82 FR 40836 - Clean Water Act Methods Update Rule for the Analysis of Effluent
ENVIRONMENTAL PROTECTION AGENCY
Federal Register Volume 82, Issue 165 (August 28, 2017)
Page Range
40836-40941
FR Document
2017-17271
This rule modifies the testing procedures approved for analysis and sampling under the Clean Water Act. The changes adopted in this final rule fall into the following categories: New and revised EPA methods (including new and/or revised methods published by voluntary consensus standard bodies (VCSB), such as ASTM International and the Standard Methods Committee); updated versions of currently approved methods; methods reviewed under the alternate test procedures (ATP) program; clarifications to the procedures for EPA approval of nationwide and limited use ATPs; and 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 82 Issue 165 (Monday, August 28, 2017)
[Federal Register Volume 82, Number 165 (Monday, August 28, 2017)]
[Rules and Regulations]
[Pages 40836-40941]
From the Federal Register Online [www.thefederalregister.org]
[FR Doc No: 2017-17271]
[[Page 40835]]
Vol. 82
Monday,
No. 165
August 28, 2017
Part II
Environmental Protection Agency
-----------------------------------------------------------------------
40 CFR Part 136
Clean Water Act Methods Update Rule for the Analysis of Effluent; Final
Rule
Federal Register / Vol. 82 , No. 165 / Monday, August 28, 2017 /
Rules and Regulations
[[Page 40836]]
-----------------------------------------------------------------------
ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 136
[EPA-HQ-OW-2014-0797; FRL-9957-24-OW]
RIN 2040-AF48
Clean Water Act Methods Update Rule for the Analysis of Effluent
AGENCY: Environmental Protection Agency (EPA).
ACTION: Final rule.
-----------------------------------------------------------------------
SUMMARY: This rule modifies the testing procedures approved for
analysis and sampling under the Clean Water Act. The changes adopted in
this final rule fall into the following categories: New and revised EPA
methods (including new and/or revised methods published by voluntary
consensus standard bodies (VCSB), such as ASTM International and the
Standard Methods Committee); updated versions of currently approved
methods; methods reviewed under the alternate test procedures (ATP)
program; clarifications to the procedures for EPA approval of
nationwide and limited use ATPs; and amendments to the procedure for
determination of the method detection limit to address laboratory
contamination and to better account for intra-laboratory variability.
DATES: This regulation is effective on September 27, 2017. The
incorporation by reference of certain publications listed in the rule
is approved by the Director of the Federal Register as of September 27,
2017. For judicial review purposes, this final rule is promulgated as
of 1:00 p.m. (Eastern time) on September 12, 2017 as provided at 40 CFR
23.2 and 23.7.
ADDRESSES: EPA has established a docket for this action under Docket ID
No. EPA-HQ-OW-2014-0797. All documents in the docket are listed on the
www.regulations.gov Web site. Although listed in the index, some
information is not publicly available, e.g., confidential business
information (CBI) or other information whose disclosure is restricted
by statute. Certain other materials, such as copyrighted material are
not placed on the Internet and will be publicly available only in hard
copy form. Publicly available docket materials are available either
electronically through 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:
A. General Information
1. Does this Action apply to me?
EPA proposed the changes in this method update rule for public
comment on February 19, 2015 (80 FR 8956).
EPA Regions, as well as States, Territories and Tribes authorized
to implement the National Pollutant Discharge Elimination System
(NPDES) program, issue permits with conditions designed to ensure
compliance with the technology-based and water quality-based
requirements of the Clean Water Act (CWA). These permits may include
restrictions on the quantity of pollutants that may be discharged as
well as pollutant measurement and reporting requirements. If EPA has
approved a test procedure for analysis of a specific pollutant, the
NPDES permittee must use an approved test procedure (or an approved
alternate test procedure if specified by the permitting authority) for
the specific pollutant when measuring the required waste constituent.
Similarly, if EPA has established sampling requirements, measurements
taken under an NPDES permit must comply with these requirements.
Therefore, entities with NPDES permits will potentially be affected by
the actions in this rulemaking.
Entities potentially affected by the requirements of this rule
include:
------------------------------------------------------------------------
Examples of potentially affected
Category entities
------------------------------------------------------------------------
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.
------------------------------------------------------------------------
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 process governs judicial review of this rule?
Under Section 509(b)(1) of the Clean Water Act (CWA), judicial
review of this CWA rule may be obtained by filing a petition for review
in a United States Circuit Court of Appeals within 120 days from the
date of promulgation of this rule. For judicial review purposes, this
final rule is promulgated as of 1 p.m. (Eastern time) on September 12,
2017 as provided at 40 CFR 23.2. Section 509(b)(2) provides that any
rule (or requirements of any rule) for which review could have been
obtained under Section 509(b)(1) may also not be challenged later in
civil or criminal proceedings for enforcement.
C. Abbreviations and Acronyms Used in the Preamble and Final Rule Text
4AAP: 4-Aminoantipyrine
AA: Atomic Absorption
ADMI: American Dye Manufacturers Institute
AOAC: AOAC International
ASTM: ASTM International
ATP: Alternate Test Procedure
BOD5: 5-day Biochemical Oxygen Demand test
CAS: Chemical Abstract Services
[[Page 40837]]
CATC: Cyanide Amenable to Chlorination
CFR: Code of Federal Regulations
CIE/UV: Capillary Ion Electrophoresis/Ultraviolet
COD: Chemical Oxygen Demand
CWA: Clean Water Act
DPD: N,N-diethyl-p-phenylenediamine
DPD-FAS: N,N-diethyl-p-phenylenediamine with ferrous ammonium
sulfate
EDTA: Ethylenediamine tetraacetic acid
EPA: Environmental Protection Agency
FLAA: Flame Atomic Absorption Spectroscopy
GC: Gas Chromatograph/Chromatography
GC/HSD: Gas chromatography/halogen-specific detector
GC/MS: Gas chromatography/mass spectrometry
HEM: Hexane extractable material
HPLC: High performance liquid chromatography
HRGC: High Resolution Gas Chromatography
HRMS: High Resolution Mass Spectrometry
HSD: Halogen-specific detector
ICP: Inductively coupled plasma
ICP/AES: Inductively Coupled Plasma-Atomic Emission Spectroscopy
ICP/MS: Inductively Coupled Plasma-Mass Spectrometry
LCS: Laboratory Control Sample
MDL: Method Detection Limit
MS: Mass Spectrometry
MPN: Most Probable Number
MS/MSD: Matrix Spike/Matrix Spike Duplicate
NARA: National Archives and Records Administration
NPDES: National Pollutant Discharge Elimination System
NIST: National Institute of Standards and Technology
PAH: Polynuclear aromatic hydrocarbons
POTW: Publicly Owned Treatment Works
QA: Quality Assurance
QC: Quality Control
RRT: Relative retention time
SDDC: Silver diethyldithiocarbamate
SGT-HEM: Silica gel treated-hexane extractable material
SM: Standard Methods
SPADNS: Common name for fluoride dye reagent which is a mixture of
chemicals
STGFAA: Stabilized Temperature Graphite Furnace Atomic Absorption
Spectroscopy
TKN: Total Kjeldahl Nitrogen
TOC: Total Organic Carbon
USGS: United States Geological Survey
UV: Ultraviolet
VCSB: Voluntary Consensus Standards Body
WET: Whole Effluent Toxicity
Table of Contents
I. Statutory Authority
II. Summary of Final Rule
A. New Versions of Previously Approved EPA Methods in 40 CFR
136.3 and Appendix A
B. Methods Incorporated by Reference
C. New Standard Methods and New Versions of Approved Standard
Methods in 40 CFR 136.3
D. New Versions of Approved ASTM Methods in 40 CFR 136.3
E. New United States Geological Survey (USGS) Methods in 40 CFR
136.3
F. New ATPs in 40 CFR 136.3
G. Changes to 40 CFR Part 136 To Align With 40 CFR Part 122
H. Corrections to 40 CFR Part 136
I. Changes to Table II at 40 CFR 136.3(e) to Required
Containers, Preservation Techniques, and Holding Times
J. Clarifications/Corrections to ATP Procedures in 40 CFR 136.4,
136.5 and Allowed Modifications in 40 CFR 136.6
K. Changes to Appendix B to 40 CFR Part 136--Definition and
Procedure for the Determination of the Method Detection Limit (MDL)
III. Changes Between the Proposed Rule and the Final Rule
A. Changes to Footnote 30 in Table IA and Footnote 27 in Table
IH
B. Changes to Table IB
C. Changes to Table II
D. Change to Method Modifications and Analytical Requirements in
Sec. 136.6, Methods Modification Paragraph
E. Changes to EPA Method 608.3
F. Change to EPA Method 611
G. Changes to EPA Method 624.1
H. Changes to EPA Method 625.1
I. Changes to Method Detection Limit (MDL) Procedure
J. Changes to WET Errata
IV. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review and
Review and Executive Order 13563: Improving Regulation and
Regulatory Review
B. Paperwork Reduction Act
C. Regulatory Flexibility Act
D. Unfunded Mandates Reform Act
E. Executive Order 13132: Federalism
F. Executive Order 13175: Consultation and Coordination With
Indian Tribal Governments
G. Executive Order 13045: Protection of Children From
Environmental Health Risks and Safety Risks
H. Executive Order 13211: Actions That Significantly Affect
Energy Supply, Distribution, or Use
I. National Technology Transfer and Advancement Act of 1995
J. Executive Order 12898: Federal Actions to Address
Environmental Justice in Minority Populations and Low-Income
Populations
K. Congressional Review Act
I. Statutory Authority
EPA is promulgating this rule pursuant to the authority of sections
301(a), 304(h), and 501(a) of the Clean Water Act (``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 National Pollutant Discharge
Elimination System (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).
II. Summary of Final Rule
The following sections describe the changes EPA is making in this
final rule. In addition, further information concerning the rule may be
found in a document prepared for this rule providing EPA's responses to
comments it received on the proposed rule. That document (``Response to
Comments Document for the Methods Update Rule Proposal (80 CFR 8956,
February 19, 2015'') is available in the electronic docket listed in
the ADDRESSES section at the beginning of this document. The following
sections describe changes EPA is making in this final rule.
A. New Versions of Previously Approved EPA Methods in 40 CFR 136.3 and
Appendix A
This rule approves new versions of already approved EPA methods and
corrects typographical errors in the methods. The following briefly
describes the EPA methods added to part 136.
1. EPA Methods 608.3, 611, 624.1 and 625.1
Method 608.3, Organochlorine Pesticides and PCBs by GC/HSD. This
method measures organochorine 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.
EPA Method 611, Haloethers. This method measures the following
haloethers: Bis(2-chloroethyl) ether, bis(2-chloroethoxy) methane, 2,
2'-oxybis (1-chloropropane), 4-bromophenyl phenyl ether, and 4-
chlorophenyl phenyl ether in municipal and industrial discharges by gas
chromatography (GC) as provided under 40 CFR 136.1. The only change EPA
has made is correcting a typographical error in the list of parameters
by changing ``4-Chlorophenyl phenyl either'' to ``4-Chlorophenyl phenyl
ether'' and has
[[Page 40838]]
corrected an analyte name to 2,2'-oxybis(1-chloropropane), which
matches the CAS Number 108-60-1.
EPA Method 624.1, Purgeables by GC/MS. This method measures
purgeable organic pollutants in industrial discharges and other
environmental samples by gas chromatography (GC) combined with mass
spectrometry (MS), as provided under 40 CFR 136.1.
EPA Method 625.1, Base/Neutrals and Acids by GC/MS. This method
measures semivolatile organic pollutants in industrial discharges and
other environmental samples by GC/MS, as provided under 40 CFR 136.1.
2. EPA Methods 1600, 1603, 1680, and 1682
This rule implements the following changes for EPA microbiological
methods 1600, 1603, 1680, and 1682 that correct typographical or other
errors that EPA identified in the methods after publication. This rule
revises all of these methods with new EPA document numbers and dates.
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 Escherichia coli to
Enterobacter aerogenes. E. coli is thermotolerant and E. aerogenes is
not, so E. coli is not an appropriate negative control when heated.
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).
EPA Method 1680 for fecal coliforms using multiple tube
fermentation: In section 3.1 Definitions, the sentence ``The
predominant fecal coliform is E. coli.'' now reads ``The predominant
fecal coliform can be E. coli.''
EPA Method 1682 for Salmonella by MSRV medium: (1) In section 9.3,
Table 2, the lab-prepared spike acceptance criteria now reads:
``Detect-254%'' and ``Detect-287%'' and (2) in section 14.5, Table 9,
the spiked Salmonella for Example 2, Liquid now reads ``3.7 x 10\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. This rule
incorporates by reference revisions to methods from two VCSBs: Standard
Methods and ASTM. The VCSB methods in this rule are in compliance, as
discussed more fully in Section IV.I below, with the National
Technology Transfer Act which directs EPA to use voluntary consensus
standards so long as they are consistent with applicable law and not
otherwise impractical. The 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 significant financial burden for a
discharger or environmental laboratory, making the methods reasonably
available. This rule 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 methods and Alternate Test Procedures (ATPs)
incorporated by reference are reasonably available. The individual
standards are discussed in greater detail below.
C. New Standard Methods and New Versions of Approved Standard Methods
in 40 CFR 136.3
This rule approves 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
requirements, or make editorial corrections. Consistent with the
previous method update rule (77 FR 29758, May 18, 2012), EPA generally
approves and includes 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 included to Standard Methods in this rule do
not contain any substantive changes. Each Standard Method entry
contains the 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 identifies new versions of previously approved
Standard Methods that EPA is including in Table IB at 40 CFR part 136.
Where there are substantive changes to the method, these are noted:
1. SM 2120 B-2011, color, platinum cobalt visual comparison method.
2. SM 2120 F-2011, color, ADMI weighted-ordinate spectrophotometer
method. EPA previously approved this method 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. A footnote
on the method specifies that the pH should be 7.6 and not 7.0 when used
for NPDES monitoring purposes, since the original method was approved
with a reference pH of 7.6. Additionally, the currently approved
methods for the Color parameter are assigned more specific parameter
names.
3. SM 2130 B-2011, turbidity, nephelometric method.
4. SM 2310 B-2011, acidity, titration using electrometric endpoint
or phenolphthalein endpoint.
5. SM 2320 B-2011, alkalinity, electrometric or colorimetric
titration to pH 4.5.
6. SM 2340 B-2011 and SM 2340 C-2011, hardness, by the calculation
method or EDTA titration.
7. SM 2510 B-2011, conductivity, Wheatstone bridge method.
8. 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.
9. SM 2550 B-2010, temperature, thermometric.
10. SM 3111 B-2011, SM 3111 C-2011, SM 3111 D-2011, and SM 3111 E-
2011, metals, direct aspiration atomic absorption (AA) methods with
different gas mixtures. Each method has a different list of metals;
these lists were not changed.
11. SM 3112 B-2011, metals, applicable to mercury, cold-vapor
atomic absorption spectrometric method.
12. SM 3113 B-2010, metals, electrothermic atomic absorption
spectrometric method. The only substantive change is 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.
[[Page 40839]]
13. 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.
14. SM 3120 B-2011, metals, inductively coupled plasma (ICP)
method; no changes were made to the approved list of metals.
15. SM 3125 B-2011, metals, inductively coupled plasma/mass
spectrometry (ICP/MS) method; no changes were made to the approved list
of metals.
16. SM 3500-Al B-2011, aluminum, colorimetric method.
17. SM 3500-As B-2011, arsenic, colorimetric method silver
diethyldithiocarbamate (SDDC) method.
18. SM 3500-Ca B-2011, calcium, titrimetric method (EDTA).
19. 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.
20. 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.
21. SM 3500-Fe B-2011, iron, colorimetric method (phenanthroline).
22. 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.
23. SM 3500-Mn B-2011, manganese, colorimetric method (persulfate).
24. SM 3500-Na B-2011, sodium, flame photometric method.
25. SM 3500-Pb B-2011, lead, colorimetric method (dithizone).
26. SM 3500-V B-2011, vanadium, colorimetric method (gallic acid).
27. SM 3500-Zn B-2011, zinc, colorimetric method (zincon).
28. SM 4110 (B-D)-2011, anions, ion chromatography; no changes were
made to the approved analyte list.
29. SM 4140 B-2011, inorganic anions, capillary ion electrophoresis
with indirect ultraviolet (UV) detection: No changes were made to the
approved analyte list.
30. SM 4500-B B-2011, boron, spectrophotometer or filter photometer
(curcumin)
31. SM 4500-Cl- (B-E)-2011, chloride, titrimetric:
(Silver nitrate), (mercuric nitrate), automated (ferricyanide),
potentiometric titration.
32. 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).
33. 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.
34. 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.
35. SM 4500-H\+\ B-2011, hydrogen ion (pH), electrometric
measurement.
36. 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.
37. SM 4500-NO2- B-2011, nitrite (as
nitrogen), spectrophotometric: Manual.
38. SM 4500-NO3- D-2011, nitrate (as
nitrogen), ion selective electrode.
39. SM 4500-NO3- (E, F, H)-2011, nitrate-
nitrite (as nitrogen), colorimetric: Cadmium reduction-manual and
automated, and colorimetric: Automated hydrazine.
40. SM 4500-NO3- (E, F)-2011, nitrite (as
nitrogen), colorimetric: Cadmium reduction-manual and automated.
41. SM 4500-Norg (B-D)-2011, total Kjeldahl nitrogen (as
nitrogen, organic), semi-automated block digester colorimetric
(distillation not required).
42. SM 4500-O (B-G)-2011, oxygen (dissolved), Winkler (azide
modification), electrode.
43. 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.
44. SM 4500-S2- (B-D, F, G)-2011, sulfide, sample
pretreatment, titrimetric (iodine) analysis, colorimetric (methylene
blue), ion selective electrode.
45. SM 4500-SiO2 (C, E, F)-2011, silica, 0.45-micron
filtration followed by any of the following: Colorimetric, manual or
automated (molybdosilicate).
46. SM 4500-SO32- B-2011, sulfite,
titrimetric (iodine-iodate).
47. SM 4500-SO42- (C-G)-2011, sulfate,
automated colorimetric, gravimetric, and turbidimetric.
48. SM 5210 B-2011, biochemical oxygen demand (BOD5), dissolved
oxygen depletion.
49. SM 5220 (B-D)-2011, chemical oxygen demand (COD), titrimetric;
spectrophotometric, manual or automatic.
50. SM 5310 (B-D)-2011, total organic carbon (TOC), combustion,
heated persulfate or UV persulfate oxidation.
51. 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.
52. SM 5530 (B, D)-2010, phenols, manual distillation, followed by
colorimetric 4-aminoantipyrine (4AAP) manual.
53. SM 5540 C-2011, surfactants, colorimetric (methylene blue).
The following identifies new versions of previously approved
Standard Methods that EPA is including in 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 identifies new versions of previously approved
methods that EPA is including in 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 revised the approval of certain Standard Methods
previously 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 identifies previously approved Standard Methods in
Table IA and/or Table IH at 40 CFR part 136 Table IB at 40 CFR part 136
where there are substantive changes to the method:
1. EPA replaced the membrane filtration method SM 9222 B-1997 with
[[Page 40840]]
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'' will be changed from ``9222 (B+B.5c)-1997'' to
``9222 (B+B.4c)-2006.''
2. This rule replaces the membrane filtration method SM 9222 D-1997
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, this rule adds the following footnote to Tables IA and IH
regarding SM 9222 D-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 to be verified to prevent
misidentification of results as false positive or false negative.
3. This rule replaces the membrane filtration method SM 9222 G-1997
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.
D. New Versions of Approved ASTM Methods in 40 CFR 136.3
This rule approves new versions of currently approved ASTM methods,
for the same reasons outlined in the first paragraph of Section II.B
above. Many of the new versions of ASTM Methods approved in 40 CFR part
136 do not contain any substantive changes. Each entry contains (in the
following order): Approved ASTM method number and date, the parameter,
a brief description of the analytical technique. Where there were
substantive changes, they are identified. The methods listed below are
organized according to the table at 40 CFR part 136 in which they
appear.
The following identifies new versions of currently approved ASTM
methods that are included in Table IB at 40 CFR part 136:
1. ASTM D 511-09 (A, B), calcium and magnesium, titrimetric
ethylenediamine tetraacetic acid (EDTA), AA direct aspiration.
2. ASTM D 516-11, sulfate ion, turbidimetric.
3. ASTM D 858-12 (A-C), manganese, atomic absorption (AA) direct
aspiration, AA furnace.
4. ASTM D 859-10, silica, colorimetric, manual.
5. ASTM D 1067-11, acidity or alkalinity, electrometric endpoint or
phenolphthalein endpoint; electrometric or colorimetric titration to pH
4.5, manual.
6. ASTM D 1068-10 (A-C), iron, AA direct aspiration; AA furnace;
colorimetric (phenanthroline).
7. ASTM D 1126-12, hardness, titrimetric (EDTA).
8. ASTM D 1179-10 (A, B), fluoride ion, electrode, manual;
colorimetric, (SPADNS).
9. ASTM D 1246-10, bromide ion, electrode.
10. ASTM D 1687-12 (A-C), chromium (total) and dissolved hexavalent
chromium, colorimetric (diphenyl-carbazide); AA direct aspiration; AA
furnace.
