8956 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

ENVIRONMENTAL PROTECTION 

AGENCY 

40 CFR Part 136 

[EPA–HQ–OW–2014–0797; FRL–9920–55– 

OW] 

RIN 2040–AF48 

Clean Water Act Methods Update Rule 

for the Analysis of Effluent 

AGENCY: Environmental Protection 

Agency (EPA). 

ACTION: Proposed rule. 

SUMMARY: EPA proposes changes to 

pollutant analysis methods that are used 

by industries and municipalities to 

analyze the chemical, physical, and 

biological components of wastewater 

and other environmental samples that 

are required by regulations under the 

Clean Water Act. EPA designed the 

proposed changes to increase flexibility 

for the regulated community, improve 

data quality, and update CWA methods 

to keep current with technology 

advances and analytical methods 

science. EPA updates and revises the 

CWA analytical methods from time to 

time, the most recent updates being 

completed in 2012. The new set of 

proposed changes described in this 

notice include revisions to current EPA 

methods and new and/or revised 

methods published by voluntary 

consensus standard bodies, such as 

ASTM International and the Standard 

Methods Committee. EPA also proposes 

to approve certain methods reviewed 

under the alternate test procedures 

program and clarify the procedures for 

EPA approval of nationwide and limited 

use alternate test procedures. Further, 

EPA proposes amendments to the 

procedure for determination of the 

method detection limit to address 

laboratory contamination and to better 

account for intra-laboratory variability. 

DATES: Comments on this proposed rule 

must be received on or before April 20, 

2015. 

ADDRESSES: Submit your comments, 

identified by Docket ID No. EPA–HQ– 

OW–2014–0797, by one of the following 

methods: 

• www.regulations.gov: Follow the 

on-line instructions for submitting 

comments. 

• Email: OW-Docket@epa.gov, 

Attention Docket ID number EPA–HQ– 

OW–2014–0797. 

• Mail: Water Docket, Environmental 

Protection Agency, Mail code: 4203M, 

1200 Pennsylvania Ave. NW., 

Washington, DC 20460. Attention 

Docket ID number EPA–HQ–OW–2014– 

0797. Please include a total of 3 copies. 

• Hand Delivery: Water Docket, EPA 

Docket Center, EPA West Building, 

Room 3334, 1301 Constitution Ave. 

NW., Washington, DC, Attention Docket 

ID number EPA–HQ–OW–2014–0797. 

Such deliveries are only accepted 

during the Docket’s normal hours of 

operation, and special arrangements 

should be made for deliveries of boxed 

information by calling 202–566–2426. 

Instructions: Direct your comments to 

Docket ID number EPA–HQ–OW–2014– 

0797. EPA’s policy is that all comments 

received will be included in the public 

docket without change and may be 

made available online at 

www.regulations.gov, including any 

personal information provided, unless 

the comment includes information 

claimed to be Confidential Business 

Information (CBI) or other information 

whose disclosure is restricted by statute. 

Do not submit information that you 

consider to be CBI or otherwise 

protected through www.regulations.gov 

or email. The www.regulations.gov Web 

site is an ‘‘anonymous access’’ system, 

which means EPA will not know your 

identity or contact information unless 

you provide it in the body of your 

comment. If you send an email 

comment directly to EPA without going 

through www.regulations.gov your email 

address will be automatically captured 

and included as part of the comment 

that is placed in the public docket and 

made available on the Internet. If you 

submit an electronic comment, EPA 

recommends that you include your 

name and other contact information in 

the body of your comment and with any 

disk or CD–ROM you submit. If EPA 

cannot read your comment due to 

technical difficulties and cannot contact 

you for clarification, EPA may not be 

able to consider your comment. 

Electronic files should avoid the use of 

special characters, any form of 

encryption, and be free of any defects or 

viruses. 

Docket: All documents in the docket 

are listed in the www.regulations.gov 

index. Although listed in the index, 

some information in the docket is not 

publicly available, e.g., CBI or other 

information whose disclosure is 

restricted by statute. Certain other 

material, such as copyrighted material, 

will be publicly available only in hard 

copy. Publicly available docket 

materials are available either 

electronically in www.regulations.gov or 

in hard copy at the Water Docket in EPA 

Docket Center, EPA/DC, EPA West 

William J. Clinton Building, Room 3334, 

1301 Constitution Ave. NW., 

Washington, DC. The Public Reading 

Room is open from 8:30 a.m. to 4:30 

p.m., Monday through Friday, excluding 

legal holidays. The telephone number 

for the Public Reading Room is 202– 

566–1744 and the telephone number for 

the Water Docket is 202–566–2426. 

FOR FURTHER INFORMATION CONTACT: 

Adrian Hanley, Engineering and 

Analysis Division (4303T), Office of 

Water, Environmental Protection 

Agency, 1200 Pennsylvania Ave. NW., 

Washington, DC 20460–0001; telephone: 

202–564–1564; email: hanley.adrian@

epa.gov. 

SUPPLEMENTARY INFORMATION: 

Table of Contents 

I. General Information 

II. Overview 

III. Statutory Authority 

IV. Purpose and Summary of Proposed 

Rule 

V. Statutory and Executive Order Reviews 

I. General Information 

A. Does this Action apply to me? 

Entities potentially affected by the 

requirements of this proposed action 

include: 

Category Examples of potentially affected entities 

State, Territorial, and Indian Tribal 

Governments.

