ``n'' method blanks where n
>= 100, sort the method blanks in rank order. The (nx0.99) ranked
method blank result (round to the nearest whole number) is the
MDLb. For example, to find MDLb from a set of 164
method blanks where the highest ranked method blank results are . . .
1.5, 1.7, 1.9, 5.0, and 10, then 164x0.99 = 162.36 which rounds to the
162nd method blank result. Therefore, MDLb is 1.9 for n =
164 (10 is the 164th result, 5.0 is the 163rd result, and 1.9 is the
162nd result). Alternatively, you may use spreadsheet algorithms to
calculate the 99th percentile to interpolate between the ranks more
precisely.
(C) If all of the method blanks for an individual analyte give
numerical results, calculate the MDLb as:
MDLb = XX + t(n-1, 1-[vprop]=0.99)
Sb
Where:
MDLb = the MDL based on method blanks
XX = mean of the method blank results
t(n-1, 1-[alpha]=0.99) = the Student's t-value
appropriate for the single tailed 99th percentile t statistic and a
standard deviation estimate with n-1 degrees of freedom. See
Addendum Table 1.
Sb = sample standard deviation of the replicate blank
sample analyses.
(e) Set the greater of MDLs or MDLb as the
initial MDL.
(3) Ongoing Data Collection
(a) During any quarter in which samples are being analyzed, prepare
and analyze a minimum of two spiked blanks on each instrument, in
separate batches if available, using the same spiking concentration
used in Section 2. If any analytes are repeatedly not detected in the
quarterly spike sample analysis, this is an indication that the spiking
level is not high enough and should be adjusted upward.
(b) Ensure that at least 7 spiked blanks and 7 method blanks are
completed for the annual verification.
(c) At least once per year, re-evaluate the spiking level.
(i) If more than 5% of the spiked blanks do not return positive
numerical results that meet all method qualitative identification
criteria, then the spiking level must be increased and the initial MDL
re-determined following the procedure in Section 2.
(d) If the method is altered in a way that can be reasonably
expected to change the detection limit, then re-determine the initial
MDL according to Section 2, and the ongoing data collection restarted.
(4) Ongoing Annual Verification
(a) At least once per year, re-calculate MDLs and
MDLb from the collected spiked blank and method blank
results using the equations in section 2.
(b) Include data generated within the last 2 years, but only data
with the same spiking level.
[[Page 9075]]
(c) Include the initial MDL spiked blanks if within two years.
(d) Only use data associated with acceptable calibrations and batch
QC. Include all routine data, with the exception of batches that are
rejected and the associated samples reanalyzed. If the method has been
altered in a way that can be reasonably expected to change the
detection limit, use only data collected after the change.
(e) The verified MDL is the greater of the MDLs or
MDLb. If the verified MDL is within a factor of 3 of the
existing MDL, and fewer than 3% of the method blank results (for the
individual analyte) have numerical results above the existing MDL, then
the existing MDL may optionally be left unchanged. Otherwise, adjust
the MDL to the new verification MDL.
Addendum: Determination of the MDL For a Specific Matrix
MDLs may be determined in specific sample matrices as well as in
reagent water.
(1) Analyze the sample matrix to determine the native concentration
of the analyte(s) of interest.
(2) If the native concentration is at a signal to noise ratio of
approximately 5-20, determine the matrix specific MDL according to
Section 2, ``Determine the initial MDL'' without spiking additional
analyte.
(3) Calculate MDLb using method blanks, not the sample
matrix.
(4) If the signal to noise is less than 5, the analyte(s) should be
spiked to obtain a concentration that will give results with a signal
to noise of approximately 10-20.
(5) If the analytes(s) of interest have signal to noise greater
than approximately 20, then the resulting MDL is likely to be biased
high.
Table 1--Single Tailed 99th Percentile t Statistic
------------------------------------------------------------------------
Degrees of
Number of replicates freedom (n-1) t (n-1, 0.99)
------------------------------------------------------------------------
7....................................... 6 3.143
8....................................... 7 2.998
9....................................... 8 2.896
10...................................... 9 2.821
11...................................... 10 2.764
16...................................... 15 2.602
21...................................... 20 2.528
26...................................... 25 2.485
31...................................... 30 2.457
61...................................... 60 2.390
100..................................... 100 2.326
------------------------------------------------------------------------
Documentation
The analytical method used must be specifically identified by
number or title and the MDL for each analyte expressed in the
appropriate method reporting units. Data and calculations used to
establish the MDL must be able to be reconstructed upon request.
The sample matrix used to determine the MDL must also be identified
with MDL value. Document the mean spiked and recovered analyte levels
with the MDL.
[FR Doc. 2015-02841 Filed 2-18-15; 8:45 am]
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