11. ASTM D 1688-12 (A-C), copper, AA direct aspiration, AA furnace.
12. ASTM D 1691-12 (A, B), zinc, AA direct aspiration.
13. ASTM D 1976-12, dissolved, total-recoverable, or total
elements, inductively coupled plasma/atomic emission spectroscopy (ICP/
AES).
14. ASTM D 3223-12, total mercury, cold vapor, manual.
15. ASTM D 3373-12, vanadium, AA furnace.
16. ASTM D 3557-12 (A-D), cadmium, AA direct aspiration, AA
furnace, voltammetry.
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).
18. ASTM D 4382-12, barium, AA furnace.
19. ASTM D 4658-09, sulfide ion, ion selective electrode.
20. ASTM D 5257-11, dissolved hexavalent chromium, ion
chromatography.
21. ASTM D 5673-10, dissolved elements and total-recoverable
elements, ICP/MS.
22. ASTM D 5907-13, filterable matter (total dissolved solids) and
nonfilterable matter (total suspended solids), gravimetric, 180 [deg]C
gravimetric, 103-105 [deg]C post washing of residue.
23. ASTM D 6508-10, inorganic anions (fluoride, bromide, chloride,
nitrite, nitrate, orthophosphate, and sulfate), capillary ion
electrophoresis with indirect UV detection.
24. ASTM D 7284-13, total cyanide, manual distillation with
MgCl2 followed by flow injection, gas diffusion amperometry.
25. ASTM D 7511-12, total cyanide, segmented flow injection, in-
line ultraviolet digestion, followed by gas diffusion amperometry.
EPA has changed Table IC at 40 CFR part 136 as follows:
1. ASTM D 7065-11, nonylphenol, bisphenol A, p-tert-octylphenol,
nonylphenol monoethoxylate, nonylphenol diethoxylate, gas
chromatography/mass spectrometry (GC/MS).
E. New United States Geological Survey (USGS) Methods in 40 CFR 136.3
1. This rule adds 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. Both methods are 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 at no cost 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 approved in this rule.
F. New ATPs in 40 CFR 136.3
This rule approves six methods submitted to EPA for review through
the alternate test procedures (ATP) program and deemed acceptable based
on the evaluation of documented method performance.
The following ATP has nationwide approval for wastewater and is
incorporated into Table IA:
[[Page 40841]]
1. 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 similar to the already approved E.
coli Colilert[supreg]-18 method, with the addition of an increased
incubation temperature for fecal coliforms, which requires the use of a
waterbath incubator. The Colilert[supreg]-18 Coliform/E. coli Enzyme
Substrate Test can be obtained from IDEXX Laboratories Inc., One IDEXX
Drive, Westbrook, ME 04092. Telephone: 800-321-0207.
The following four ATPs have nationwide approval for all matrix
types and are incorporated into Table IB:
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 N07-0003 can be obtained from The
Nitrate Elimination Company, 334 Hecla Street, Lake Linden, Michigan,
49945. Telephone: 888-NITRATE.
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 Instruments, LLC Method Ammonia-001 can be obtained
from Timberline Instruments, LLC, 1880 South Flatiron Court, Boulder,
Colorado 80301. Telephone: 303-440-8779.
3. 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 can be obtained from Hach Company, 5600 Lindbergh Drive,
Loveland, CO 80539. Telephone: 970-669-3050.
4. 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 10206 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 can be obtained from Hach Company, 5600
Lindbergh Drive, Loveland, CO 80539. Telephone: 970-669-3050.
The following ATP has nationwide approval for only pulp, paper and
paperboard mill biologically treated effluent and is incorporated into
Table IB:
1. 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). 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.
G. Changes to 40 CFR Part 136 To Align With 40 CFR Part 122
This rule amends 40 CFR 136.1 to substitute the term ``Director''
for the terms ``Administrator'' and ``State having an authorized
program.'' In addition, the rule amends 40 CFR 136.2(d) to state that
the term ``Director'' by cross-reference to the definition of
``Director'' in the NPDES regulations at 40 CFR 122.2.
EPA eliminated the words ``be sufficiently sensitive and'' from 40
CFR 136.6(b)(2) to eliminate unnecessary confusion with the term
``sufficiently sensitive,'' as used in 40 CFR 122. Deleting this term
did not change the requirements of 40 CFR 136.6(b)(2).
H. Corrections to 40 CFR Part 136
This rule corrected typographical errors, updated methods from
VCSBs that went unnoticed during the last update to 40 CFR part 136,
and added technology updates to toxicity methods.
1. This rule makes multiple clarifications and corrections to the
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 included definition of
terms (e.g., the acronym YCT--yeast, cereal leaves, and trout chow, was
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 included deletion
of unavailable products, typographical errors, etc. Among the
corrections that EPA proposed was a change to the language for Fathead
Minnows, Daphnids, and Green Alga in the document Short-term Methods
for Estimating the Chronic Toxicity of Effluents and Receiving Waters
to Freshwater Organisms, Fourth Edition, U.S. Environmental Protection
Agency, Office of Water, Washington, DC EPA/821/R-02/013, October 2002.
For Fathead Minnows and Daphnids, EPA proposed to change
``Conductivity, alkalinity, and hardness are measured in each new
sample (100% effluent or receiving water) and in the control'' to read
``Conductivity, alkalinity, and hardness are measured at the beginning
of the test for all test concentrations in each new sample and in the
control before they are dispersed to the test chambers.'' EPA received
a number of comments stating that this change would constitute a change
to the test rather than a correction or clarification. EPA is in
agreement with these comments, and for that reason, will not add the
inserted language ``at the beginning of the test for all test
concentrations.'' EPA is retaining its deletion of ``(100% effluent or
receiving water)'' and the insertion of ``before they are dispensed to
the test chamber'' to the end of the sentence. Thus, the sentence will
now read ``Conductivity, alkalinity, and hardness are measured in each
new sample and in the control before they are dispensed to the test
chamber.'' For Green Alga, the proposed change has been eliminated from
the errata because only the increased testing was proposed.
2. This rule changes 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 9221 B.1. As a result,
section 9221 B.1 in previously approved versions has become section
9221 B.2. EPA changed SM 9221 B.1 to 9221 B.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 did not propose to change them.
3. This rule adds a line for Enterococci that was erroneously
deleted in the 2012 Methods Update Rule. The line states ``MPN,
multiple
[[Page 40842]]
tube'' with Standard Method 9230B-2007.
4. This rule revises a hardness entry in Table IB to state ``Ca
plus Mg as their carbonates, by any approved method for Ca and Mg (See
Parameters 13 and 33), provided that the sum of the lowest point of
quantitation for Ca and Mg is below the NPDES permit requirement for
Hardness.'' Previously, this was only allowed for inductively coupled
plasma or AA direct aspiration Ca and Mg methods. The rationale behind
this change is that if one calcium and magnesium method approved by EPA
can be used to calculate hardness, then other EPA approved methods
should also be permitted to do so.
5. This rule deletes ``p 14'' from footnote 24 of Table IB because
the method is not on that page.
6. This rule deletes 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. This rule removes the reference to costs in 40 CFR 136.3(b)
because costs are not included in the referenced documents.
8. This rule removes the first instance of ``are'' in 40 CFR
136.3(e) because it is a typographical error.
I. Changes to Table II at 40 CFR 136.3(e) to Required Containers,
Preservation Techniques, and Holding Times
This rule revises Table II at 40 CFR 136.3(e) as follows.
1. The rule adds rows to Table II that specify holding times for
total/fecal coliforms, and fecal streptococci in Table IH. Previously
the holding times for these bacterial tests were unspecified. Now these
methods have the same holding time requirements as the other bacterial
tests.
2. This rule changes 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. The rule re-inserts language that was accidentally deleted from
footnote 5 of Table II during the previous update to 40 CFR part 136.
Footnote 5 now reads ``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.'' Previously, the words: ``for
microbiological analyses,'' were not present, so the footnote did not
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 requested public comment on how to approve variances to
sample preservation, containers or holding times listed in Table II for
specific dischargers. Currently, 40 CFR 136.3(e) grants authority to
either the permitting authority in the Region or the Regional ATP
Program Coordinator to grant exceptions to Table II for a specific
discharger.
Of the eight comments received, four commenters thought that the
permitting authority should have the sole authority to approve these
variance requests. Three commenters thought that the Regional ATP
Program Coordinators should have sole authority to approve variance
requests, and one commenter thought that the best approach was for the
permitting authority and the Regional ATP Program Coordinator to
approve Table II variances for specific dischargers collaboratively.
Each of these commenters provided sound reasoning for their suggested
approach to the review and approval of these types of requests.
EPA has chosen to defer any decision on revising the current
language and to leave 40 CFR 136.3(e) unchanged in this final rule.
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 procedure 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 (75 FR 58024, September 23, 2010), 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 evidenced EPA's intent that only the Region--not the State--
would be 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 only makes sense if read to authorize only the
Regional ATP Coordinator, 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 previously 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
superfluous requirement.
This rule deletes 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 has
the authority to approve limited use ATPs.
This rule also changes 40 CFR 136.4 and 136.5 to clarify the
process for nationwide ATP approvals 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 the text simpler and clearer.
Finally, this rule adds 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 their
Director or EPA Regional ATP Coordinator.
K. Changes to Appendix B to 40 CFR Part 136--Definition and Procedure
for the Determination of the Method Detection Limit (MDL)
EPA is revising the procedure for determination of the MDL
primarily to address laboratory blank contamination and to better
account for intra-laboratory variability. The MDL procedure has not
been revised since it was originally promulgated in 1983. The
suggestion for these revisions came first from The National
Environmental Laboratory Accreditation Conference (NELAC)
[[Page 40843]]
Institute. EPA proposed to adopt these revisions. Following proposal,
EPA further evaluated the proposed revision in conjunction with input
from the states and commercial laboratories. EPA received extensive
comments on the proposed revisions.
The revisions address the following issues and add new requirements
in the following areas.
Background contamination. Under the revisions to appendix B,
laboratories are 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. These revisions will reduce false positive
detects.
MDLs that represent multiple instruments. Under the revisions, if a
laboratory uses MDL values that represent multiple instruments, then
the laboratory is required to calculate the MDL by analyzing MDL
samples and method blanks on all of these instruments. (Note: MDL
samples are a reference matrix, such as reagent water, spiked with a
known and consistent quantity of the analyte.) Previously, laboratories
were known to run all of their prepared MDL samples on the most
sensitive instrument, and then use that MDL for other instruments. This
modification makes the MDL more representative of the laboratory's
actual analytical capability. Deriving an MDL that is representative of
multiple instruments is an option, not a requirement; laboratories can
determine individual MDL values for individual instruments if they
prefer.
Under the revisions, laboratories are required to run MDL samples
and method blanks every quarter that samples are analyzed using a
specific method. Previously, laboratories redetermined the MDL once a
year, often under the most ideal circumstances (e.g., immediately after
the instrument has been serviced or after an annual maintenance
routine). Quarterly MDL samples and method blanks will determine if the
detection limit has significantly drifted over time. Laboratories will
be exempt from running the quarterly MDL samples and method blanks for
a method during quarters when no samples are analyzed using that
method. The ongoing quarterly MDL samples and method blanks are used to
calculate the MDL every year, recalculation of the MDL is required once
every thirteen months. Thirteen months was selected to give
laboratories more flexibility. For example, a laboratory can
recalculate an MDL on January 8th one year and then January 17th the
next, and still be in compliance.
EPA received comments from industries that purchase laboratory
services that stated the revised MDL procedure may increase laboratory
costs, but not significantly. EPA also received comments from some
laboratories stating the revised MDL procedure would impose increased
costs to laboratories, while other laboratories stated the opposite.
The majority of commenters supported the revised MDL procedure. All of
the laboratory associations, who represent the laboratory community,
commented in favor of the revised MDL procedure. Comments not in favor
of the MDL revision were received from individual laboratories,
individuals, one utility, and two state government departments.
As a result of the comments, EPA has made minor clarifications to
the MDL procedure. Two options were added to the MDL procedure as a
result of comments received: (1) A streamlined approach to determine
whether a new instrument can be added to a group of instruments with an
already established MDL and (2) laboratories have the option to use
only the last six months of method blank data or the fifty most recent
method blanks, whichever yields the greater number of method blanks to
calculate the MDL value derived from method blanks (MDLb). Both of
these changes are in line with the goals of the revised MDL procedure,
and are responsive to the comments received. Neither of these additions
are mandatory; however, they provide the laboratory with more options
for calculating the MDL. Commenters also noted that the detection limit
definition in Sec. 136.2(f) should undergo a minor revision to match
the revisions in the MDL procedure (which the definition references).
The words, ``distinguishable from the method blank results'' has been
replaced with ``greater than zero'' in the definition.
III. Changes Between the Proposed Rule and the Final Rule
Except as noted below, the content of the final rule is the same as
that of the proposed rule.
A. Changes to Footnote 30 in Table IA and Footnote 27 in Table IH
These footnotes regard SM 9222 D-2006 for fecal coliform
verification frequency. EPA proposed a requirement of ``at least five
typical and five atypical colonies per sampling site on the day of
collection and analysis.'' A number of commenters identified
deficiencies with the proposed changes. After further review, EPA has
determined that footnote 30 in Table IA and footnote 27 in Table IH
require both modification and clarification and is changing both
footnotes to read ``On a monthly basis, at least ten blue colonies from
the medium must be verified using Lauryl Tryptose Broth and EC broth,
followed by count adjustment based on these results; and representative
non-blue colonies should be verified using Lauryl Tryptose Broth. Where
possible, verifications should be done from randomized sample
sources.''
B. Changes to Table IB
As pointed out by multiple commenters, and verified by EPA, the
color parameter in Table IB contains methodologies and methods that are
mislabeled. EPA reorganized the Color methodology descriptions and
methods as follows: (1) The ADMI colorimetric procedure SM 2120 F-2011
is now listed on a new ``ADMI'' methodology row. (2) Footnote 18 is
listed on the table row with the methodology ``spectrophotometric,''
and footnote 18 lists both NCASI Technical Bulletin 253 (1971) and
NCASI Technical Bulletin 803 (2000). NCASI Technical Bulletin 803 is an
update to NCASI Technical Bulleting 253 for the measurement of color in
pulp mill wastewaters. The update adds a stabilizing pH buffer and
turbidity reduction approaches. (3) SM 2120 B-2011 and USGS Method I-
1250-85 are on a methodology row labeled ``platinum cobalt visual
comparison'' methods.
The Capillary Ion Electrophoresis/Ultraviolet (CIE/UV) method,
D6508, Rev. 2 has been moved from the ASTM column to the USGS/AOAC/
Other column because this method is available from Waters Corporation
(see footnote 54 in Table IB). This affects the following parameters:
Bromide, mg/L; chloride, mg/L; fluoride--total, mg/L; nitrate (as N),
mg/L; nitrite (as N), mg/L; orthophosphate (as P), mg/L; and sulfate
(as SO4) mg/L.
C. Changes to Table II
A time clarification of 15 minutes has been added to the parameter
for Temperature.
The parameter 2-Chloroethylvinyl ether has been moved from the
first row for Table IC organic tests to a separate row. Section 9.7 of
the revised EPA Method 624.1 notes that acidification will destroy 2-
chlooethylvinyl ether. Thus, adding HCl to pH 2 would not be acceptable
for this parameter.
[[Page 40844]]
D. Change to Method Modifications and Analytical Requirements in Sec.
136.6, Methods Modification Paragraph
For clarification purposes, the following two lines have been added
to the methods modification paragraph (b): Where the laboratory is
using a vendor-supplied method, it is the QC criteria in the reference
method, not the vendor's method that must be met to show equivalency.
Where a sample preparation step is required (i.e., digestion,
distillation), QC tests are to be run using standards treated in the
same way as samples.
Also in this paragraph, the paragraph (b)(4)(xvi), ``Changes are
allowed in purge-and-trap sample volumes or operating conditions,'' was
incorrectly deleted and is being reinstated.
Further, paragraph (b)(4)(xvii), regarding allowable modifcations
to Method 625, is being deleted as Method 625 has been replaced in its
entirety with an updated version with this rulemaking.
E. Changes to EPA Method 608.3
EPA received numerous comments on Method 608.3, ranging from
pointing out minor typographical errors to questioning substantive
technical aspects of the proposed method. In response, EPA revised the
method to address many of those comments. See the Response to Comments
document available in the electronic docket listed in the ADDRESSES
section at the beginning of this document for a detailed description of
the changes.
Additionally, based on comments received in response to the
proposal, EPA is reverting to the MDL values in the earlier version of
Method 608 for those analytes that were included in Table 1 of Method
608.3. The MDLs in the proposed version of 608.3 were chosen for the
proposed revision because they were determined with a capillary GC
column. However, as noted by commenters, the values are not derived
from a multiple laboratory validation study. Therefore, EPA has
restored the original Method 608 MDL values. At such time as EPA
develops new multi-laboratory MDL and ML values for the method, they
will be included in a future revision and rulemaking.
Although EPA received comments about updating the QC acceptance
criteria in Method 608.3, EPA did not adopt such changes because EPA
lacks data from a multi-laboratory validation study from which to
develop such criteria.
F. Change to EPA Method 611
In Section 1.1, EPA corrected the last parameter in the list of
parameters table, that read ``4-Chlorophenyl phenyl either,'' a
typographical error. The word ``either'' should be ``ether.'' The
correct parameter name is ``4-Chlorophenyl phenyl ether.''
G. Changes to EPA Method 624.1
EPA received numerous comments on Method 624.1, ranging from
pointing out minor typographical errors to questioning substantive
technical aspects of the proposed method. In response, EPA revised the
method to address many of those comments. See the response to comments
document available in the docket listed in the ADDRESSES section at the
beginning of this document for a detailed description of the changes.
Additionally, section 8.1.2.1.2, subsection e, Sample matrices on
which MS/MSD tests must be performed for nationwide use of an allowed
modification, has been changed to update the web link for the list of
industrial categories with existing effluent guidelines to https://www.epa.gov/cwa-methods/alternate-test-procedure-documents.
Although EPA received comments about updating the QC acceptance
criteria in Method 624.1, EPA did not adopt such changes because EPA
lacks data from a multi-laboratory validation study from which to
develop such criteria.
H. Changes to EPA Method 625.1
EPA received numerous comments on Method 625.1, ranging from
pointing out minor typographical errors to questioning substantive
technical aspects of the proposed method. In response, EPA revised the
method to address many of those comments. See the response to comments
document available in the electronic docket listed in the ADDRESSES
section at the beginning of this document for a detailed description of
the changes.
Additionally, as was the case with EPA Method 624.1, section
8.1.2.1.2, subsection e, Sample matrices on which MS/MSD tests must be
performed for nationwide use of an allowed modification, has been
changed to update the web link for the list of industrial categories
with existing effluent guidelines to https://www.epa.gov/cwa-methods/alternate-test-procedure-documents.
Although EPA received comments about updating the QC acceptance
criteria in Method 625.1, EPA did not implement such changes because
EPA lacks data from a multi-laboratory validation study from which to
develop such criteria.
I. Changes to Method Detection Limit (MDL) Procedure, Apppendix B
No significant revisions were made to the proposed MDL procedure.
Some flexibility was added to the procedure, as is discussed in Section
II.K above.
J. Changes to WET Errata
Among the corrections that EPA proposed was a change to the
language for Fathead minnows, Daphnids, and Green Alga in the document
Short-term Methods for Estimating the Chronic Toxicity of Effluents and
Receiving Waters to Freshwater Organisms, Fourth Edition, U.S.
Environmental Protection Agency, Office of Water, Washington, DC EPA/
821/R-02/013, October 2002. For Fathead Minnows and Daphnids, EPA
proposed to change ``Conductivity, alkalinity, and hardness are
measured in each new sample (100% effluent or receiving water) and in
the control'' to read ``Conductivity, alkalinity, and hardness are
measured at the beginning of the test for all test concentrations in
each new sample and in the control before they are dispersed to the
test chambers.'' EPA agrees with commenters that this change would
constitute a change to the test rather than a correction or
clarification. For that reason, EPA will not add the inserted language
``at the beginning of the test for all test concentrations.'' EPA is
retaining its deletion of ``(100% effluent or receiving water)'' and
the insertion of ``before they are dispensed to the test chamber'' to
the end of the sentence. Thus, the sentence will now read
``Conductivity, alkalinity, and hardness are measured in each new
sample and in the control before they are dispensed to the test
chamber.'' For Green Alga, the proposed change has been eliminated from
the errata because only the increased testing was proposed.
IV. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review and Executive
Order 13563: Improving Regulation and Regulatory Review
This rule is not a ``significant regulatory action'' under the
terms of Executive Order (EO) 12866 (58 FR 51735, October 4, 1993) and
is therefore not subject to review under EO 12866 and EO 13563.
B. Paperwork Reduction Act
This action does not impose an information collection burden under
the provisions of the Paperwork Reduction
[[Page 40845]]
Act, 44 U.S.C. 3501 et seq. Burden is defined at 5 CFR 1320.3(b). This
rule does not impose any information collection, reporting, or
recordkeeping requirements. This rule merely adds new and revised
versions of testing procedures, and sample preservation requirements.
C. Regulatory Flexibility Act
The Regulatory Flexibility Act (RFA) generally requires an agency
to prepare a regulatory flexibility analysis of any rule subject to
notice and comment rulemaking requirements under the Administrative
Procedure Act or any other statute unless the agency certifies that the
rule will not have a significant economic impact on a substantial
number of small entities. Small entities include small businesses,
small organizations, and small governmental jurisdictions.
For purposes of assessing the impacts of this rule on small
entities for methods under the Clean Water Act, small entity is defined
as: (1) A small business that meets RFA default definitions (based on
SBA size standards) found in 13 CFR 121.201; (2) a small governmental
jurisdiction that is a government of a city, county, town, school
district or special district with a population less than 50,000; and
(3) a small organization that is any not-for-profit enterprise which is
independently owned and operated and is not dominant in its field.
After considering the economic impacts of this final rule on small
entities, I certify that this action will not have a significant
economic impact on a substantial number of small entities. This action
approves new and revised versions of testing procedures. Generally,
these changes will have a positive impact on small entities by
increasing method flexibility, thereby allowing entities to reduce
costs by choosing more cost-effective methods.
D. Unfunded Mandates Reform Act
This action contains no Federal mandates under the provisions of
Title II of the Unfunded Mandates Reform Act of 1995 (UMRA), 2 U.S.C.
1531-1538 for State, local, or tribal governments, or the private
sector.
EPA has determined that this final rule contains no regulatory
requirements that might significantly or uniquely affect small
governments. Generally, this action will have a positive impact by
increasing method flexibility, thereby allowing method users to reduce
costs by choosing more cost effective methods. In some cases,
analytical costs may increase slightly due to changes in methods, but
these increases are neither significant, nor unique to small
governments. This rule merely approves new and revised versions of
testing procedures, and new sample collection, preservation, and
holding time requirements.
Thus, this rule is not subject to the requirements of Section 203
of UMRA.
E. Executive Order 13132: Federalism
This final rule does not have federalism implications. It will not
have substantial direct effects on the States, on the relationship
between the national government and the States, or on the distribution
of power and responsibilities among the various levels of government,
as specified in Executive Order 13132 (64 FR 43255, Aug. 10, 1999).
This rule merely approves new and revised versions of testing
procedures, and new sample collection, preservation, and holding time
requirements. The costs to State and local governments will be minimal.
In fact, governments may see a cost savings because the rule adds
flexibility for laboratories and permittees to choose between
additional approved test methods and it also provides additional
flexibility to modify existing test methods. Thus, laboratories and
permittees will not make as many requests for approval of alternative
test methods or method modifications, and the rule does not preempt
State law. Thus, Executive Order 13132 does not apply to this rule.
In the spirit of Executive Order 13132, and consistent with EPA
policy to promote communications between EPA and State and local
governments, EPA specifically solicited comment on the proposed rule
from State and local officials.
F. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments
This final rule does not have tribal implications, as specified in
Executive Order 13175, (65 FR 67249, Nov. 9, 2000). It will not have
substantial direct effects on Tribal governments, on the relationship
between the federal government and Indian tribes, or on the
distribution of power and responsibilities between the federal
government and Indian tribes. This rule merely approves new and revised
versions of testing procedures, and new sample collection,
preservation, and holding time requirements. The costs to tribal
governments will be minimal. In fact, tribal governments may see a cost
savings because the rule adds flexibility for laboratories and
permittees to choose between additional approved test methods and it
also provides additional flexibility to modify existing test methods.
Thus, laboratories and permittees will not make as many requests for
approval of alternative test methods or method modifications. Thus,
Executive Order 13175 does not apply to this rule.
In the spirit of Executive Order 13175, and consistent with EPA
policy to promote communications between EPA and Indian tribes, EPA
specifically solicited comment on the proposed rule from tribal
officials. EPA did not receive any comments from Indian tribes.
G. Executive Order 13045: Protection of Children From Environmental
Health Risks and Safety Risks
EPA interprets E.O. 13045 (62 FR 19885, April 23, 1997) as applying
only to those regulatory actions that concern health or safety risks,
such that the analysis required under section 5-501 of the E.O. has the
potential to influence the regulation. This action is not subject to
E.O. 13045 because it does not establish an environmental standard
intended to mitigate health or safety risks. This rule approves new and
revised versions of testing procedures, and new sample collection,
preservation, and holding time requirements.
H. Executive Order 13211: Actions That Significantly Affect Energy
Supply, Distribution, or Use
This action is not subject to Executive Order 13211, ``Actions
Concerning Regulations That Significantly Affect Energy Supply,
Distribution, or Use'' (66 FR 28355 (May 22, 2001)) because it is not a
significant regulatory action under Executive Order 12866.
I. National Technology Transfer and Advancement Act of 1995
Section 12(d) of the National Technology Transfer and Advancement
Act of 1995, (NTTAA), Public Law 104-113, section 12(d) (15 U.S.C. 272
note), directs EPA to use voluntary consensus standards in its
regulatory activities unless to do so would be inconsistent with
applicable law or otherwise impractical. Voluntary consensus standards
are technical standards (e.g., material specifications, test methods,
sampling procedures, and business practices) that are developed or
adopted by voluntary consensus standard bodies. The NTTAA directs EPA
to provide Congress, through the OMB, explanations when the Agency
decides not to use available and applicable voluntary consensus
standards.
This final rule approves the use of technical standards developed
by the Standard Methods Committee, and
[[Page 40846]]
ASTM International for use in compliance monitoring where the Agency
has determined that those standards meet the needs of Clean Water Act
programs. EPA did not propose to add one Standard Method because that
method had not undergone full inter-laboratory validation as
recommended in current Agency guidance (see Section IV.C of the
proposal for this rule (80 FR 8956, February 19, 2015)). All proposed
voluntary consensus standards are approved in this rule.
J. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations
Executive Order (E.O.) 12898 (59 FR 7629 (Feb. 16, 1994))
establishes federal executive policy on environmental justice. Its main
provision directs federal agencies, to the greatest extent practicable
and permitted by law, to make environmental justice part of their
mission by identifying and addressing, as appropriate,
disproportionately high and adverse human health or environmental
effects of their programs, policies, and activities on minority
populations and low-income populations in the United States.
This final rule provides additional compliance methods for use by
any facility or laboratory with no disproportionate impact on minority
or low-income populations because it merely approves new and revised
versions of testing procedures to measure pollutants in water.
K. Congressional Review Act
The Congressional Review Act, 5 U.S.C. 801 et seq., as added by the
Small Business Regulatory Enforcement Fairness Act of 1996, generally
provides that before a rule may take effect, the agency promulgating
the rule must submit a rule report, which includes a copy of the rule,
to each House of the Congress and to the Comptroller General of the
United States. EPA will submit a report containing this rule and other
required information to the U.S. Senate, the U.S. House of
Representatives, and the Comptroller General of the United States prior
to publication of the rule in the Federal Register. This action is not
a ``major rule'' as defined by 5 U.S.C. 804(2). This rule will be
effective September 27, 2017.
List of Subjects in 40 CFR Part 136
Environmental protection, Incorporation by reference, Reporting and
recordkeeping requirements, Test procedures, Water pollution control.
Dated: August 7, 2017.
E. Scott Pruitt,
Administrator.
For the reasons set out in the preamble, title 40, chapter I of the
Code of Federal Regulations is 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 through 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 paragraphs (d) and (f) to read
as follows:
Sec. 136.2 Definitions.
* * * * *
(d) Director means the director as defined in 40 CFR 122.2.
* * * * *
(f) Detection limit means the minimum concentration of an analyte
(substance) that can be measured and reported with a 99% confidence
that the analyte concentration is distinguishable from the method blank
results as determined by the procedure set forth at appendix B of this
part.
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) 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)(lix), (b)(15)(lxi),
(b)(15)(lxiv), (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 new 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)(i).
0
h. Add paragraphs (b)(25)(ii) and (iii).
0
i. 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
j. Add new paragraphs (b)(26) and (34).
0
k. Revise newly redesignated paragraph (b)(35).
0
l. Revise paragraph (c) and Table II 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 texts of the
referenced test procedures are incorporated by reference into Tables
IA, IB, IC, ID, IE, IF, IG, and IH. The year after the method number
indicates the latest editorial change of the method. The discharge
parameter values for which reports are required must be
[[Page 40847]]
determined by one of the standard analytical test procedures
incorporated by reference and described in Tables IA, 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, in 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
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter and units Method \1\ EPA Standard methods AOAC, ASTM, USGS Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Bacteria
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Coliform (fecal), number per 100 Most Probable Number p. 132,\3\ 1680,11 15 9221 C E-2006........
mL or number per gram dry weight. (MPN), 5 tube, 3 1681 11 20.
dilution, or.
Multiple tube/multiple ...................... ..................... ..................... Colilert-18[supreg]13
well, or. 8 21 29.
Membrane filter (MF) p. 124 \3\............ 9222 D-2006 \30\..... B-0050-85 \4\........
\2\, single step.
2. Coliform (fecal) in presence of MPN, 5 tube, 3 p. 132 \3\............ 9221 C E-2006........
chlorine, number per 100 mL. dilution, or.
MF \2\, single step p. 124 \3\............ 9222 D-2006 \30\.....
\5\.
3. Coliform (total), number per 100 MPN, 5 tube, 3 p. 114 \3\............ 9221 B-2006..........
mL. dilution, or.
MF \2\, single step or p. 108 \3\............ 9222 B-2006.......... B-0025-85 \4\........
two step.
4. Coliform (total), in presence of MPN, 5 tube, 3 p. 114 \3\............ 9221 B-2006..........
chlorine, number per 100 mL. dilution, or.
MF \2\ with enrichment p. 111 \3\............ 9222 B-2006..........
\5\.
5. E. coli, number per 100 mL \21\. MPN 6 8 16 multiple ...................... 9221B.2-2006/9221F-
tube, or. 2006 12 14.
multiple tube/multiple ...................... 9223 B-2004 \13\..... 991.15 \10\.......... Colilert[supreg] 13
well, or. 18.
Colilert-18[supreg]
13 17 18
MF 2 6 7 8 single step 1603 \22\............. ..................... ..................... mColiBlue-
24[supreg]\19\.
6. Fecal streptococci, number per MPN, 5 tube, 3 p. 139 \3\............ 9230 B-2007..........
100 mL. dilution, or.
MF \2\, or............ p. 136 \3\............ 9230 C-2007.......... B-0055-85 \4\........ .....................
Plate count........... p. 143 \3\............
7. Enterococci, number per 100 mL MPN, 5 tube, 3 p. 139 \3\............ 9230 B-2007.......... ..................... .....................
\21\. dilution, or.
MPN 6 8, multiple tube/ ...................... 9230 D-2007.......... D6503-99 \9\......... Enterolert[supreg] 13
multiple well, or. 24.
MF 2 6 7 8 single step 1600 \25\............. 9230 C-2007..........
or.
Plate count........... p. 143 \3\............
8.Salmonella number per gram dry MPN multiple tube..... 1682 \23\.............
weight \11\.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Aquatic Toxicity
--------------------------------------------------------------------------------------------------------------------------------------------------------
9. Toxicity, acute, fresh water Ceriodaphnia dubia 2002.0 \26\...........
organisms, LC50, percent effluent. acute.
Daphnia puplex and 2021.0 \26\...........
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, estuarine and Mysid, Mysidopsis 2007.0 \26\...........
marine organisms of the Atlantic bahia, acute.
Ocean and Gulf of Mexico, LC50,
percent effluent.
Sheepshead Minnow, 2004.0 \26\...........
Cyprinodon
variegatus, acute.
Silverside, Menidia 2006.0 \26\...........
beryllina, Menidia
menidia, and Menidia
peninsulae, acute.
11. Toxicity, chronic, fresh water Fathead minnow, 1000.0 \27\...........
organisms, NOEC or IC25, percent Pimephales promelas,
effluent. larval survival and
growth.
[[Page 40848]]
Fathead minnow, 1001.0 \27\...........
Pimephales promelas,
embryo-larval
survival and
teratogenicity.
Daphnia, Ceriodaphnia 1002.0 \27\...........
dubia, survival and
reproduction.
Green alga, 1003.0 \27\...........
Selenastrum
capricornutum, growth.
12. Toxicity, chronic, estuarine Sheepshead minnow, 1004.0 \28\...........
and marine organisms of the Cyprinodon
Atlantic Ocean and Gulf of Mexico, variegatus, larval
NOEC or IC25, percent effluent. survival and growth.
Sheepshead minnow, 1005.0 \28\...........
Cyprinodon
variegatus, embryo-
larval survival and
teratogenicity.
Inland silverside, 1006.0 \28\...........
Menidia beryllina,
larval survival and
growth.
Mysid, Mysidopsis 1007.0 \28\...........
bahia, survival,
growth, and fecundity.
Sea urchin, Arbacia 1008.0 \28\...........
punctulata,
fertilization.
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IA notes:
\1\ The method must be specified when results are reported.
\2\ A 0.45-[mu]m membrane filter (MF) or other pore size certified by the manufacturer to fully retain organisms to be cultivated and to be free of
extractables which could interfere with their growth.
\3\ Microbiological Methods for Monitoring the Environment, Water, and Wastes, EPA/600/8-78/017. 1978. U.S. EPA.
\4\ U.S. Geological Survey Techniques of Water-Resource Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and Analysis of
Aquatic Biological and Microbiological Samples. 1989. USGS.
\5\ Because the MF technique usually yields low and variable recovery from chlorinated wastewaters, the Most Probable Number method will be required to
resolve any controversies.
\6\ Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes
to account for the quality, character, consistency, and anticipated organism density of the water sample.
\7\ When the MF method has been used previously to test waters with high turbidity, large numbers of noncoliform bacteria, or samples that may contain
organisms stressed by chlorine, a parallel test should be conducted with a multiple-tube technique to demonstrate applicability and comparability of
results.
\8\ To assess the comparability of results obtained with individual methods, it is suggested that side-by-side tests be conducted across seasons of the
year with the water samples routinely tested in accordance with the most current Standard Methods for the Examination of Water and Wastewater or EPA
alternate test procedure (ATP) guidelines.
\9\ Annual Book of ASTM Standards-Water and Environmental Technology, Section 11.02. 2000, 1999, 1996. ASTM International.
\10\ Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998. AOAC International.
\11\ Approved 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 [mu]g/mL of MUG may be used.
\15\ Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using Lauryl-Tryptose Broth (LTB) and EC Medium, EPA-821-R-
14-009. September 2014. U.S. EPA.
\16\ Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube and
dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert[supreg] may be enumerated with
the multiple-well procedures, Quanti-Tray[supreg] 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\ Approved for enumeration of target organism in wastewater effluent.
\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. September 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\ To use Colilert-18[supreg] to assay for fecal coliforms, the incubation temperature is 44.5 0.2 [deg]C, and a water bath incubator is
used.
[[Page 40849]]
\30\ On a monthly basis, at least ten blue colonies from the medium must be verified using Lauryl Tryptose Broth and EC broth, followed by count
adjustment based on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications
should be done from randomized sample sources.
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-2011.......... 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 aspiration ...................... 3111 D-2011 or 3111 E- ..................... I-3051-85.\2\
\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, 4500- ..................... I-4523-85.\2\
salicylate, or other (1993). 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 aspiration ...................... 3111 B-2011..........
\36\.
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\
6. Arsenic-Total,\4\ mg/L.......... Digestion,\4\ followed 206.5 (Issued 1978)
by any of the \1\.
following:.
AA gaseous hydride.... ...................... 3114 B-2011 or 3114 C- D2972-08 (B)......... I-3062-85.\2\
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 aspiration ...................... 3111 D-2011.......... ..................... I-3084-85.\2\
\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 aspiration.. ...................... 3111 D-2011 or 3111 E- D3645-08 (A)......... I-3095-85.\2\
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).
[[Page 40850]]
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,\9\
(BOD5), mg/L. Depletion. I-1578-78,\8\ See
footnote.10 63
10. Boron--Total,\37\ mg/L......... Colorimetric ...................... 4500-B B-2011........ ..................... I-3112-85.\2\
(curcumin).
ICP/AES............... 200.5, Rev 4.2 (2003); 3120 B-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, 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:
AA direct aspiration ...................... 3111 B-2011 or 3111 C- D3557-12 (A or B).... 974.27,\3\ p. 37,\9\
\36\. 2011. 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 aspiration.. ...................... 3111 B-2011.......... D511-09(B)........... I-3152-85.\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\
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 63
demand (CBOD5), mg/L \12\. Depletion with
nitrification
inhibitor.
15. Chemical oxygen demand (COD), Titrimetric........... 410.3 (Rev. 1978) \1\. 5220 B-2011 or C-2011 D1252-06 (A)......... 973.46,\3\ p. 17,\9\
mg/L. I-3560-85.\2\
Spectrophotometric, 410.4, Rev. 2.0 (1993) 5220 D-2011.......... D1252-06 (B)......... See footnotes.13 14,
manual or automatic. 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: Manual.. ...................... ..................... ..................... I-1187-85.\2\
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, 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 ether ...................... 4500-Cl C-2011.......
end-point \15\.
DPD-FAS............... ...................... 4500-Cl F-2011.......
Spectrophotometric, ...................... 4500-Cl G-2011.......
DPD.
Electrode............. ...................... ..................... ..................... See footnote.\16\
17A. Chlorine-Free Available, mg/L. Amperometric direct... ...................... 4500-Cl D-2011....... D1253-08.............
Amperometric direct ...................... 4500-Cl E-2011.......
(low level).
DPD-FAS............... ...................... 4500-Cl F-2011.......
Spectrophotometric, ...................... 4500-Cl G-2011.......
DPD.
18. Chromium VI dissolved, mg/L.... 0.45-micron filtration
followed by any of
the following:
AA chelation- ...................... 3111 C-2011.......... ..................... I-1232-85.\2\
extraction.
Ion Chromatography.... 218.6, Rev. 3.3 (1994) 3500-Cr C-2011....... D5257-11............. 993.23.\3\
Colorimetric (diphenyl- ...................... 3500-Cr B-2011....... D1687-12 (A)......... I-1230-85.\2\
carbazide).
19. Chromium--Total,\4\ mg/L....... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2011.......... D1687-12 (B)......... 974.27,\3\ I-3236-
\36\. 85.\2\
AA chelation- ...................... 3111 C-2011..........
extraction.
AA furnace............ ...................... 3113 B-2010.......... D1687-12 (C)......... I-3233-93.\46\
[[Page 40851]]
STGFAA................ 200.9, Rev. 2.2 (1994)
ICP/AES \36\.......... 200.5, Rev 4.2 3120 B-2011.......... D1976-12............. I-4471-97.\50\
(2003),\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 (diphenyl- ...................... 3500-Cr B-2011.......
carbazide).
20. Cobalt--Total,\4\ mg/L......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2011 or 3111 C- D3558-08 (A or B).... p. 37,\9\ I-3239-
2011. 85.\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 \78\.....
dominant wavelength, hue,
luminance purity.
Platinum cobalt visual ...................... 2120 B-2011.......... ..................... I-1250-85.\2\
comparison.
Spectrophotometric.... ...................... ..................... ..................... See footnote.\18\
22. Copper--Total,\4\ mg/L......... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2011 or 3111 C- D1688-12 (A or B).... 974.27,\3\ p. 37,\9\
\36\. 2011. 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.
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 C- D2036-09(A), D7284-13 10-204-00-1-X.\56\
with MgCl2, followed \57\. 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 Distillation ...................... ..................... ..................... Kelada-01.\55\
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-diffusion ...................... ..................... D4282-02.............
and colorimetry.
25. Fluoride--Total, mg/L.......... Manual ...................... 4500-F- B-2011.......
distillation,\6\
followed by any of
the following:
Electrode, manual..... ...................... 4500-F- C-2011....... D1179-10 (B).........
Electrode, automated.. ...................... ..................... ..................... I-4327-85.\2\
Colorimetric, (SPADNS) ...................... 4500-F- D-2011....... D1179-10 (A).........
[[Page 40852]]
Automated complexone.. ...................... 4500-F- E-2011.......
Ion Chromatography.... 300.0, Rev 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30.\3\
and 300.1, 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 aspiration.. ...................... 3111 B-2011..........
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\
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 aspiration.. ...................... 3111 B-2011..........
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 aspiration ...................... 3111 B-2011 or 3111 C- D1068-10 (A)......... 974.27,\3\ I-3381-
\36\. 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 3120 B-2011.......... D1976-12............. I-4471-97.\50\
(2003); \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 B-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 phenate 350.1, Rev. 2.0 (1993) 4500-NH3 G-2011 4500-
NH3 H-2011.
Manual phenate, ...................... 4500-NH3 F-2011...... ..................... See footnote.\60\
salicylate, or other
substituted phenols
in Berthelot reaction
based methods.
Automated gas ...................... ..................... ..................... Timberline Ammonia-
diffusion, followed 001.\74\
by conductivity cell
analysis.
--------------------------------------------------------------------------------------------------------------------
Automated Methods for TKN that do not require manual distillation.
--------------------------------------------------------------------------------------------------------------------
Automated phenate, 351.1 (Rev. 1978) \1\. ..................... ..................... I-4551-78.\8\
salicylate, or other
substituted phenols
in Berthelot reaction
based methods
colorimetric (auto
digestion and
distillation).
Semi-automated block 351.2, Rev. 2.0 (1993) 4500-Norg D-2011..... D3590-11 (B)......... I-4515-91.\45\
digestor colorimetric
(distillation not
required).
Block digester, ...................... ..................... ..................... See footnote.\39\
followed by Auto
distillation and
Titration.
[[Page 40853]]
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.\76\
peroxdisulfate,
followed by
Spectrophotometric
(2,6-dimethyl phenol).
Digestion with ...................... ..................... ..................... NCASI TNTP
persulfate, followed W10900.\77\
by Colorimetric.
32. Lead--Total,\4\ mg/L........... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2011 or 3111 C- D3559-08 (A or B).... 974.27,\3\ I-3399-
\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 3120 B-2011.......... D1976-12............. I-4471-97.\50\
(2003); \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 aspiration.. ...................... 3111 B-2011.......... D511-09 (B).......... 974.27,\3\ I-3447-
85.\2\
ICP/AES............... 200.5, Rev. 4.2 3120 B-2011.......... D1976-12............. I-4471-97.\50\
(2003); \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 aspiration ...................... 3111 B-2011.......... D858-12 (A or B)..... 974.27,\3\ I-3454-
\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 3120 B-2011.......... D1976-12............. I-4471-97.\50\
(2003); \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\
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, Automated. 245.2 (Issued 1974)
\1\.
Cold vapor atomic 245.7 Rev. 2.0 (2005) ..................... ..................... I-4464-01.\71\
fluorescence \17\.
spectrometry (CVAFS).
Purge and Trap CVAFS.. 1631E \43\............
36. Molybdenum--Total,\4\ mg/L..... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 D-2011.......... ..................... I-3490-85.\2\
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 aspiration ...................... 3111 B-2011 or 3111 C- D1886-08 (A or B).... I-3499-85.\2\
\36\. 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 3120 B-2011.......... D1976-12............. I-4471-97.\50\
(2003); \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, Rev. 1.0
(1997).
CIE/UV................ ...................... 4140 B-2011.......... D6508-10............. D6508, Rev. 2.\54\
Ion Selective ...................... 4500-NO3- D-2011.....
Electrode.
Colorimetric (Brucine 352.1 (Issued 1971) ..................... ..................... 973.50,\3\ 419D1, 7
sulfate). \1\. p. 28.\9\
Spectrophotometric ...................... ..................... ..................... Hach 10206.\75\
(2,6-dimethylphenol).
Nitrate-nitrite N
minus Nitrite N (See
parameters 39 and 40).
39. Nitrate-nitrite (as N), mg/L... Cadmium reduction, ...................... 4500-NO3- E-2011..... D3867-04 (B).........
Manual.
[[Page 40854]]
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/Colorimetric ...................... ..................... ..................... See footnote.\62\
Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30.\3\
and 300.1, Rev. 1.0
(1997).
CIE/UV................ ...................... 4140 B-2011.......... D6508-10............. D6508, Rev. 2.\54\
Enzymatic reduction, ...................... ..................... ..................... I-2547-11,\72\ I-2548-
followed by automated 11,\72\ N07-
colorimetric 0003.\73\
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, Rev. 1.0
(1997).
CIE/UV................ ...................... 4140 B-2011.......... D6508-10............. D6508, Rev. 2.\54\
Automated (*bypass ...................... ..................... ..................... I-2547-11,\72\ I-2548-
Enzymatic reduction). 11,\72\ N07-
0003.\73\
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 HEM 1664 Rev. A; 1664 Rev. 5520 B-2011 \38\ and
(SGT-HEM): Silica gel B \42\. 5520 F-2011\38\.
treatment and
gravimetry.
42. Organic carbon--Total (TOC), mg/ Combustion............ ...................... 5310 B-2011.......... D7573-09............. 973.47,\3\ p. 14.\24\
L.
Heated persulfate or ...................... 5310 C-2011, 5310 D- D4839-03............. 973.47,\3\ p. 14.\24\
UV persulfate 2011.
oxidation.
43. Organic nitrogen (as N), mg/L.. Total Kjeldahl N
(Parameter 31) minus
ammonia N (Parameter
4).
44. Ortho-phosphate (as P), mg/L... Ascorbic acid method:
Automated............. 365.1, Rev. 2.0 (1993) 4500-P F-2011 or G- ..................... 973.56,\3\ I-4601-
2011. 85.\2\
Manual single reagent. ...................... 4500-P E-2011........ D515-88 (A).......... 973.55.\3\
Manual two reagent.... 365.3 (Issued 1978)
\1\.
Ion Chromatography.... 300.0, Rev. 2.1 (1993) 4110 B-2011 or C-2011 D4327-03............. 993.30.\3\
and 300.1, 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 aspiration.. ...................... 3111 D-2011..........
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\
Luminescence Based ...................... ..................... D888-09 (C).......... See footnote.\63\ See
Sensor. footnote.\64\
47. Palladium--Total,\4\ mg/L...... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2011..........
AA furnace............ 253.2 (Issued 1978)
\1\.
ICP/MS................ ...................... 3125 B-2011..........
DCP................... ...................... ..................... ..................... See footnote.\34\
48. Phenols, mg/L.................. Manual 420.1 (Rev. 1978) \1\. 5530 B-2010.......... D1783-01.............
distillation,\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 colorimetric 420.4 Rev. 1.0 (1993).
(4AAP).
49. Phosphorus (elemental), mg/L... Gas-liquid ...................... ..................... ..................... See footnote.\28\
chromatography.
50. Phosphorus--Total, mg/L........ Digestion,\20\ ...................... 4500-P B(5)-2011..... ..................... 973.55.\3\
followed by any of
the following:
Manual................ 365.3 (Issued 1978) 4500-P E-2011........ D515-88 (A)..........
\1\.
[[Page 40855]]
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 block 365.4 (Issued 1974) ..................... D515-88 (B).......... I-4610-91.\48\
digestor (TKP \1\.
digestion).
Digestion with ...................... ..................... ..................... NCASI TNTP
persulfate, followed W10900.\77\
by Colorimetric.
51. Platinum--Total \4\, mg/L...... Digestion,\4\ followed
by any of the
following:
AA direct aspiration.. ...................... 3111 B-2011..........
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 aspiration.. ...................... 3111 B-2011.......... ..................... 973.53,\3\ I-3630-
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 aspiration, ...................... 3111 B-2011..........
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 aspiration, ...................... 3111 B-2011..........
or.
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, Manual.. ...................... 4500-SiO2 C-2011..... D859-10.............. I-1700-85.\2\
Automated ...................... 4500-SiO2 E-2011 or F- ..................... I-2700-85.\2\
(Molybdosilicate). 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 aspiration.. ...................... 3111 B-2011 or 3111 C- ..................... 974.27,\3\ p. 37,\9\
2011. 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 aspiration.. ...................... 3111 B-2011.......... ..................... 973.54,\3\ I-3735-
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\
[[Page 40856]]
65. Sulfate (as SO4), mg/L......... Automated colorimetric 375.2, Rev. 2.0 (1993) 4500-SO42- F-2011 or
G-2011.
Gravimetric........... ...................... 4500-SO42- C-2011 or ..................... 925.54.\3\
D-2011.
Turbidimetric......... ...................... 4500-SO42- 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, 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-S2- B, C-2011...
Titrimetric (iodine).. ...................... 4500-S2- F-2011...... ..................... I-3840-85.\2\
Colorimetric ...................... 4500-S2- D-2011......
(methylene blue).
Ion Selective ...................... 4500-S2- G-2011...... D4658-09.............
Electrode.
67. Sulfite (as SO3), mg/L......... Titrimetric (iodine- ...................... 4500-SO32- 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 aspiration.. ...................... 3111 B-2011..........
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 aspiration.. ...................... 3111 B-2011.......... ..................... I-3850-78.\8\
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 aspiration.. ...................... 3111 D-2011..........
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 aspiration.. ...................... 3111 D-2011..........
AA furnace............ ...................... 3113 B-2010.......... D3373-12.............
ICP/AES............... 200.5, Rev. 4.2 3120 B-2011.......... D1976-12............. I-4471-97.\50\
(2003); \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 (Gallic ...................... 3500-V B-2011........
Acid).
75. Zinc--Total,\4\ mg/L........... Digestion,\4\ followed
by any of the
following:
AA direct aspiration ...................... 3111 B-2011 or 3111 C- D1691-12 (A or B).... 974.27,\3\ p. 37,\9\
\36\. 2011. 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 (Zincon). ...................... 3500 Zn B-2011....... ..................... See footnote.\33\
76. Acid Mine Drainage............. ...................... 1627 \69\.............
--------------------------------------------------------------------------------------------------------------------------------------------------------
Table IB Notes:
\1\ Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020. Revised March 1983 and 1979, where applicable. U.S. EPA.
\2\ Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resource Investigations of the U.S. Geological
Survey, Book 5, Chapter A1., unless otherwise stated. 1989. USGS.
\3\ Official Methods of Analysis of the Association of Official Analytical Chemists, Methods Manual, Sixteenth Edition, 4th Revision, 1998. AOAC
International.
\4\ For the determination of total metals (which are equivalent to total recoverable metals) the sample is not filtered before processing. A digestion
procedure is required to solubilize analytes in suspended material and to break down organic-metal complexes (to convert the analyte to a detectable
form for colorimetric analysis). For non-platform graphite furnace atomic absorption determinations, a digestion using nitric acid (as specified in
Section 4.1.3 of Methods for 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.
[[Page 40857]]
\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 5-day BOD.'' The
addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit
requires reporting the traditional BOD5 may not use a nitrification inhibitor in the procedure for reporting the results. Only when a discharger's
permit specifically states CBOD5 is required can the permittee report data using a nitrification inhibitor.
\13\ OIC Chemical Oxygen Demand Method. 1978. Oceanography International Corporation.
\14\ Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company.
\15\ The back titration method will be used to resolve controversy.
\16\ Orion Research Instruction Manual, Residual Chlorine Electrode Model 97-70. 1977. Orion Research Incorporated. The calibration graph for the Orion
residual chlorine method must be derived using a reagent blank and three standard solutions, containing 0.2, 1.0, and 5.0 mL 0.00281 N potassium
iodate/100 mL solution, respectively.
\17\ Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-05-001. Revision 2.0, February 2005. US EPA.
\18\ National Council of the Paper Industry for Air and Stream Improvement (NCASI) Technical Bulletin 253 (1971) and Technical Bulletin 803, May 2000.
\19\ Method 8506, Bicinchoninate Method for Copper, Hach Handbook of Water Analysis. 1979. Hach Company.
\20\ When using a method with block digestion, this treatment is not required.
\21\ Industrial Method Number 378-75WA, Hydrogen ion (pH) Automated Electrode Method, Bran & Luebbe (Technicon) Autoanalyzer II. October 1976. Bran &
Luebbe Analyzing Technologies.
\22\ Method 8008, 1,10-Phenanthroline Method using FerroVer Iron Reagent for Water. 1980. Hach Company.
\23\ Method 8034, Periodate Oxidation Method for Manganese, Hach Handbook of Wastewater Analysis. 1979. Hach Company.
\24\ Methods for Analysis of Organic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S. Geological
Survey, Book 5, Chapter A3, (1972 Revised 1987). 1987. USGS.
\25\ Method 8507, Nitrogen, Nitrite-Low Range, Diazotization Method for Water and Wastewater. 1979. Hach Company.
\26\ Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH.
\27\ The colorimetric reaction must be conducted at a pH of 10.0 0.2.
\28\ Addison, R.F., and R.G. Ackman. 1970. Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography, Journal of Chromatography,
47(3):421-426.
\29\ Approved methods for the analysis of silver in industrial wastewaters at concentrations of 1 mg/L and above are inadequate where silver exists as
an inorganic halide. Silver halides such as the bromide and chloride are relatively insoluble in reagents such as nitric acid but are readily soluble
in an aqueous buffer of sodium thiosulfate and sodium hydroxide to pH of 12. Therefore, for levels of silver above 1 mg/L, 20 mL of sample should be
diluted to 100 mL by adding 40 mL each of 2 M Na2S2O3and NaOH. Standards should be prepared in the same manner. For levels of silver below 1 mg/L the
approved method is satisfactory.
\30\ The use of EDTA decreases method sensitivity. Analysts may omit EDTA or replace with another suitable complexing reagent provided that all method
specified quality control acceptance criteria are met.
\31\ For samples known or suspected to contain high levels of silver (e.g., in excess of 4 mg/L), cyanogen iodide should be used to keep the silver in
solution for analysis. Prepare a cyanogen iodide solution by adding 4.0 mL of concentrated NH4OH, 6.5 g of KCN, and 5.0 mL of a 1.0 N solution of I2
to 50 mL of reagent water in a volumetric flask and dilute to 100.0 mL. After digestion of the sample, adjust the pH of the digestate to >7 to prevent
the formation of HCN under acidic conditions. Add 1 mL of the cyanogen iodide solution to the sample digestate and adjust the volume to 100 mL with
reagent water (NOT acid). If cyanogen iodide is added to sample digestates, then silver standards must be prepared that contain cyanogen iodide as
well. Prepare working standards by diluting a small volume of a silver stock solution with water and adjusting the pH>7 with NH4OH. Add 1 mL of the
cyanogen iodide solution and let stand 1 hour. Transfer to a 100-mL volumetric flask and dilute to volume with water.
\32\ ``Water Temperature-Influential Factors, Field Measurement and Data Presentation,'' Techniques of Water-Resources Investigations of the U.S.
Geological Survey, Book 1, Chapter D1. 1975. USGS.
\33\ Method 8009, Zincon Method for Zinc, Hach Handbook of Water Analysis, 1979. Hach Company.
\34\ Method AES0029, Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes. 1986-Revised
1991. Thermo Jarrell Ash Corporation.
\35\ In-Situ Method 1004-8-2009, Carbonaceous Biochemical Oxygen Demand (CBOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.
\36\ Microwave-assisted digestion may be employed for this metal, when analyzed by this methodology. Closed Vessel Microwave Digestion of Wastewater
Samples for Determination of Metals. April 16, 1992. CEM Corporation.
\37\ When determining boron and silica, only plastic, PTFE, or quartz laboratory ware may be used from start until completion of analysis.
\38\ Only use n-hexane (n-Hexane--85% minimum purity, 99.0% min. saturated C6 isomers, residue less than 1 mg/L) extraction solvent when determining Oil
and Grease parameters--Hexane Extractable Material (HEM), or Silica Gel Treated HEM (analogous to EPA Methods 1664 Rev. A and 1664 Rev. B). Use of
other extraction solvents is prohibited.
\39\ Method PAI-DK01, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Titrimetric Detection. Revised December 22, 1994. OI Analytical.
\40\ Method PAI-DK02, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Colorimetric Detection. Revised December 22, 1994. OI Analytical.
\41\ Method PAI-DK03, Nitrogen, Total Kjeldahl, Block Digestion, Automated FIA Gas Diffusion. Revised December 22, 1994. OI Analytical.
\42\ Method 1664 Rev. B is the revised version of EPA Method 1664 Rev. A. U.S. EPA. February 1999, Revision A. Method 1664, n-Hexane Extractable
Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM; Non-polar Material) by Extraction and Gravimetry. EPA-
821-R-98-002. U.S. EPA. February 2010, Revision B. Method 1664, n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane
Extractable Material (SGT-HEM; Non-polar Material) by Extraction and Gravimetry. EPA-821-R-10-001.
\43\ Method 1631, Revision E, Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-02-019. Revision
E. August 2002, U.S. EPA. The application of clean techniques described in EPA's Method 1669: Sampling Ambient Water for Trace Metals at EPA Water
Quality Criteria Levels, EPA-821-R-96-011, are recommended to preclude contamination at low-level, trace metal determinations.
\44\ Method OIA-1677-09, Available Cyanide by Ligand Exchange and Flow Injection Analysis (FIA). 2010. OI Analytical.
\45\ Open File Report 00-170, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Ammonium Plus
Organic Nitrogen by a Kjeldahl Digestion Method and an Automated Photometric Finish that Includes Digest Cleanup by Gas Diffusion. 2000. USGS.
\46\ Open File Report 93-449, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Chromium in Water by
Graphite Furnace Atomic Absorption Spectrophotometry. 1993. USGS.
\47\ Open File Report 97-198, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Molybdenum by
Graphite Furnace Atomic Absorption Spectrophotometry. 1997. USGS.
\48\ Open File Report 92-146, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Total Phosphorus by
Kjeldahl Digestion Method and an Automated Colorimetric Finish That Includes Dialysis. 1992. USGS.
\49\ Open File Report 98-639, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Arsenic and Selenium
in Water and Sediment by Graphite Furnace-Atomic Absorption Spectrometry. 1999. USGS.
\50\ Open File Report 98-165, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Elements in Whole-
water Digests Using Inductively Coupled Plasma-Optical Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry. 1998. USGS.
\51\ Open File Report 93-125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination of Inorganic and
Organic Constituents in Water and Fluvial Sediments. 1993. USGS.
\52\ Unless otherwise indicated, all EPA methods, excluding EPA Method 300.1, are published in U.S. EPA. May 1994. Methods for the Determination of
Metals in Environmental Samples, Supplement I, EPA/600/R-94/111; or U.S. EPA. August 1993. Methods for the Determination of Inorganic Substances in
Environmental Samples, EPA/600/R-93/100. EPA Method 300.1 is 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.
[[Page 40858]]
\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.
\70\ Techniques and Methods Book 5-B1, Determination of Elements in Natural-Water, Biota, Sediment and Soil Samples Using Collision/Reaction Cell
Inductively Coupled Plasma-Mass Spectrometry, Chapter 1, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis,
2006. USGS.
\71\ Water-Resources Investigations Report 01-4132, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination
of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural Water with Cold Vapor-Atomic Fluorescence Spectrometry, 2001. USGS.
\72\ USGS Techniques and Methods 5-B8, Chapter 8, Section B, Methods of the National Water Quality Laboratory Book 5, Laboratory Analysis, 2011 USGS.
\73\ NECi Method N07-0003, ''Nitrate Reductase Nitrate-Nitrogen Analysis,'' Revision 9.0, March 2014, The Nitrate Elimination Co., Inc.
\74\ Timberline Instruments, LLC Method Ammonia-001, ``Determination of Inorganic Ammonia by Continuous Flow Gas Diffusion and Conductivity Cell
Analysis,'' June 2011, Timberline Instruments, LLC.
\75\ Hach Company Method 10206, ``Spectrophotometric Measurement of Nitrate in Water and Wastewater,'' Revision 2.1, January 2013, Hach Company.
\76\ Hach Company Method 10242, ``Simplified Spectrophotometric Measurement of Total Kjeldahl Nitrogen in Water and Wastewater,'' Revision 1.1, January
2013, Hach Company.
\77\ National Council for Air and Stream Improvement (NCASI) Method TNTP-W10900, ``Total (Kjeldahl) Nitrogen and Total Phosphorus in Pulp and Paper
Biologically Treated Effluent by Alkaline Persulfate Digestion,'' June 2011, National Council for Air and Stream Improvement, Inc.
\78\ The pH adjusted sample is to be adjusted to 7.6 for NPDES reporting purposes.
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........................ 6440 B-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 40859]]
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................. 624.1, 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............... .................................... ....................................
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.
[[Page 40860]]
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-dibenzo- GC/MS................. 1613B...................... .......................... .................................... ....................................
p-dioxin.
71. 1,2,3,6,7,8-Hexachloro-dibenzo- GC/MS................. 1613B...................... .......................... .................................... ....................................
p-dioxin.
72. 1,2,3,7,8,9-Hexachloro-dibenzo- GC/MS................. 1613B...................... .......................... .................................... ....................................
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.
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\
[[Page 40861]]
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-dibenzo- GC/MS................. 1613B...................... .......................... .................................... ....................................
p-dioxin.
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-p- GC/MS................. 613, 625.1,\5a\ 1613B...... .......................... .................................... ....................................
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. The standardized test procedure to be used to
determine the method detection limit (MDL) for these test procedures is given at appendix B of this part, Definition and Procedure for the Determination of the Method Detection Limit. These
methods are available at: https://www.epa.gov/cwa-methods as individual PDF files.
\3\ Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA.
\4\ Method 624.1 may be used for quantitative determination of acrolein and acrylonitrile, provided that the laboratory has documentation to substantiate the ability to detect and quantify
these analytes at levels necessary to comply with any associated regulations. In addition, the use of sample introduction techniques other than simple purge-and-trap may be required. QC
acceptance criteria from Method 603 should be used when analyzing samples for acrolein and acrylonitrile in the absence of such criteria in Method 624.1.
\5\ Method 625.1 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, N-nitrosodi-n-propylamine, and N-nitrosodiphenylamine. However, when they are known to
be present, Methods 605, 607, and 612, or Method 1625B, are preferred methods for these compounds.
\5a\ Method 625.1 screening only.
\6\ Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency, Supplement to the 15th Edition of Standard Methods for the Examination of Water and
Wastewater. 1981. American Public Health Association (APHA).
\7\ Each analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601-603, 1624B, and 1625B in accordance with
procedures 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
quality control (QC) acceptance criteria in the pertinent method, analytical results for that parameter in the unspiked sample are suspect. The results should be reported but cannot be used
to demonstrate regulatory compliance. If the method does not contain QC acceptance criteria, control limits of +/- three standard deviations around the mean of a minimum of five replicate
measurements must be used. These quality control requirements also apply to the Standard Methods, ASTM Methods, and other methods cited.
\8\ Organochlorine Pesticides and PCBs in Wastewater Using Empore\TM\ Disk. Revised October 28, 1994. 3M Corporation.
\9\ Method O-3116-87 is in Open File Report 93-125, Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory--Determination of Inorganic and Organic Constituents in
Water and Fluvial Sediments. 1993. USGS.
[[Page 40862]]
\10\ Analysts may use Fluid Management Systems, Inc. Power-Prep system in place of manual cleanup provided the analyst meets the requirements of Method 1613B (as specified in Section 9 of the
method) and permitting authorities. Method 1613, Revision B, Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS. Revision B, 1994. U.S. EPA. The full text of
this method is provided in appendix A to this part and at https://www.epa.gov/cwa-methods/approved-cwa-methods-organic-compounds.
\11\ Method 1650, Adsorbable Organic Halides by Adsorption and Coulometric Titration. Revision C, 1997 U.S. EPA. Method 1653, Chlorinated Phenolics in Wastewater by In Situ Acetylation and
GCMS. Revision A, 1997 U.S. EPA. The full text for both of these methods is provided at appendix A in part 430 of this chapter, The Pulp, Paper, and Paperboard Point Source Category.
\12\ The compound was formerly inaccurately labeled as 2,2'-oxybis(2-chloropropane) and bis(2-chloroisopropyl) ether. Some versions of Methods 611, and 1625 inaccurately list the analyte as
``bis(2-chloroisopropyl)ether,'' but use the correct CAS number of 108-60-1.
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.
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..........
[[Page 40863]]
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.
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, 6410 B-2000..........
625.1\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.................. ..................... ..................... ..................... See footnote,\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.
GC/MS.................. 525.1, 525.2, 625.1.. ..................... ..................... See footnote,\11\ O-
1126-95.
[[Page 40864]]
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.
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 of this
section, where entries are listed by chemical name.
\2\ The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at appendix B of this
part, Definition and Procedure for the Determination of the Method Detection Limit.
\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.
[[Page 40865]]
\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 https://www.epa.gov/cwa-methods/approved-cwa-test-methods-organic-compounds.
\11\ Method O-1126-95 is in Open-File Report 95-181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination
of pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring. 1995.
USGS.
\12\ Method O-2060-01 is in Water-Resources Investigations Report 01-4134, Methods of Analysis by the U.S. Geological Survey National Water Quality
Laboratory--Determination of Pesticides in Water by Graphitized Carbon-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass
Spectrometry. 2001. USGS.
\13\ Method O-2002-01 is in Water-Resources Investigations Report 01-4098, Methods of Analysis by the U.S. Geological Survey National Water Quality
Laboratory--Determination of moderate-use pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass
spectrometry. 2001. USGS.
\14\ Method O-1121-91 is in Open-File Report 91-519, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory--Determination
of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion
monitoring. 1992. USGS.
* * * * *
Table IF--List of Approved Methods for Pharmaceutical Pollutants
----------------------------------------------------------------------------------------------------------------
CAS registry
Pharmaceuticals pollutants No. Analytical 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
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 IF 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 IG--Test Methods for Pesticide Active Ingredients
[40 CFR part 455]
------------------------------------------------------------------------
EPA analytical
EPA survey code Pesticide name CAS No. method No.(s)
\3\
------------------------------------------------------------------------
8................... Triadimefon..... 43121-43-3 507/633/525.1/
525.2/1656/
625.1.
[[Page 40866]]
12.................. Dichlorvos...... 62-73-7 1657/507/622/
525.1/525.2/
625.1.
16.................. 2,4-D; 2,4-D 94-75-7 1658/515.1/615/
Salts and 515.2/555.
Esters [2,4-
Dichloro-
phenoxyacetic
acid].
17.................. 2,4-DB; 2,4-DB 94-82-6 1658/515.1/615/
Salts and 515.2/555.
Esters [2,4-
Dichlorophenoxy
butyric 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 94-74-6 1658/615/555.
and Esters.
[2-Methyl-4-
chlorophenoxyac
etic acid].
30.................. Dichlorprop; 120-36-5 1658/515.1/615/
Dichlorprop 515.2/555.
Salts and
Esters [2-(2,4-
Dichlorophenoxy
) propionic
acid].
31.................. MCPP; MCPP Salts 93-65-2 1658/615/555.
and Esters [2-
(2-Methyl-4-
chlorophenoxy)
propionic acid].
35.................. TCMTB [2- 21564-17-0 637.
(Thiocyanomethy
lthio) 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; 314-40-9 507/633/525.1/
Bromacil Salts 525.2/1656/
and Esters. 608.3/625.1.
69.................. Bromoxynil...... 1689-84-5 1625/1661/625.1.
69.................. Bromoxynil 1689-99-2 1656/608.3.
Octanoate.
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.
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 1861-32-1 508/608.2/525.1/
2,3,5,6- 525.2/515.1 \2\/
tetrachloro- 515.2 \2\/1656/
terephthalate]. 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 138-93-2 630.1.
[Disodium
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.
(Phosphonomethy
l) 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 12379-54-3 Ind-01/200.7/
pesticides. 200.9.
197................. Bolstar......... 35400-43-2 1657/622.
[[Page 40867]]
203................. Parathion....... 56-38-2 1657/614/625.1.
204................. Pendimethalin... 40487-42-1 1656.
205................. Pentachloronitro 82-68-8 1656/608.1/617/
benzene. 608.3/625.1.
206................. Pentachloropheno 87-86-5 1625/515.2/555/
l. 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 85 128-03-0 630/630.1.
[Potassium
dimethyldithioc
arbamate].
219................. Busan 40 51026-28-9 630/630.1.
[Potassium N-
hydroxymethyl-N-
methyldithiocar
bamate].
220................. KN Methyl 137-41-7 630/630.1.
[Potassium N-
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- 78-48-8 1657.
Tributyl
phosphorotrithi
oate].
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.
methyldithiocar
bamate].
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 150-50-5 1657/507/525.1/
[Tributyl 525.2/622/
phosphorotrithi 625.1.
oate].
264................. Trifluralin \1\. 1582-09-8 1656/508/617/627/
525.2/608.3/
625.1.
268................. Ziram [Zinc 137-30-4 630/630.1.
dimethyldithioc
arbamate].
------------------------------------------------------------------------
Table IG 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. The full text of Method 200.7 is provided at appendix C of this
part. Methods 608.3 and 625.1 are available at https://www.epa.gov/cwa-methods/approved-cwa-test-methods-organic-compounds.
\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 IH--List of Approved Microbiological Methods for Ambient Water
--------------------------------------------------------------------------------------------------------------------------------------------------------
Parameter and units Method \1\ EPA Standard methods AOAC, ASTM, USGS Other
--------------------------------------------------------------------------------------------------------------------------------------------------------
Bacteria
--------------------------------------------------------------------------------------------------------------------------------------------------------
1. Coliform (fecal), number per Most Probable Number p. 132 \3\.................. 9221 C E-2006.
100 mL or number per gram dry (MPN), 5 tube, 3
weight. dilution, or.
Membrane filter p. 124 \3\.................. 9222 D-2006 \ 27\... B-0050-85. \4\
(MF),\2\ single
step.
2. Coliform (fecal) in presence of MPN, 5 tube, 3 p. 132 \3\.................. 9221 C E-2006.
chlorine, number per 100 mL. dilution, or.
MF,\2\ single step p. 124 \3\.................. 9222 D-2006. \ 27\
\5\.
3. Coliform (total), number per MPN, 5 tube, 3 p. 114 \3\.................. 9221 B-2006.
100 mL. dilution, or.
MF,\2\ single step p. 108 \3\.................. 9222 B-2006......... B-0025-85. \4\
or two step.
4. Coliform (total), in presence MPN, 5 tube, 3 p. 114 \3\.................. 9221 B-2006.
of chlorine, number per 100 mL. dilution, or.
MF \2\ with p. 111 \3\.................. 9222 B-2006.
enrichment.
5. E. coli, number per 100 mL..... MPN,6 8 14 multiple ............................ 9221 B.2-2006/9221 F-
tube, or. 2006 11 13.
Multiple tube/ ............................ 9223 B-2004 \12\.... 991.15 \10\......... Colilert[supreg],12
multiple well, or. 16 Colilert-
18[supreg].12 15 16
MF,2 5 6 7 8 two 1103.1 \19\................. 9222 B-2006/9222 G- D-5392-93. \9\
step, or. 2006,\18\ 9213 D-
2007.
Single step......... 1603,\20\ 1604 \21\......... .................... .................... mColiBlue-
24[supreg].\17\
6. Fecal streptococci, number per MPN, 5 tube, 3 p. 139 \3\.................. 9230 B-2007.
100 mL. dilution, or.
MF \2\, or.......... p. 136 \3\.................. 9230 C-2007......... B-0055-85 \4\....... ....................
[[Page 40868]]
Plate count......... p. 143. \3\
7. Enterococci, number per 100 mL. MPN,6 8 multiple ............................ 9230 D-2007......... D6503-99 \9\........ Enterolert[supreg].1
tube/multiple well, 2 22
or.
MF 2 5 6 7 8 two 1106.1 \23\................. 9230 C-2007......... D5259-92. \9\
step, or.
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 IH 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. U.S. EPA.
\4\ U.S. Geological Survey Techniques of Water-Resource Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and Analysis of
Aquatic Biological and Microbiological Samples. 1989. USGS.
\5\ Because the MF technique usually yields low and variable recovery from chlorinated wastewaters, the Most Probable Number method will be required to
resolve any controversies.
\6\ Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes
to account for the quality, character, consistency, and anticipated organism density of the water sample.
\7\ When the MF method has 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], and Quanti-Tray[supreg] 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-2006 or other membrane filter procedure to 9222G-2006 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. U.S. 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. U.S. 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,
U.S. 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.
U.S. 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. U.S. 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. U.S. 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. U.S. EPA.
\27\ On a monthly basis, at least ten blue colonies from the medium must be verified using Lauryl Tryptose Broth and EC broth, followed by count
adjustment based on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications
should be done from randomized sample sources.
(b) Certain material is incorporated by reference into this part
with the approval of the Director of the Federal Register under 5
U.S.C. 552(a) and 1 CFR part 51. All approved material is available for
inspection at EPA's Water Docket, EPA West, 1301 Constitution Avenue
NW., Room 3334, Washington, DC 20004, Telephone: 202-566-2426, and is
available from the sources listed below. It is also available for
inspection 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: https://www.archives.gov/federal-register/cfr/ibr-locations.html.
* * * * *
(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.
[[Page 40869]]
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.
(ix) 2130, Turbidity. 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. 2010. 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.
(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-S2-, Sulfide. 2011. Table IB.
(l) 4500-SO32-, Sulfite. 2011. Table IB.
(li) 4500-SO42-, 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
[[Page 40870]]
Inductively Coupled Plasma--Mass Spectrometry. September 2010. Table
IB.
(lix) ASTM D5(19)907-13, Standard Test Method for Filterable Matter
(Total Dissolved Solids) and Nonfilterable Matter (Total Suspended
Solids) 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.
* * * * *
(lxiv) ASTM. D7065-11, Standard Test Method for Determination of
Nonylphenol, Bisphenol A, p-tert-Octylphenol, Nonylphenol
Monoethoxylate and Nonylphenol Diethoxylate in Environmental Waters by
Gas Chromatography Mass Spectrometry. July 2011. Table IB.
* * * * *
(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, Hach Company TNTplus 835/836 Nitrate Method
10206, Spectrophotometric Measurement of Nitrate in Water and
Wastewater. Revision 2.1, January 10, 2013. Table IB, Note 75.
(viii) Method 10242, Hach Company TNTplus 880 Total Kjeldahl
Nitrogen Method 10242, Simplified Spectrophotometric Measurement of
Total Kjeldahl Nitrogen in Water and Wastewater. Revision 1.1, January
10, 2013. Table IB, Note 76.
* * * * *
(20) * * *
(i) Colilert. 2013. Table IA, Notes 17 and 18; Table IH, Notes 14,
15 and 16.
(ii) Colilert-18. 2013. Table IA, Notes 17 and 18; Table IH, Notes
14, 15 and 16.
(iii) Enterolert. 2013. Table IA, Note 24; Table IH, Note 12.
(iv) Quanti-Tray Insert and Most Probable Number (MPN) Table. 2013.
Table IA, Note 18; Table IH, Notes 14 and 16.
* * * * *
(25) * * *
(i) NCASI Method TNTP-W10900, Total Nitrogen and Total Phophorus in
Pulp and Paper Biologically Treated Effluent by Alkaline Persulfate
Digestion. 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) Timberline Amonia-001, 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--Laboratory Analysis,
Section B--Methods of the National Water Quality Laboratory, Chapter 8.
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--
[[Page 40871]]
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 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
Chormatography/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 >10,5 6
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.
[[Page 40872]]
38. Nitrate.......................... P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
39. Nitrate-nitrite.................. P, FP, G............... Cool, <=6 28 days.
[deg]C,\18\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,\18\ 28 days.
HCl or H2SO4 to pH <2.
42. Organic Carbon................... P, FP, G............... Cool to <=6 [deg]C,\18\ 28 days.
HCl, H2SO4, or H3PO4
to pH <2.
44. Orthophosphate................... P, FP, G............... Cool, to <=6 [deg]C 18 Filter within 15
24. minutes; Analyze
within 48 hours.
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 within 15
minutes.
73. Turbidity........................ P, FP, G............... Cool, <=6 [deg]C \18\.. 48 hours.
----------------------------------------------------------------------------------------------------------------
Table IC--Organic Tests \8\
----------------------------------------------------------------------------------------------------------------
13, 18-20, 22, 24, 25, 27,28, 34-37, G, FP-lined septum..... Cool, <=6 [deg]C,\18\ 14 days.
39-43, 45-47, 56, 76, 104, 105, 108- 0.008% Na2S2O3,\5\ HCl
111, 113. Purgeable Halocarbons. to pH 2.
26. 2-Chloroethylvinyl ether......... G, FP-lined septum..... Cool, <=6 [deg]C,\18\ 14 days.
0.008% Na2S2O3\5\.
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
0.008% Na2S2O3\5\. extraction.\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.
[[Page 40873]]
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.
----------------------------------------------------------------------------------------------------------------
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, 0. 8 hours.\22\
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, 0. 8 hours.\22\
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.
[[Page 40874]]
\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.
\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
[[Page 40875]]
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.
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)(xvii).
0
c. Redesignate paragraphs (b)(4)(xviii) through the first occurrence of
(xxii) as paragraphs (b)(4)(xvii) through (xxi), respectively and
retaining the second occurrence of paragraph (b)(4)(xxii).
0
d. Add paragraph (c).
The revisions 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. Where the laboratory is using a vendor-
supplied method, it is the QC criteria in the reference method, not the
vendor's method, that must be met to show equivalency. Where a sample
preparation step is required (i.e., digestion, distillation), QC tests
are to be run using standards treated in the same way as the samples.
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. Remove Method 608;
0
b. Add Method 608.3;
0
c. Revise Method 611 section 1.1.;
0
d. Remove Method 624;
0
e. Add Method 624.1;
0
f. Remove Method 625; and
0
g. Add Method 625.1.
The additions and 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, 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
[[Page 40876]]
qualitative technique. This method gives analytical conditions for a
second GC column that can be used to confirm and quantify
measurements. Additionally, Method 625.1 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 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. 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 15.6 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.
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--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 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 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. Do not heat volumetric
labware above 90 [deg]C. After drying and cooling, store inverted or
capped with solvent-rinsed or baked aluminum foil in a clean
environment to prevent accumulation of dust or other contaminants.
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
[[Page 40877]]
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 matrix spike 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 Tables 1 and 2.
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
1910.12009(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, rinse the
compressible tubing thoroughly 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.
Note: The approved ATP for solid-phase extraction is limited to
disk-based extraction media and associated peripheral equipment.
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.
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 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.
5.2.5.3.1 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.
5.2.5.3.2 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.
5.2.6 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.
[[Page 40878]]
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).
5.5.4 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:
(a) Carrier gas flow rate: Approximately 7 mL/min,
(b) Initial temperature: 150 [deg]C for 0.5 minute,
(c) Temperature program: 150-270 [deg]C at 5 [deg]C/min, and
(d) 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,
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.
6.7.1.1 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 6.7.1.3) 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.
6.7.1.2 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), the recovery of trichlorophenol shall be less
than 5%, and no peaks interfering with the target analytes shall be
detected. Otherwise the Florisil cartridge is not performing
properly and the cartridge lot shall be rejected.
6.7.1.3 Florisil cartridge calibration solution--2,4,6-
Trichlorophenol, 0.1 [mu]g/mL in acetone.
6.7.2 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.
[[Page 40879]]
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 before it may 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. Inspect the copper foil or powder before each
use. It must have a bright, non-oxidized appearance to be effective.
Copper foil or powder that has oxidized may be reactivated using the
procedure described above.
6.7.4.2 Tetrabutylammonium sulfite (TBA sulfite)--Prepare as
described below.
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.
6.7.5 Sodium chloride--Reagent grade, prepare at 5% (w/v)
solution in reagent water.
6.8 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 or international standard, when
available. Stock solution concentrations alternative 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.
6.8.1 Accurately weigh about 0.0100 g of pure material in a 10-
mL volumetric flask. Dilute to volume in pesticide quality hexane,
isooctane, or other suitable solvent. 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 may be used at any concentration if they
are certified by the manufacturer or by an independent source.
6.8.1.1 Unless stated otherwise in this method, store non-
aqueous standards in fluoropolymer-lined screw-cap, or heat-sealed,
glass containers, in the dark at -20 to -10 [deg]C. Store aqueous
standards; e.g., the aqueous LCS (section 8.4), in the dark at <=6
[deg]C, but do not freeze.
6.8.1.2 Standards prepared by the laboratory may be stored for
up to one year, except when comparison with QC check standards
indicates that a standard has degraded or become more concentrated
due to evaporation, or unless the laboratory has data on file to
prove stability for a longer period. Commercially prepared standards
may be stored until the expiration date provided by the vendor,
except when comparison with QC check standards indicates that a
standard has degraded or become more concentrated due to
evaporation, or unless the laboratory has data from the vendor on
file to prove stability for a longer period.
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 at or below
the ML specified in Table 1, or 2, or as specified by a regulatory/
control authority or in a permit. The ML value may be rounded to a
whole number that is more convenient for preparing the standard, but
must not exceed the ML value listed in Tables 1 or 2 for those
analytes which list ML values. Alternatively, the laboratory may
establish an ML for each analyte based on the concentration of the
lowest calibration standard in a series of standards produced by the
laboratory or obtained from a commercial vendor, again, provided
that the ML does not exceed the ML 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\.
(a) 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 = 0) calibration (section 7.5.2 or 7.6.2).
Calibrations higher than second order are not allowed. A separate
standard near the MDL may be analyzed as a check on sensitivity, but
should not be included in the linearity assessment. 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.
(b) 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. Divide the analytes into 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). Table 7 provides
information on dividing the target analytes into separate
calibration mixtures that should minimize or eliminate co-elutions.
This table is provided solely as guidance, based on the GC columns
suggested in this method. If an analyte listed in Table 7 is not an
analyte of interest in a given laboratory setting, then it need not
be included in a calibration mixture.
Note: Many commercially available standards are divided into
separate mixtures to address this issue.
(c) If co-elutions occur in analysis of a sample, a co-elution
on one column is acceptable so long as effective separation of the
co-eluting compounds can be achieved on the second column.
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
[[Page 40880]]
real samples and should bracket the linear range of the detector.
6.8.3 Quality Control (QC) Check Sample Concentrate--Prepare one
or more mid-level standard mixtures (concentrates) in acetone (or
other water miscible solvent). The concentrate is used as the
spiking solution with which to prepare the Demonstration of
Capabilities (DOC) samples, the Laboratory Control Sample (LCS), and
Matrix Spike (MS) and Matrix Spike Duplicate (MSD) samples described
in section 8. If prepared by the laboratory (as opposed the
purchasing it from a commercial supplier), the concentrate must be
prepared independently from the standards used for calibration, but
may be prepared from the same source as the second-source standard
used for calibration verification (section 7.7). Regardless of the
source, the concentrate must be in a water-miscible solvent, as
noted above. The concentrate is used to prepare the DOC and LCS
(sections 8.2.1 and 8.4) and MS/MSD samples (section 8.3). Depending
on the analytes of interest for a given sample (see Section 1.4),
multiple solutions and multiple LCS or MS/MSD samples may be
required to account for co-eluting analytes. However, a co-elution
on one column is acceptable so long as effective separation of the
co-eluting compounds can be achieved on the second column. In
addition, the concentrations of the MS/MSD samples should reflect
any relevant compliance limits for the analytes of interest, as
described in section 8.3.1. If a custom spiking solution is required
for a specific discharge (section 8.3.1), prepare it separately from
the DOC and LCS solution.
Note: Some commercially available standards are divided into
separate mixtures to address the co-elution issue.
6.8.4 Calibration Verification Standards--In order to verify the
results of the initial calibration standards, prepare one or more
mid-level standard mixtures in isooctane or hexane, using standards
obtained from a second source (different manufacturer or different
certified lot from the calibration standards). These standards will
be analyzed to verify the accuracy of the calibration (sections 7.7
and 13.6.2). As with the QC sample concentrate in section 6.8.3,
multiple solutions may be required to address co-elutions among all
of the analytes.
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 alternative 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. Alternative surrogates and concentrations may be
used, provided 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.
6.8.7 DDT and endrin decomposition (breakdown) solution--Prepare
a solution containing endrin at a concentration of 50 ng/mL and
4,4'-DDT at a concentration of 100 ng/mL, in isooctane or hexane. A
1-[micro]L injection of this standard will contain 50 picograms (pg)
of endrin and 100 pg of DDT. The concentration of the solution may
be adjusted by the laboratory to accommodate other injection volumes
such that the same masses of the two analytes are introduced into
the instrument.
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 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. An alternative volume (see Section
12.3) may be used provided all requirements in this method are met.
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. An instrument
blank should be analyzed after the highest standard to demonstrate
that there is no carry-over within the system for this calibration
range.
7.4 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] TR28AU17.000
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, As,
vs. concentration Cs. 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
0.920. 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] TR28AU17.001
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 coefficient of determination of the weighted
regression must be greater than 0.920. Alternatively, the relative
standard error (Reference 10) may 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 The working calibration curve, CF, or RF must be verified
immediately after calibration and at the beginning and end of each
24-hour shift by the analysis of a mid-level calibration standard.
The calibration verification standard(s) must be obtained from a
second manufacturer or a manufacturer's batch prepared
[[Page 40881]]
independently from the batch used for calibration (Section 6.8.4).
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). The time for the
injections may not exceed 24 hours.
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 injections may be used as the beginning verification for the next
group of injections.
7.8 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 must repeat demonstration of
capability (DOC) at least 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 alternative 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 publicly owned treatment works (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 https://www.epa.gov/eg/industrial-effluent-guidelines for a list of industrial categories with existing
effluent guidelines).
(i) At least one of the above wastewater matrix types must have
at least one of the following characteristics:
(A) Total suspended solids greater than 40 mg/L.
(B) Total dissolved solids greater than 100 mg/L.
(C) Oil and grease greater than 20 mg/L.
(D) NaCl greater than 120 mg/L.
(E) CaCO3 greater than 140 mg/L.
(ii) The interim acceptance criteria for MS, MSD recoveries that
do not have recovery limits in Table 4 or developed in section
8.3.3, and for surrogates that do not have recovery limits developed
in section 8.6, 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 in Table 4 or developed in section
8.3.3, 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, and business 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).
(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).
[[Page 40882]]
(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 Tables 1 and 2 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 samples to monitor and evaluate method and laboratory
performance on the sample matrix. 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
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
Tables 1 or 2, 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. When analyzing
the PCBs as Aroclors, it is only necessary to establish an MDL for
one of the multi-component analytes (e.g., PCB 1254), or the mixture
of Aroclors 1016 and 1260 may be used to establish MDLs for all of
the Aroclors. Similarly, MDLs for other multi-component analytes
(e.g., Chlordanes) may be determined using only one of the major
components. 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.
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 (X) 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 X 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 X for all analytes of interest meet the acceptance
criteria, system performance is acceptable and analysis of blanks
and samples can 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.
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
purpose of the MS/MSD requirement is to provide data that
demonstrate the effectiveness of the method as applied to the
samples in question by a given laboratory, and both the data user
(discharger, permittee, regulated entity, regulatory/control
authority, customer, other) and the laboratory share responsibility
for provision of such data. The data user should identify the sample
and the analytes of interest (section 1.4) to be spiked and provide
sufficient sample volume to perform MS/MSD analyses. The laboratory
must, on an ongoing basis, spike at least 5% of the samples in
duplicate from each discharge being monitored to assess accuracy
(recovery and precision). If direction cannot be obtained from the
data user, the laboratory must spike at least one sample in
duplicate per extraction batch of up to 20 samples 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. When no information is available, the mid-point of the
calibration may be used.
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] TR28AU17.002
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] TR28AU17.003
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.
(a) 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
[[Page 40883]]
for permitting or regulatory compliance. See section 8.1.7 for
disposition of failures.
(b) 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 12
and 13).
8.3.4 After analysis of a minimum of 20 MS/MSD samples for each
target analyte and surrogate, and if the laboratory chooses to
develop and apply optional in-house QC limits, the laboratory should
calculate and apply the optional in-house QC limits for recovery and
RPD of future MS/MSD samples (Section 8.3). The optional in-house 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 and the remaining analytes (those not
included in the 80%) must meet the acceptance criteria 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. Alternatively, surrogate recovery limits may
be developed from laboratory control charts. In-house QC acceptance
criteria must be updated at least every two years.
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
(sections 6.8.3 and 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] TR28AU17.004
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), or limits based
on laboratory control charts. 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 analysis of the LCS prepared with a fresh
sample concentrate, or to system 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.
8.4.5 After analysis of 20 LCS samples, and if the laboratory
chooses to develop and apply optional in-house QC limits, the
laboratory should calculate and apply the optional in-house QC
limits for recovery of future LCS samples (section 8.4). Limits for
recovery in the LCS should be 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, and the remaining analytes (those not included in the
80%) must meet the acceptance criteria in Table 4. If an in-house
lower limit for 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. Many of the analytes and
surrogates do not contain 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 4, and at least 80% of the surrogates must meet the 60-140%
interim criteria until in-house LCS and surrogate limits are
developed. Alternatively, acceptance criteria for analytes that do
not have recovery limits in Table 4 may be based on laboratory
control charts. In-house QC acceptance criteria must be updated at
least every two years.
8.5 Blank--Extract and analyze a blank with each extraction
batch (section 3.1) 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--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 (section 8.4). 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; otherwise, see section 8.1.7
for disposition of repeated failures.
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 8.3, 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 to ensure process
control (e.g., after each 5-10 new accuracy measurements). If
desired, statements of accuracy for laboratory performance,
independent of performance on samples, may be developed using LCSs.
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
[[Page 40884]]
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 a 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 8.3 or 8.4) 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 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, use of phase-separation paper, centrifugation,
salting, 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
[mu]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 sulfur removal or
acid back extraction, 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) or acid back extraction
(section 11.6). 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--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]
[[Page 40885]]
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 <=6 [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 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 to a range of 5.0-9.0 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 must 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 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 (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,
[[Page 40886]]
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.
11.1.5 Acid back extraction (section 11.6) may be useful for
cleanup of PCBs and other compounds not adversely affected by
sulfuric acid.
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 (50:3:47). 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.
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 7.8 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 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
[[Page 40887]]
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.
11.6 Acid back extraction (section 6.1.2).
11.6.1 Quantitatively transfer the extract (section 10.3.1.5) to
a 250-mL separatory funnel.
11.6.2 Partition the extract against 50 mL of sulfuric acid
solution (section 6.1.2). Discard the aqueous layer. Repeat the acid
washing until no color is visible in the aqueous layer, to a maximum
of four washings.
11.6.3 Partition the extract against 50 mL of sodium chloride
solution (section 6.7.5). Discard the aqueous layer.
11.6.4 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 [mu]L of 10 [mu]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. Injection
volumes must be the same for all extracts. Record the volume
injected to the nearest 0.05 [mu]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 calibration verification 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 6.8.7). As noted in section 6.8.7, other injection
volumes may be used as long as the concentrations of DDT and endrin
in the solution are adjusted to introduce the masses of the two
analytes into the instrument that are listed in section 6.8.7.
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] TR28AU17.005
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 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 LCS (section 6.8.3) extracted
with each sample batch (Section 8.4). See Section 8.4 for criteria
acceptance of the LCS.
13.7.2 It is suggested, but not required, that the laboratory
update statements of data
[[Page 40888]]
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
calibration verification (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). If the analytes are affected, re-prepare and
reanalyze the sample, blank, LCS, MS, or MSD, and repeat the
pertinent test.
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. Alternatively, GC/MS
identification may be used to provide another means of
identification.
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 The retention time windows must be recentered 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 calibration
(Section 7.4) varies by more than 5 seconds across the calibration
range as a function of the concentration of the standard, using the
standard deviation of the retention times (section 14.2.3) 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 analyte 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 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. Alternatively, GC/MS
identification may be used. Differentiation among some of the
Aroclors may require evaluation of more than five peaks to ensure
correct identification.
14.4 GC/MS confirmation. When the concentration of an analyte is
sufficient and 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 would need to be by GC/MS-SIM, or the
estimated concentration would need to be 100 times higher than the
GC/ECD calibration range. The extract may be concentrated by an
additional amount to allow a further attempt at GC/MS confirmation.
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 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] TR28AU17.006
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] TR28AU17.007
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)
[[Page 40889]]
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] TR28AU17.008
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 section 7.5.1. Determine the
concentration of each of the characteristic peaks, using the average
calibration factor calculated for that peak in section 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 specified otherwise 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 or QC standard
at or above the ML to 3 significant figures. Report a result for
each analyte in each sample or QC standard below the ML as ``12, are hazardous and must be
handled and disposed of as hazardous waste, or neutralized and
disposed of in accordance with all federal, state, and local
regulations. It is the laboratory's responsibility to comply with
all federal, state, and local regulations governing waste
management, particularly the hazardous waste identification rules
and land disposal restrictions. The laboratory using this method has
the responsibility 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. For further information on waste management, see ``The
Waste Management Manual for Laboratory Personnel,'' also available
from the American Chemical Society at the address in section 18.3.
19.3 Many analytes in this method decompose above 500 [deg]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.
19.4 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.
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 1910.1450), 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
[[Page 40891]]
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.
21. Tables
Table 1--Pesticides \1\
----------------------------------------------------------------------------------------------------------------
Analyte CAS No. MDL \2\ (ng/L) ML \3\ (ng/L)
----------------------------------------------------------------------------------------------------------------
Aldrin.......................................................... 309-00-2 4 12
alpha-BHC....................................................... 319-84-6 3 9
beta-BHC........................................................ 319-85-7 6 18
delta-BHC....................................................... 319-86-8 9 27
gamma-BHC (Lindane)............................................. 58-89-9 4 12
alpha-Chlordane \ 4\............................................ 5103-71-9 14 42
gamma-Chlordane \ 4\............................................ 5103-74-2 14 42
4,4'-DDD........................................................ 72-54-8 11 33
4,4'-DDE........................................................ 72-55-9 4 12
4,4'-DDT........................................................ 50-29-3 12 36
Dieldrin........................................................ 60-57-1 2 6
Endosulfan I.................................................... 959-98-8 14 42
Endosulfan II................................................... 33213-65-9 4 12
Endosulfan sulfate.............................................. 1031-07-8 66 198
Endrin.......................................................... 72-20-8 6 18
Endrin aldehyde................................................. 7421-93-4 23 70
Heptachlor...................................................... 76-44-8 3 9
Heptachlor epoxide.............................................. 1024-57-3 83 249
----------------------------------------------------------------------------------------------------------------
\1\ All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A).
\2\ 40 CFR part 136, appendix B, June 30, 1986.
\3\ ML = Minimum Level--see Glossary for definition and derivation, calculated as 3 times the MDL.
\4\ MDL based on the MDL for Chlordane.
Table 2--Additional Analytes
----------------------------------------------------------------------------------------------------------------
Analyte CAS No. MDL \3\ (ng/L) ML \4\ (ng/L)
----------------------------------------------------------------------------------------------------------------
Acephate........................................................ 30560-19-1 .............. ..............
Alachlor........................................................ 15972-60-8 .............. ..............
Atrazine........................................................ 1912-24-9 .............. ..............
Benfluralin (Benefin)........................................... 1861-40-1 .............. ..............
Bromacil........................................................ 314-40-9 .............. ..............
Bromoxynil octanoate............................................ 1689-99-2 .............. ..............
Butachlor....................................................... 23184-66-9 .............. ..............
Captafol........................................................ 2425-06-1 .............. ..............
Captan.......................................................... 133-06-2 .............. ..............
Carbophenothion (Trithion)...................................... 786-19-6 .............. ..............
Chlorobenzilate................................................. 510-15-6 .............. ..............
Chloroneb (Terraneb)............................................ 2675-77-6 .............. ..............
Chloropropylate (Acaralate)..................................... 5836-10-2 .............. ..............
Chlorothalonil.................................................. 1897-45-6 .............. ..............
Cyanazine....................................................... 21725-46-2 .............. ..............
DCPA (Dacthal).................................................. 1861-32-1 .............. ..............
2,4'-DDD........................................................ 53-19-0 .............. ..............
2,4'-DDE........................................................ 3424-82-6 .............. ..............
2,4'-DDT........................................................ 789-02-6 .............. ..............
Diallate (Avadex)............................................... 2303-16-4 .............. ..............
1,2-Dibromo-3-chloropropane (DBCP).............................. 96-12-8 .............. ..............
Dichlone........................................................ 117-80-6 .............. ..............
Dichloran....................................................... 99-30-9 .............. ..............
Dicofol......................................................... 115-32-2 .............. ..............
[[Page 40892]]
Endrin ketone................................................... 53494-70-5 .............. ..............
Ethalfluralin (Sonalan)......................................... 55283-68-6 .............. ..............
Etridiazole..................................................... 2593-15-9 .............. ..............
Fenarimol (Rubigan)............................................. 60168-88-9 .............. ..............
Hexachlorobenzene \1\........................................... 118-74-1 .............. ..............
Hexachlorocyclopentadiene \1\................................... 77-47-4 .............. ..............
Isodrin......................................................... 465-73-6 .............. ..............
Isopropalin (Paarlan)........................................... 33820-53-0 .............. ..............
Kepone.......................................................... 143-50-0 .............. ..............
Methoxychlor.................................................... 72-43-5 .............. ..............
Metolachlor..................................................... 51218-45-2 .............. ..............
Metribuzin...................................................... 21087-64-9 .............. ..............
Mirex........................................................... 2385-85-5 .............. ..............
Nitrofen (TOK).................................................. 1836-75-5 .............. ..............
cis-Nonachlor................................................... 5103-73-1 .............. ..............
trans-Nonachlor................................................. 39765-80-5 .............. ..............
Norfluorazon.................................................... 27314-13-2 .............. ..............
Octachlorostyrene............................................... 29082-74-4 .............. ..............
Oxychlordane.................................................... 27304-13-8 .............. ..............
PCNB (Pentachloronitrobenzene).................................. 82-68-8 .............. ..............
Pendamethalin (Prowl)........................................... 40487-42-1 .............. ..............
cis-Permethrin.................................................. 61949-76-6 .............. ..............
trans-Permethrin................................................ 61949-77-7 .............. ..............
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 .............. ..............
Strobane........................................................ 8001-50-1 .............. ..............
Technazene...................................................... 117-18-0 .............. ..............
Technical Chlordane \2\......................................... .............. .............. ..............
Terbacil........................................................ 5902-51-2 .............. ..............
Terbuthylazine.................................................. 5915-41-3 .............. ..............
Toxaphene \1\................................................... 8001-35-2 240 720
Trifluralin..................................................... 1582-09-8 .............. ..............
PCB-1016 \1\.................................................... 12674-11-2 .............. ..............
PCB-1221 \1\.................................................... 11104-28-2 .............. ..............
PCB-1232 \1\.................................................... 11141-16-5 .............. ..............
PCB-1242 \1\.................................................... 53469-21-9 65 95
PCB-1248 \1\.................................................... 12672-29-6 .............. ..............
PCB-1254 \1\.................................................... 11097-69-1 .............. ..............
PCB-1260 \1\.................................................... 11096-82-5 .............. ..............
PCB-1268........................................................ 11100-14-4 .............. ..............
----------------------------------------------------------------------------------------------------------------
\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, June 30, 1986.
\4\ ML = Minimum Level--see Glossary for definition and derivation, calculated as 3 times the MDL.
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
[[Page 40893]]
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-1016................................ .............. ..............
PCB-1221................................ .............. ..............
PCB-1232................................ .............. ..............
PCB-1242................................ .............. ..............
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 40894]]
Table 4--QC Acceptance Criteria
--------------------------------------------------------------------------------------------------------------------------------------------------------
Calibration Test
Analyte verification concentration Limit for s (% Range for X Range for P Maximum MS/MSD
(%) ([mu]g/L) SD) (%) (%) 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 for the DOC (section 8.2.4).
X = Average of four recovery measurements for the DOC (section 8.2.4).
P = Recovery for the LCS (section 8.4.3).
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 40895]]
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.
Table 7--Suggested Calibration Groups \1\
------------------------------------------------------------------------
Analyte
-------------------------------------------------------------------------
Calibration Group 1:
Acephate
Alachlor
Atrazine
beta-BHC
Bromoxynil octanoate
Captafol
Diallate
Endosulfan sulfate
Endrin
Isodrin
Pendimethalin (Prowl)
trans-Permethrin
Calibration Group 2:
alpha-BHC
DCPA
4,4'-DDE
4,4'-DDT
Dichlone
Ethalfluralin
Fenarimol
Methoxychlor
Metribuzin
Calibration Group 3:
gamma-BHC (Lindane)
gamma-Chlordane
Endrin ketone
Heptachlor epoxide
Isopropalin
Nitrofen (TOK)
PCNB
cis-Permethrin
Trifluralin
Callibration Group 4:
Benfluralin
Chlorobenzilate
Dieldrin
Endosulfan I
Mirex
Terbacil
Terbuthylazine
Triadimefon
Calibration Group 5:
alpha-Chlordane
Captan
Chlorothalonil
4,4'-DDD
Norfluorazon
Simazine
Calibration Group 6:
Aldrin
delta-BHC
Bromacil
Butachlor
Endosulfan II
Heptachlor
Kepone
Calibration Group 7:
Carbophenothion
Chloroneb
Chloropropylate
DBCP
Dicofol
Endrin aldehyde
Etridiazone
Perthane
Propachlor
Propanil
Propazine
------------------------------------------------------------------------
\1\ The analytes may be organized in other calibration groups, provided
that there are no coelution problems and that all QC requirements are
met.
22. Figures
BILLING CODE 6560-50-P
[[Page 40896]]
[GRAPHIC] [TIFF OMITTED] TR28AU17.010
[[Page 40897]]
[GRAPHIC] [TIFF OMITTED] TR28AU17.011
BILLING CODE 6560-50-C
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
[mu]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
hr hour
ID inside diameter
[[Page 40898]]
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 standard (section 6.8.4)
used to verify calibration (sections 7.8 and 13.6).
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 section 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.
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.
* * * * *
[[Page 40899]]
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 ether............. 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, and on an interlaboratory method validation study (Reference
4). Although this method was validated through an interlaboratory
study conducted in the early 1980s, 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. 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.
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. 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. After
purging is completed, the trap is heated and backflushed with the
gas to desorb the purgeables onto a gas chromatographic column. 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 initially
and with each analytical batch (samples analyzed on a given 12-hour
shift, to a maximum of 20 samples), 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.
[[Page 40900]]
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 (Fisher #13075 or equivalent). Unless pre-
cleaned, detergent wash, rinse with tap and reagent water, and dry
at 105 5 [deg]C before use.
5.1.2 Septum--Fluoropolymer-faced silicone (Fisher #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 with
autosamplers. 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.
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). 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 this temperature during desorption. The trap should
not be heated higher than the maximum temperature recommended by the
manufacturer.
5.2.4 The purge-and-trap system may be assembled as a separate
unit or coupled to a gas chromatograph.
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 alternative 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.
6.3.4 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 or international standard, when
available. Stock solution concentrations alternative 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.
[[Page 40901]]
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. Unless stated otherwise in this method,
store non-aqueous standards in fluoropolymer-lined screw-cap, or
heat-sealed, glass containers, in the dark at -20 to -10 [deg]C.
Store aqueous standards; e.g., the aqueous LCS (section 8.4.1) in
the dark at <=6 [deg]C (but do not freeze) with zero headspace;
e.g., in VOA vials (section 5.1.1). Standards prepared by the
laboratory may be stored for up to one month, except when comparison
with QC check standards indicates that a standard has degraded or
become more concentrated due to evaporation, or unless the
laboratory has data on file to prove stability for a longer period.
Commercially prepared standards may be stored until the expiration
date provided by the vendor, except when comparison with QC check
standards indicates that a standard has degraded or become more
concentrated due to evaporation, or unless the laboratory has data
from the vendor on file to prove stability for a longer period.
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
surrogate in methanol as described in section 6.5, and prepare a
solution for spiking the surrogates into all blanks, LCSs, and MS/
MSDs. Prepare the spiking solution such that spiking a small volume
will result in a constant concentration of the surrogates. For
example, add 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 to produce a concentration of 30 [mu]g/L for each
surrogate. Other surrogate concentrations may be used. Store per
section 6.5.4.
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.
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 after each analysis at a
temperature and time sufficient to prevent detectable concentrations
of the analytes or contaminants in successive analyses.
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 measurements
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 in methanol as described in Section 6.5, and prepare a
solution for spiking the internal standards into all blanks, LCSs,
and MS/MSDs. Prepare the spiking solution such that spiking a small
volume will result in a constant concentration of the internal
standards. For example, add 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 to produce 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
per section 6.5.4.
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, but no fewer than 3 levels may be used, and only the highest or
lowest point(s) may be dropped from the calibration. One of the
calibration standards should be at a concentration at or below the
ML or as specified by a regulatory/control authority or in a permit.
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 produced in the laboratory or obtained from a
commercial vendor, again, provided that the ML value 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 = 0) 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. 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. Once the scan conditions are
established, they must be used for analyses of all standards,
blanks, and samples.
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
[[Page 40902]]
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 alternative 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, 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.
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. Refer to the footnotes to Table 3 for establishing
operating conditions and to section 7.3.2.2 for establishing scan
conditions.
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. Analyze unfamiliar samples in the scan mode to assure that
the analytes of interest are determined.
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] TR28AU17.012
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. On a
continuing basis, the laboratory must repeat demonstration of
capability (DOC) at least 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 1.5 and 40 CFR
136.6(b)) to improve separations or lower the costs of measurements.
These options may include an alternative purge-and-trap device, and
changes in both column and type of mass spectrometer (see 40 CFR
136.6(b)(4)(xvi)). Alternative 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 8.8).
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 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/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
[[Page 40903]]
could be performed by the vendor of the alternative 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 publicly owned treatment works (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 https://www.epa.gov/eg/industrial-effluent-guidelines for a list of industrial categories with existing
effluent guidelines).
(i) At least one of the above wastewater matrix types must have
at least one of the following characteristics:
(A) Total suspended solids greater than 40 mg/L.
(B) Total dissolved solids greater than 100 mg/L.
(C) Oil and grease greater than 20 mg/L.
(D) NaCl greater than 120 mg/L.
(E) CaCO3 greater than 140 mg/L.
(ii) Results of MS/MSD tests must meet QC acceptance criteria in
section 8.3.
(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, and business 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 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 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 samples to monitor and evaluate method and laboratory
performance on the sample matrix. 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 must 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 must document and report the failures
(e.g., as qualifiers on results), unless the failures are not
required to be reported as determined by the regulatory/control
authority. Results associated with a QC failure for an analyte
regulated in a discharge cannot be used to demonstrate regulatory
compliance. QC failures do 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 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 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 (LCS
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). Alternatively, acceptance criteria for analytes not listed
in Table 7 may be based on laboratory control charts. 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 section 8.2.6.
[[Page 40904]]
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
purpose of the MS/MSD requirement is to provide data that
demonstrate the effectiveness of the method as applied to the
samples in question by a given laboratory, and both the data user
(discharger, permittee, regulated entity, regulatory/control
authority, customer, other) and the laboratory share responsibility
for provision of such data. The data user should identify the sample
and the analytes of interest (section 1.3) to be spiked and provide
sufficient sample volume to perform MS/MSD analyses. The laboratory
must, on an ongoing basis, spike at least 5% of the samples in
duplicate from each discharge being monitored to assess accuracy
(recovery and precision). If direction cannot be obtained from the
data user, the laboratory must spike at least one sample in
duplicate per extraction batch of up to 20 samples 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 mid-point 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 A1-A2/
(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 7, 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. 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) and is applied to
spike concentrations of 20 [mu]g/L and higher. If spiking is
performed at a concentration lower than 20 [mu]g/L, the laboratory
must use the QC acceptance criteria in Table 7, the optional QC
acceptance criteria calculated for the specific spike concentration
in Table 8, or optional in-house criteria (Section 8.3.4). To use
the acceptance criteria in Table 8: (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).
Alternatively, acceptance criteria may be based on laboratory
control charts. In-house LCS QC acceptance criteria must be updated
at least every two years.
8.3.4 After analysis of a minimum of 20 MS/MSD samples for each
target analyte and surrogate, and if the laboratory chooses to
develop and apply in-house QC limits, the laboratory should
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. If
in-house QC limits are developed, 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 7 and the remaining analytes (those
other than the analytes included in the 80%) must meet the
acceptance criteria in 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.
8.4 Calibration verification/laboratory control sample (LCS)--
The working calibration curve or RF must be verified immediately
after calibration and at the beginning of each 12-hour shift by the
measurement of an LCS. The LCS must be from a source different from
the source used for calibration (section 7.3.2.1), but may be the
same as the sample prepared for the DOC (section 8.2.1).
Note: The 12-hour shift begins after analysis of BFB, the LCS,
and the blank, and ends 12 hours later. BFB, the LCS, and blank are
outside of the 12-hour shift (Section 11.4). 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 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 LCS (section 8.4.5). 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
(section 8.4.2). 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). 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.
[[Page 40905]]
8.4.5 After analysis of 20 LCS samples, and if the laboratory
chooses to develop and apply in-house QC limits, the laboratory
should calculate and apply in-house QC limits for recovery to future
LCS samples (section 8.4). Limits for recovery in the LCS 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, and the remaining analytes
(those other than the analytes included in the 80%) must meet the
acceptance criteria in Table 7. 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. Many of the analytes and surrogates do not have
acceptance criteria. The laboratory should use 60-140% as interim
acceptance criteria for recoveries of spiked analytes that do not
have recovery limits specified in Table 7, and least 80% of the
analytes should meet the 60-140% interim criteria until in-house LCS
limits are developed. Alternatively, acceptance criteria for
analytes that do not have recovery limits in Table 7 may be based on
laboratory control charts. In-house QC acceptance criteria must be
updated at least every two years.
8.5 Blank--A blank must be analyzed prior to 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: 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 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. If, however,
continued re-testing results in repeated blank contamination, the
laboratory must document and report the failures (e.g., as
qualifiers on results), unless the failures are not required to be
reported as determined by the regulatory/control authority. Results
associated with blank contamination for an analyte regulated in a
discharge cannot be used to demonstrate regulatory compliance. QC
failures do not relieve a discharger or permittee of reporting
timely results.
8.6 Surrogate recoveries--The laboratory must evaluate surrogate
recovery data in each sample against its in-house surrogate recovery
limits for surrogates that do not have acceptance criteria in Table
7. The laboratory may use 60-140% as interim acceptance criteria for
recoveries for surrogates not listed in Table 5. At least 80% of the
surrogates must meet the 60-140% interim criteria until in-house
limits are developed. Alternatively, surrogate recovery limits may
be developed from laboratory control charts.
8.6.1 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). Alternatively, surrogate recovery limits may
be developed from laboratory control charts. In-house QC acceptance
criteria must be updated at least every two years.
8.6.2 If any recovery fails its criteria, attempt to find and
correct the cause of the failure. See section 8.1.7 for disposition
of failures.
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 each internal standard in each sample, blank,
and MS/MSD must be within 50% to 200% (1/2 to 2x) of its respective
response in the mid-point calibration standard. 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 alternative
internal standard for quantitation of the analyte referenced to the
affected internal standard. It may be necessary to use the data
system to calculate a new response factor from calibration data for
the alternative internal standard/analyte pair. If an internal
standard fails the 50-200% criteria and no analytes are detected in
the sample, ignore the failure or report it if required by the
regulatory/control authority.
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 (Px)
and the standard deviation of the percent recovery (sp). Express the
accuracy assessment as a percent interval from Px-
2sp to Px + 2sp. For example, if
Px = 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). If
desired, statements of accuracy for laboratory performance,
independent of performance on samples, may be developed using LCSs.
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 alternative 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.
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
[[Page 40906]]
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 MDLs and MLs for many of the analytes are given
in Table 1. Retention times for many of the analytes are given in
Table 3. 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. Prior to performing analyses, and between
analyses, it may be necessary to bake the purge-and-trap and GC
systems (section 3.3).
10.2 Attach the trap inlet to the purging device, and set the
purge-and-trap system to purge. 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, and begin the temperature program of 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
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. 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
standards or samples will be analyzed, perform the tests in sections
11.2-11.3 to verify system performance. Use the instrument operating
conditions in the footnotes to Table 3 for these performance tests.
Alternative 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 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.
Tests for BFB, the LCS, and the blank are outside of the 12-hour
shift, and the 12-hour shift includes samples and matrix spikes and
matrix spike duplicates (section 8.4). The total time for analysis
of BFB, the LCS, the blank, and the 12-hour shift must not exceed 14
hours.
12. Qualitative Identification
12.1 Identification is accomplished 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 the quantitation and secondary 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 The retention time for the analyte should be within
10 seconds of the analyte in the LCS run at the
beginning of the shift (section 8.4).
Note: Retention time windows other than 10 seconds
may be appropriate depending on the performance of the gas
chromatograph or observed retention time drifts due to certain types
of matrix effects. Relative retention time (RRT) may be used as an
alternative to absolute retention times if retention time drift is a
concern. RRT is a unitless quantity (see section 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. When significant retention time
drifts are observed, dilutions or spiked samples may help the
analyst determine the effects of the matrix on elution of the target
analytes and to assist in qualitative identification.
12.1.3 Either the background corrected EICP areas, or 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
the quantitation and secondary 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 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 produce very similar mass spectra
should be identified as individual isomers if they have sufficiently
different gas chromatographic retention times. Sufficient gas
chromatographic resolution is achieved if the height of the valley
between two isomer peaks is less than 50% of the average of the two
peak heights. Otherwise, structural isomers are identified as
isomeric pairs. The resolution should be verified on the mid-point
concentration of the initial calibration as well as the laboratory
designated continuing calibration verification level if closely
eluting isomers are to be reported.
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.
[[Page 40907]]
[GRAPHIC] [TIFF OMITTED] TR28AU17.013
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 this 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 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,'' ``limit of quantitation,'' ``quantitation limit,'' and
``minimum level'' to be synonymous.
13.2.2.1 Report a result for each analyte in each field sample
or QC standard at or above the ML to 3 significant figures. Report a
result for each analyte found in each field sample or QC standard
below the ML as ``12, are hazardous and must be
handled and disposed of as hazardous waste, or neutralized and
disposed of in accordance with all federal, state, and local
regulations. It is the laboratory's responsibility to comply with
all federal, state, and local regulations governing waste
management, particularly the hazardous waste identification rules
and land disposal restrictions. The laboratory using this method has
the responsibility 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. For further information on waste management, see ``The
Waste Management Manual for Laboratory Personnel,'' also available
from the American Chemical Society at the address in Section 15.3.
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
``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.
[[Page 40908]]
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
Table 1--Purgeables \1\
----------------------------------------------------------------------------------------------------------------
CAS Registry MDL ([mu]g/L) ML ([mu]g/L)
Analyte No. \2\ \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
Acrolein................................................ 107-02-8
Acrylonitrile........................................... 107-13-1
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
[[Page 40909]]
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
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 time
Analyte (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.
Alternative tuning criteria from other published EPA reference methods
may be used, provided method performance is not adversely affected.
Alternative tuning criteria specified by an instrument manufacturer
may also be used for another type of mass spectrometer, or for an
alternative carrier gas, provided method performance is not adversely
affected.
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
[[Page 40910]]
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.
Table 6--Characteristic m/z's for Purgeable Organics
------------------------------------------------------------------------
Analyte Primary m/z Secondary m/z's
------------------------------------------------------------------------
Acrolein.......................... 56 55 and 58.
Acrylonitrile..................... 53 52 and 51.
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 Q Limit for s Range for X Range for P1,
Analyte (%) (%) (%) P2 (%) Limit for RPD
----------------------------------------------------------------------------------------------------------------
Acrolein........................ 60-140 30 50-150 40-160 60
Acrylonitrile................... 60-140 30 50-150 40-160 60
Benzene......................... 65-135 33 75-125 37-151 61
Benzene-d6...................... .............. .............. .............. .............. ..............
Bromodichloromethane............ 65-135 34 50-140 35-155 56
Bromoform....................... 70-130 25 57-156 45-169 42
[[Page 40911]]
Bromomethane.................... 15-185 90 D-206 D-242 61
2-Butanone-d5................... .............. .............. .............. .............. ..............
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................. .............. .............. .............. .............. ..............
2-Chloroethylvinyl ether........ D-225 130 D-252 D-305 71
Chloroform...................... 70-135 32 68-121 51-138 54
Chloroform-\13\C................ .............. .............. .............. .............. ..............
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.......... .............. .............. .............. .............. ..............
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........... .............. .............. .............. .............. ..............
1,1-Dichloroethene.............. 50-150 40 19-212 D-234 32
1,1-Dichloroethene-d2........... .............. .............. .............. .............. ..............
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.......... .............. .............. .............. .............. ..............
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.... .............. .............. .............. .............. ..............
Ethyl benzene................... 60-140 34 75-134 37-162 63
2-Hexanone-d5................... .............. .............. .............. .............. ..............
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.... .............. .............. .............. .............. ..............
Tetrachloroethene............... 70-130 23 65-133 64-148 39
Toluene......................... 70-130 22 75-134 47-150 41
Toluene-d8...................... .............. .............. .............. .............. ..............
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............... .............. .............. .............. .............. ..............
----------------------------------------------------------------------------------------------------------------
\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
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
Analyte Recovery, X' precision, sr' precision, S'
([mu]g/L) ([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
[[Page 40912]]
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.
19. Glossary
These definitions and purposes are specific to this method, but
have been conformed to common usage to the extent possible.
19.1 Units of weight and measure and their abbreviations.
19.1.1 Symbols.
[deg]C degrees Celsius
[mu]g microgram
[mu]L microliter
< less than
> greater than
% percent
19.1.2 Abbreviations (in alphabetical order).
cm centimeter
g gram
h hour
ID inside diameter
in. inch
L liter
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
19.2 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 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 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
[[Page 40913]]
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 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.
VOA--Volatile organic analysis: e.g., the analysis performed by
this method.
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, and on an interlaboratory method validation study
(Reference 2). Although this method was validated through an
interlaboratory study conducted in the early 1980s, 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 example, benzidine is subject to
oxidative losses during extraction and/or 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. The sample may be extracted at neutral pH if necessary to
overcome these or other decomposition problems that could occur at
alkaline or acidic pH. EPA also has provided other methods (e.g.,
Method 607--Nitrosamines) that may be used for determination of some
of these analytes. EPA encourages use of Method 625.1 to determine
additional compounds amenable to extraction and GC/MS.
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
[[Page 40914]]
authority or in a permit. Method 608.3 should be used for
determination of pesticides and PCBs. However, if pesticides and/or
PCBs are to be determined, an additional sample must be collected
and extracted using the pH adjustment and extraction procedures
specified in Method 608.3. 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 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. 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.
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, including solid-phase extraction (SPE) are described in
section 8.1.2.
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 24-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. Do not heat volumetric
labware above 90 [deg]C. After drying and cooling, store inverted or
capped with solvent-rinsed or baked aluminum foil in a clean
environment to prevent accumulation of dust or other contaminants.
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) or triple
quadrupole (MRM) mass spectrometry may make identification easier.
Tables 4 and 5 give characteristic CI and MRM m/z's for many of the
analytes covered by this method. The use of CI or MRM mass
spectrometry may be utilized to support electron ionization (EI)
mass spectrometry or as a primary method for identification and
quantification. While the use of these enhanced techniques is
encouraged, it is 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.
[[Page 40915]]
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, however, rinse the compressible tubing 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-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,
NJ, 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 vaporization 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.
5.9 Muffle furnace or kiln--Capable of baking glassware or
sodium sulfate in the range of 400-450 [deg]C.
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 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 or
international 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 may be used at any concentration if they
are certified by the manufacturer or by an independent source.
6.7.2 Unless stated otherwise in this method, store non-aqueous
standards in fluoropolymer-lined screw-cap, or heat-sealed, glass
containers, in the dark at -20 to -10 [deg]C. Store aqueous
standards; e.g., the aqueous LCS (section 8.4.1), in the dark at <=
6 [deg]C, but do not freeze. Standards prepared by the laboratory
may be stored for up to one year, except when comparison with QC
check standards indicates that a standard has degraded or become
more concentrated due to evaporation, or unless the laboratory has
data on file to prove stability for a longer period. Commercially
prepared standards may be stored until the expiration date provided
by the vendor, except when
[[Page 40916]]
comparison with QC check standards indicates that a standard has
degraded or become more concentrated due to evaporation, or unless
the laboratory has data from the vendor on file to prove stability
for a longer period.
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. 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. Store per section
6.7.2.
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. Store per section 6.7.3.
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 alternative 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, 20 mg pentachlorophenol, 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 before it may be used, as
described below:
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. Inspect the
copper foil or powder before each use. It must have a bright, non-
oxidized appearance to be effective. Copper foil or powder that has
oxidized may be reactivated using the procedure described above.
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.
6.14 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. A
1-[mu]L injection of this standard will contain 1 nanogram (ng) of
endrin and 2 ng of DDT. The concentration of the solution may be
adjusted by the laboratory to accommodate other injection volumes
such that the same masses of the two analytes are introduced into
the instrument.
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 at or below the ML specified in Table 1, 2, or 3, or
as specified by a regulatory/control authority or in a permit. The
ML value may be rounded to a whole number that is more convenient
for preparing the standard, but must not exceed the ML in Table 1,
2, or 3 for those analytes which list ML values. Alternatively, the
laboratory may establish a laboratory ML for each analyte based on
the concentration in a nominal whole-volume sample that is
equivalent to the concentration of the lowest calibration standard
in a series of standards produced in the laboratory or obtained from
a commercial vendor. The laboratory's ML must not exceed the ML in
Table 1, 2, or 3, and the resulting calibration must meet the
acceptance criteria in Section 7.2.3, based on the RSD, RSE, or
R\2\. The concentrations of the other calibration 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 = 0) calibration (section 7.2.3).
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
[[Page 40917]]
replace the column or break off a short section of the front end of
the column, and repeat the test. Once the scan conditions are
established, they must be used for analyses of all standards,
blanks, and samples.
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 m/z for each analyte (the quantitation
m/z 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 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.
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. Refer to the footnotes to Table 4 or 5 for establishing
operating conditions and to section 7.2.1.1 for establishing scan
conditions.
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. Analyze unfamiliar samples in the scan mode to assure that
the analytes of interest are determined.
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] TR28AU17.014
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. 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 (this value roughly corresponds to the RSD
limit of 35%). 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 standard at or near the
concentration of the mid-point calibration standard (section 7.2.1).
The standard(s) 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. 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, DDT/endrin, and calibration
verification 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).
Alternatively, analytes that do not have acceptance criteria in
Table 6 or Table 8 may
[[Page 40918]]
be based on laboratory control charts, or 60 to 140% may be used.
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 vendor of the SPE 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)-(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 https://www.epa.gov/eg/industrial-effluent-guidelines for a list of industrial categories with existing
effluent guidelines).
(i) At least one of the above wastewater matrix types must have
at least one of the following characteristics:
(A) Total suspended solids greater than 40 mg/L.
(B) Total dissolved solids greater than 100 mg/L.
(C) Oil and grease greater than 20 mg/L.
(D) NaCl greater than 120 mg/L.
(E) CaCO3 greater than 140 mg/L.
(ii) Results of MS/MSD tests must meet QC acceptance criteria in
Section 8.3.
(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, and business 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 (ssection 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 1, 2, or 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,
labware, and reagents, are under control. Each time a batch of
samples is extracted or reagents are changed, a blank
[[Page 40919]]
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 to monitor and evaluate method and laboratory performance on
the sample matrix. 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 must 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 must document and report the failures
(e.g., as qualifiers on results), unless the failures are not
required to be reported as determined by the regulatory/control
authority. Results associated with a QC failure for an analyte
regulated in a discharge cannot be used to demonstrate regulatory
compliance. QC failures do 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 part 136, appendix B under the
same conditions used to determine the MDLs for the analytes listed
in Tables 1, 2, and 3. 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 (LCS
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
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 volume of 1-L and a
concentration of 100 [mu]g/L were used to develop the QC acceptance
criteria in Table 6. 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). Alternatively, acceptance criteria for analytes not listed
in Table 6 may be based on laboratory control charts. 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 section 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
purpose of the MS/MSD requirement is to provide data that
demonstrate the effectiveness of the method as applied to the
samples in question by a given laboratory, and both the data user
(discharger, permittee, regulated entity, regulatory/control
authority, customer, other) and the laboratory share responsibility
for provision of such data. The data user should identify the sample
and the analytes of interest (section 1.3) to be spiked and provide
sufficient sample volume to perform MS/MSD analyses. The laboratory
must, on an ongoing basis, spike at least 5% of the samples in
duplicate from each discharge being monitored to assess accuracy
(recovery and precision). If direction cannot be obtained from the
data user, the laboratory must spike at least one sample in
duplicate per extraction batch of up to 20 samples 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 [verbar]A1 - A2[verbar]/
(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. 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) and is applied to
spike concentrations of 100 [mu]g/L and higher. If spiking is
performed at a concentration lower than 100 [mu]g/L, the laboratory
must use the QC acceptance criteria in Table 6, the optional QC
acceptance criteria calculated for the specific spike concentration
in Table 7, or optional in-house criteria (section 8.3.4). To use
the acceptance criteria in Table 7: (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
[[Page 40920]]
13). Alternatively, acceptance criteria may be based on laboratory
control charts.
8.3.4 After analysis of a minimum of 20 MS/MSD samples for each
target analyte and surrogate, and if the laboratory chooses to
develop and apply the optional in-house QC limits (Section 8.3.3),
the laboratory should calculate and apply the optional 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. If in-house QC limits are developed, 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, and the
remaining analytes (those other than the analytes included in the
80%) must meet the acceptance criteria in Table 6. If an in-house QC
limit for the RPD is greater than the limit in Table 6, 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.
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 LCS (section 8.4.5), or limits based on
laboratory control charts. 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 analysis of the LCS prepared with a
fresh sample concentrate, or to system 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, and if the laboratory
chooses to develop and apply in-house QC limits, the laboratory
should calculate and apply in-house QC limits for recovery to future
LCS samples (section 8.4). Limits for recovery in the LCS should be
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, and the remaining
analytes (those other than the analytes included in the 80%) must
meet the acceptance criteria in Table 6. 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. Many of the analytes and surrogates do not
contain 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,
and at least 80% of the surrogates must meet the 60-140% interim
criteria until in-house LCS and surrogate limits are developed.
Alternatively, acceptance criteria for analytes that do not have
recovery limits in Table 6 may be based on laboratory control
charts. In-house QC acceptance criteria must be updated at least
every two years.
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 an 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 extraction batch, whichever is
greater, analysis of samples must be halted, and the problem
corrected. If the contamination is traceable to the extraction
batch, samples affected by the blank must be re-extracted and the
extracts re-analyzed. If, however, continued re-testing results in
repeated blank contamination, the laboratory must document and
report the failures (e.g., as qualifiers on results), unless the
failures are not required to be reported as determined by the
regulatory/control authority. Results associated with blank
contamination for an analyte regulated in a discharge cannot be used
to demonstrate regulatory compliance. QC failures do not relieve a
discharger or permittee of reporting timely results.
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 test.
8.6.2 Samples, blanks, LCSs, and MS/MSDs--The responses (GC peak
heights or areas) of each internal standard in each sample, blank,
and MS/MSD must be within 50% to 200% (1/2 to 2x) of its respective
response in the LCS for the extraction batch. If, as a group, all
internal standards are not within this range, perform and document
system repair, repeat the calibration verification (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. It may be necessary to use the data system to
calculate a new response factor from calibration data for the
alternate internal standard/analyte pair. If an internal standard
fails the 50-200% criteria and no analytes are detected in the
sample, ignore the failure or report it if required by the
regulatory/control authority.
8.7 Surrogate recoveries--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 recoveries for surrogates not listed in Table 8. At
least 80% of the surrogates must meet the 60-140% interim criteria
until in-house limits are developed. Alternatively, surrogate
recovery limits may be developed from laboratory control charts, but
such limits must be at least as restrictive as those in Table 8.
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 or 8.4.5. If any
[[Page 40921]]
recovery fails its criteria, attempt to find and correct the cause
of the failure. See section 8.1.7 for disposition of failures.
8.8 DDT and endrin decomposition (breakdown)--If DDT and/or
endrin are to be analyzed using this method, the DDT/endrin
decomposition test in section 13.8 must be performed to reliably
quantify these two pesticides.
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 (Px) and the standard
deviation of the percent recovery (sp). Express the accuracy
assessment as a percent interval from Px -2sp to
Px +2sp. For example, if Px = 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). If desired, statements of
accuracy for laboratory performance, independent of performance on
samples, may be developed using LCSs.
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 amber or clear glass
bottles, or in refrigerated bottles using automatic sampling
equipment. If clear glass is used, protect samples from light.
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). Add more sodium sulfate if 80
mg/L is insufficient but 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. 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 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.
Solid-phase extraction (SPE) may be used provided requirements in
section 8.1.2 are met.
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 or phase-separation paper, salting,
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 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
[[Page 40922]]
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 11.2) 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.
Alternative means of compensating the loss during GPC are acceptable
so long as they produce results as accurate as results produced
using the procedure detailed in this Section. An alternative final
volume may be used, if desired, and the calculations adjusted
accordingly.
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, 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
[[Page 40923]]
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 an additional compound (Table 3) is to be determined;
sulfur is to be removed; copper will be used for sulfur removal; and
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 MDLs and MLs for the analytes are
given in Tables 1, 2, and 3. Retention times for many of the
analytes are given in Tables 4 and 5. 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.
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 13.2-13.4 to verify system performance. 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.
13.3 GC resolution--The resolution should be verified on the
mid-point concentration of the initial calibration as well as the
laboratory designated continuing calibration verification level if
closely eluting isomers are to be reported (e.g.,
benzo(b)fluoranthene and benzo(k)fluoranthene). Sufficient gas
chromatographic resolution is achieved if the height of the valley
between two isomer peaks is less than 50% of the average of the two
peak heights.
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 Analysis of DFTPP, the DDT/Endrin decomposition test (if
used), the LCS, and the blank are outside of the 12-hour analysis
shift (section 3.1). The total time for DFTPP, DDT/Endrin, the LCS,
the blank, and the 12-hour shift must not exceed 15 hours.
13.8 Decomposition of DDT and endrin--If DDT and/or endrin are
to be determined, this test must be performed prior to calibration
verification (section 13.4). The QC acceptance criteria (section
13.8.3) must be met before analyzing samples for DDE and/or Endrin.
DDT decomposes to DDE and DDD. Endrin decomposes to endrin aldehyde
and endrin ketone.
13.8.1 Inject 1 [mu]L of the DDT and endrin decomposition
solution (section 6.14). As noted in section 6.14, other injection
volumes may be used as long as the concentrations of DDT and endrin
in the solution are adjusted to introduce the masses of the two
analytes into the instrument that are listed in section 6.14.
13.8.2 Measure the areas of the peaks for DDT, DDE, DDD, Endrin,
Endrin aldehyde, and Endrin ketone. Calculate the percent breakdown
as shown in the equations below:
[[Page 40924]]
[GRAPHIC] [TIFF OMITTED] TR28AU17.015
13.8.3 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
accumulation 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.
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). Identification of an analyte is
confirmed per sections 14.1.1 through 14.1.4.
14.1.1 The signals for the quantitation and secondary 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 The retention time for the analyte should be within
10 seconds of the analyte in the calibration
verification run at the beginning of the shift (section 7.3 or
13.4).
Note: Retention time windows other than 10 seconds
may be appropriate depending on the performance of the gas
chromatograph or observed retention time drifts due to certain types
of matrix effects. Relative retention time (RRT) may be used as an
alternative to absolute retention times if retention time drift is a
concern. RRT is a unitless quantity (see Sec. 22.2), 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. When significant
retention time drifts are observed, dilutions or spiked samples may
help the analyst determine the effects of the matrix on elution of
the target analytes and to assist in qualitative identification.
14.1.3 Either the background corrected EICP areas, or 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 the
quantitation and secondary 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.
If identification is ambiguous, an experienced spectrometrist
(section 1.7) must determine the presence or absence of the
compound.
14.2 Structural isomers that produce very similar mass spectra
should be identified as individual isomers if they have sufficiently
different gas chromatographic retention times. Sufficient gas
chromatographic resolution is achieved if the height of the valley
between two isomer peaks is less than 50% of the average of the two
peak heights. 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] TR28AU17.016
where:
Cex = Concentration of the analyte in the extract, in
[micro]g/mL, and the other terms are as defined in section 7.2.2.
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:
[GRAPHIC] [TIFF OMITTED] TR28AU17.017
where:
Csamp = Concentration of the analyte in the sample
Cex = Concentration of the analyte in the extract, in
[micro]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 specified otherwise by a
regulatory authority or in a discharge permit, results for analytes
that meet the identification criteria are reported
[[Page 40925]]
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,'' ``limit of
quantitation,'' and ``minimum level'' to be synonymous.
15.2.2.1 Report a result for each analyte in each field sample
or QC standard at or above the ML to 3 significant figures. Report a
result for each analyte found in each field sample or QC standard
below the ML as ``ML'' where ML is the concentration of the analyte
at the ML, or as required by the regulatory/control authority or
permit. Report a result for each analyte in a blank at or above the
MDL to 2 significant figures. Report a result for each analyte found
in a blank below the MDL as ``MDL,'' where MDL is the concentration
of the analyte at the MDL, or as required by the regulatory/control
authority or permit.
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 any QC test in this method) must be documented and reported
(e.g., as a qualifier on results), unless the failure is not
required to be reported as determined by the regulatory/control
authority. Results associated with a QC failure cannot be used to
demonstrate regulatory compliance. QC failures 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 section 1.1, this method was validated through
an interlaboratory study in the early 1980s. 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
handled and disposed of as hazardous waste, or neutralized and
disposed of in accordance with all federal, state, and local
regulations. It is the laboratory's responsibility to comply with
all federal, state, and local regulations governing waste
management, particularly the hazardous waste identification rules
and land disposal restrictions. The laboratory using this method has
the responsibility 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. For further information on waste management, see ``The
Waste Management Manual for Laboratory Personnel,'' also available
from the American Chemical Society at the address in section 17.3.
18.3 Many analytes in this method decompose above 500 [ordm]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.
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. Johnson, R.A., and Wichern, D.W., ``Applied Multivariate
Statistical Analysis,'' 3rd edition, Prentice Hall, Englewood
Cliffs, NJ, 1992.
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.)
[[Page 40926]]
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\ (ug/L) ML \5\ (ug/L)
----------------------------------------------------------------------------------------------------------------
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).
\2\ Included for tailing factor testing.
\3\ See section 1.2.
\4\ MDL values from the 1984 promulgated version of Method 625.
\5\ ML = Minimum Level--see Glossary for definition and derivation.
Table 2--Acid Extractables \1\
----------------------------------------------------------------------------------------------------------------
Analyte CAS registry MDL \3\ (ug/L) ML \4\ (ug/L)
----------------------------------------------------------------------------------------------------------------
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).
[[Page 40927]]
\2\ See section 1.2; included for tailing factor testing.
\3\ MDL values from the 1984 promulgated version of Method 625.
\4\ ML = Minimum Level--see Glossary for definition and derivation.
Table 3--Additional Extractable Analytes \1\, \2\
----------------------------------------------------------------------------------------------------------------
Analyte CAS registry MDL \7\ (ug/L) ML \8\ (ug/L)
----------------------------------------------------------------------------------------------------------------
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 .............. ..............
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 .............. ..............
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-Chloronitrobenzene............................................ 121-73-3 .............. ..............
4-Chloro-1,2-phenylenediamine................................... 95-83-0 .............. ..............
[[Page 40928]]
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 .............. ..............
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 .............. ..............
[[Page 40929]]
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-Isopropylnaphthalene.......................................... 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 .............. ..............
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 .............. ..............
[[Page 40930]]
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 .............. ..............
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 \9\..................................................... 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 .............. ..............
[[Page 40931]]
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\ Detected as azobenzene.
\7\ MDL values from the 1984 promulgated version of Method 625.
\8\ ML = Minimum Level--see Glossary for definition and derivation.
\9\ Styrene may be susceptible to losses during sampling, preservation, and/or extraction of full-volume (1 L)
water samples. However, styrene is not regulated at 40 CFR part 136, and it is also listed as an analyte in
EPA Method 624.1 and EPA Method 1625C, where such losses may be less than using Method 625.1.
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
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
[[Page 40932]]
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.
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\ -----------------------------------------------------------------------------
Prime 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
[[Page 40933]]
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 Q Limit for s Range for X Range for P1, Limit for RPD
Analyte (%) \2\ (%) \3\ (%) \3\ P2(%) \3\ (%)
----------------------------------------------------------------------------------------------------------------
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
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
[[Page 40934]]
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).
P1, P2 = 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 Overall
Analyte Recovery, X' precision, sr' precision, S'
([mu]g/L) ([mu]g/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
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
[[Page 40935]]
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
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.
[[Page 40936]]
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 from other published EPA
reference methods may be used provided method performance is not
adversely affected. Alternative tuning criteria specified by an
instrument manufacturer may also be used for another type of mass
spectrometer, 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 from other published EPA
reference methods may be used provided method performance is not
adversely affected. Alternative tuning criteria specified by an
instrument manufacturer may also be used for another type of mass
spectrometer, or for an alternative carrier gas, provided method
performance is not adversely affected.
[[Page 40937]]
21. Figures
[GRAPHIC] [TIFF OMITTED] TR28AU17.018
[[Page 40938]]
[GRAPHIC] [TIFF OMITTED] TR28AU17.019
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.
[deg]C degrees Celsius
[mu]g microgram
[mu]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 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 24-
hour shift (section 3.1). Each extraction batch must be accompanied
by a blank (section 8.5), a laboratory control 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 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
placed under identical conditions, and treated identically
throughout field and laboratory procedures. Results of analyses of
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
[[Page 40939]]
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 part 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 section 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.
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. Appendix B to part 136 is revised 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.
I. Scope and Application
(1) 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.
(2) The MDL procedure is not applicable to methods that do not
produce results with a continuous distribution, such as, but not
limited to, methods for whole effluent toxicity, presence/absence
methods, and microbiological methods that involve counting colonies.
The MDL procedure also is not applicable to measurements such as,
but not limited to, biochemical oxygen demand, color, pH, specific
conductance, many titration methods, and any method where low-level
spiked samples cannot be prepared. Except as described in the
addendum, for the purposes of this procedure, ``spiked samples'' are
prepared from a clean reference matrix, such as reagent water,
spiked with a known and consistent quantity of the analyte. MDL
determinations using spiked samples may not be appropriate for all
gravimetric methods (e.g., residue or total suspended solids), but
an MDL based on method blanks can be determined in such instances.
II. Procedure
(1) Estimate the initial MDL using one or more of the following:
[[Page 40940]]
(a) The mean determined concentration plus three times the
standard deviation of a set of method blanks.
(b) The concentration value that corresponds to an instrument
signal-to-noise ratio in the range of 3 to 5.
(c) The concentration equivalent to three times the standard
deviation of replicate instrumental measurements of spiked blanks.
(d) That region of the calibration where there is a significant
change in sensitivity, i.e., a break in the slope of the
calibration.
(e) Instrumental limitations.
(f) Previously determined MDL.
Note: 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.
Note: The Initial MDL is used when the laboratory does not have
adequate data to perform the Ongoing Annual Verification specified
in Section (4), typically when a new method is implemented or if a
method was rarely used in the last 24 months.
(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., for an analyte with 10% recovery, spiked at 100 micrograms/L,
with mean recovery of 10 micrograms/L; the calculated MDL may be
around 3 micrograms/L. Therefore, in this example, the spiking level
would be 33 times the MDL, but spiking lower may result in no
recovery at all).
(b) Process a minimum of seven spiked samples and seven method
blank samples through all steps of the method. The samples used for
the MDL must be prepared in at least three batches on three separate
calendar dates and analyzed on three separate calendar dates.
(Preparation and analysis may be on the same day.) Existing data may
be used, if compliant with the requirements for at least three
batches, and generated within the last twenty four months. The most
recent available data for method blanks and spiked samples must be
used. Statistical outlier removal procedures should not be used to
remove data for the initial MDL determination, since the total
number of observations is small and the purpose of the MDL procedure
is to capture routine method variability. However, documented
instances of gross failures (e.g., instrument malfunctions,
mislabeled samples, cracked vials) may be excluded from the
calculations, provided that at least seven spiked samples and seven
method blanks are available. (The rationale for removal of specific
outliers must be documented and maintained on file with the results
of the MDL determination.)
(i) If there are multiple instruments that will be assigned the
same MDL, then the sample analyses 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. Each analytical batch may contain one
spiked sample and one method blank sample run together. A spiked
sample and a method blank sample may be analyzed in the same batch,
but are not required to be.
(iii) The same prepared extract may be analyzed on multiple
instruments so long as the minimum requirement of seven preparations
in at least three separate batches is maintained.
(c) Evaluate the spiking level: If any result for any individual
analyte from the spiked samples does not meet the method qualitative
identification criteria or does not provide a numerical result
greater than zero, then repeat the spiked samples 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 as specified in the analytical method
and express the final results in the method-specified reporting
units.
(i) Calculate the sample standard deviation (S) of the replicate
spiked sample measurements and the sample standard deviation of the
replicate method blank measurements from all instruments to which
the MDL will be applied.
(ii) Compute the MDLs (the MDL based on spiked
samples) as follows:
MDLS = t(n -1, 1-[alpha] = 0.99)Ss
Where:
MDLs = the method detection limit based on spiked samples
t(n-1, 1-[alpha] = 0.99) = the Student's t-
value appropriate for a single-tailed 99th percentile t statistic
and a standard deviation estimate with n-1 degrees of freedom. See
Addendum Table 1.
Ss = sample standard deviation of the replicate spiked
sample analyses.
(iii) Compute the MDLb (the 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 method blank results. For ``n'' method blanks
where n >= 100, sort the method blanks in rank order. The (n * 0.99)
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 164 x 0.99 = 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, then calculate the MDLb as:
MDLb = X + tn-1,1-[alpha]
= (0.99)Sb
Where:
MDLb = the MDL based on method blanks
X = mean of the method blank results (use zero in place of the mean
if the mean is negative)
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 method
blank sample analyses.
Note: If 100 or more method blanks are available, as an option,
MDLb may be set to the concentration that is greater than
or equal to the 99th percentile of the method blank results, as
described in Section (2)(d)(iii)(B).
(e) Select 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 samples on each
instrument, in separate batches, using the same spiking
concentration used in Section 2. If any analytes are repeatedly not
detected in the quarterly spiked sample analyses, or do not meet the
qualitative identification criteria of the method (see section 2(c)
of this procedure), then this is an indication that the spiking
level is not high enough and should be adjusted upward. Note that it
is not necessary to analyze additional method blanks together with
the spiked samples, the method blank population should include all
of the routine method blanks analyzed with each batch during the
course of sample analysis.
(b) Ensure that at least seven spiked samples and seven method
blanks are completed for the annual verification. If only one
instrument is in use, a minimum of seven spikes are still required,
but they may be drawn from the last two years of data collection.
(c) At least once per year, re-evaluate the spiking level.
(i) If more than 5% of the spiked samples 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.
(ii) [Reserved]
(d) If the method is altered in a way that can be reasonably
expected to change its sensitivity, then re-determine the initial
MDL according to section 2, and the restart the ongoing data
collection.
(e) If a new instrument is added to a group of instruments whose
data are being pooled to create a single MDL, analyze a minimum of
two spiked replicates and two method blank replicates on the new
instrument. If both method blank results are below the existing MDL,
then the existing MDLb is validated. Combine the new
spiked sample results to the existing spiked sample results and
recalculate the MDLs as in Section 4. If the recalculated
MDLs does not vary by more than the factor specified in
section 4(f) of this
[[Page 40941]]
procedure, then the existing MDLs is validated. If either
of these two conditions is not met, then calculate a new MDL
following the instructions in section 2.
(4) Ongoing Annual Verification.
(a) At least once every thirteen months, re-calculate
MDLs and MDLb from the collected spiked
samples and method blank results using the equations in section 2.
(b) Include data generated within the last twenty four months,
but only data with the same spiking level. Only documented instances
of gross failures (e.g., instrument malfunctions, mislabeled
samples, cracked vials) may be excluded from the calculations. (The
rationale for removal of specific outliers must be documented and
maintained on file with the results of the MDL determination.) If
the laboratory believes the sensitivity of the method has changed
significantly, then the most recent data available may be used,
maintaining compliance with the requirement for at least seven
replicates in three separate batches on three separate days (see
section 2b).
(c) Include the initial MDL spiked samples, if the data were
generated within twenty four months.
(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 its sensitivity, then use only data collected after the
change.
(e) Ideally, use all method blank results from the last 24
months for the MDLb calculation. The laboratory has the
option to use only the last six months of method blank data or the
fifty most recent method blanks, whichever criteria yields the
greater number of method blanks.
(f) The verified MDL is the greater of the MDLs or
MDLb. If the verified MDL is within 0.5 to 2.0 times 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. (The range of 0.5 to 2.0
approximates the 95th percentile confidence interval for the initial
MDL determination with six degrees of freedom.)
Addendum to Section II: Determination of the MDL for a Specific Matrix
The MDL may be determined in a specific sample matrix as well as
in reagent water.
(1) Analyze the sample matrix to determine the native
(background) concentration of the analyte(s) of interest.
(2) If the response for the native concentration is at a signal-
to-noise ratio of approximately 5-20, determine the matrix-specific
MDL according to Section 2 but without spiking additional analyte.
(3) Calculate MDLb using the method blanks, not the
sample matrix.
(4) If the signal-to-noise ratio is less than 5, then the
analyte(s) should be spiked into the sample matrix to obtain a
concentration that will give results with a signal-to-noise ratio of
approximately 10-20.
(5) If the analytes(s) of interest have signal-to-noise ratio(s)
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
32...................................... 31 2.453
48...................................... 47 2.408
50...................................... 49 2.405
61...................................... 60 2.390
64...................................... 63 2.387
80...................................... 79 2.374
96...................................... 95 2.366
100..................................... 99 2.365
------------------------------------------------------------------------
III. 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. The rationale for removal of outlier results, if any,
must be documented and maintained on file with the results of the
MDL determination.
[FR Doc. 2017-17271 Filed 8-25-17; 8:45 am]
BILLING CODE 6560-50-P
Office of the Federal Register, National Archives and Records Administration
Section
Rules and Regulations
Action
Final rule.
Dates
This regulation is effective on September 27, 2017. The incorporation by reference of certain publications listed in the rule is approved by the Director of the Federal Register as of September 27, 2017. For judicial review purposes, this final rule is promulgated as of 1:00 p.m. (Eastern time) on September 12, 2017 as provided at 40 CFR 23.2 and 23.7.
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]
FR Citation
82
FR
40836
RIN Number
2040-AF48
CFR Associated
Environmental Protection; Incorporation by Reference; Reporting and Recordkeeping Requirements; Test Procedures
and
Water Pollution Control