States, territories, and tribes authorized to administer the National Pollutant Discharge Elimination System 

(NPDES) permitting program; states, territories, and tribes providing certification under CWA section 

401; state, territorial, and tribal owned facilities that must conduct monitoring to comply with NPDES permits. 

Industry ........................................... Facilities that must conduct monitoring to comply with NPDES permits. 

Municipalities ................................... Publicly Owned Treatment Works (POTWs) or other municipality owned facilities that must conduct monitoring to comply with NPDES permits. 

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Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 8957 

1NPDES permit regulations also specify that the 

approved method needs to be sufficiently sensitive. 

See 40 CFR 122.21.e.3. 

This table is not exhaustive, but rather 

provides a guide for readers regarding 

entities likely to be affected by this 

action. This table lists types of entities 

that EPA is now aware of that could 

potentially be affected by this action. 

Other types of entities not listed in the 

table could also be affected. To 

determine whether your facility is 

affected by this action, you should 

carefully examine the applicability 

language at 40 CFR 122.1 (NPDES 

purpose and scope), 40 CFR 136.1 

(NPDES permits and CWA) and 40 CFR 

403.1 (pretreatment standards purpose 

and applicability). If you have questions 

regarding the applicability of this action 

to a particular entity, consult the 

appropriate person listed in the 

preceding FOR FURTHER INFORMATION

CONTACT section. 

B. What should I consider as I prepare 

my comments for EPA? 

1. Submitting CBI. Do not submit CBI 

to EPA through www.regulations.gov or 

email. Clearly mark the part or all of the 

information that you claim to be CBI. 

For CBI information in a disk that you 

mail to EPA, mark the outside of the 

disk as CBI and then identify 

electronically within the disk the 

specific information that is claimed as 

CBI. In addition to one complete version 

of the comment that includes 

information claimed as CBI, a copy of 

the comment that does not contain the 

information claimed as CBI must be 

submitted for inclusion in the public 

docket. Information so marked will not 

be disclosed except in accordance with 

procedures for handling and protection 

of CBI set forth in 40 CFR part 2. 

2. Tips for Preparing Your Comments. 

When submitting comments, remember 

to: 

• Identify the rulemaking by Docket 

ID number and other identifying 

information (subject heading, Federal 

Register date and page number). 

• Explain why you agree or disagree, 

suggest alternatives, and substitute 

language for your requested changes. 

• Describe any assumptions and 

provide any technical information and/ 

or data that you used. 

• If you estimate potential costs or 

burdens, explain how you arrived at 

your estimate in sufficient detail to 

allow for it to be reproduced. 

• Provide specific examples to 

illustrate your concerns, and suggest 

alternatives. 

• Explain your views as clearly as 

possible, avoiding the use of profanity 

or personal threats. 

• Make sure to submit your 

comments by the comment period 

deadline identified. 

II. Overview 

This preamble describes the reasons 

for the proposed rule; the legal authority 

for the proposed rule; a summary of the 

proposed changes and clarifications; 

and explanation of the abbreviations 

and acronyms used in this document. In 

addition, this preamble solicits 

comment and data from the public. 

Abbreviations and Acronyms Used in 

the Preamble and Proposed Rule Text 

AA: Atomic Absorption 

ADMI: American Dye Manufacturers Institute 

ASTM: ASTM International 

ATP: Alternate Test Procedure 

CAS: Chemical Abstract Services 

CFR: Code of Federal Regulations 

CWA: Clean Water Act 

EPA: Environmental Protection Agency 

FLAA: Flame Atomic Absorption 

Spectroscopy 

GC: Gas Chromatograph 

ICP/AES: Inductively Coupled Plasma— 

Atomic Emission Spectroscopy 

ICP/MS: Inductively Coupled Plasma—Mass 

Spectrometry 

LCS: Laboratory Control Sample 

MS: Mass Spectrometry 

MS/MSD: Matrix Spike/Matrix Spike 

Duplicate 

NPDES: National Pollutant Discharge 

Elimination System 

POTW: Publicly Owned Treatment Works 

QA: Quality Assurance 

QC: Quality Control 

SM: Standard Methods 

STGFAA: Stabilized Temperature Graphite 

Furnace Atomic Absorption Spectroscopy 

USGS: United States Geological Survey 

VCSB: Voluntary Consensus Standards Body 

III. Statutory Authority 

EPA proposes this regulation under 

the authorities of sections 301(a), 

304(h), and 501(a) of the CWA, 33 

U.S.C. 1311(a), 1314(h), and 1361(a). 

Section 301(a) of the CWA prohibits the 

discharge of any pollutant into 

navigable waters unless the discharge 

complies with, among other provisions, 

a NPDES permit issued under section 

402 of the CWA. Section 304(h) of the 

CWA requires the Administrator of the 

EPA to ‘‘. . . promulgate guidelines 

establishing test procedures for the 

analysis of pollutants that shall include 

the factors which must be provided in 

any certification pursuant to [section 

401 of the CWA] or permit application 

pursuant to [section 402 of the CWA].’’ 

Section 501(a) of the CWA authorizes 

the Administrator to ‘‘. . . prescribe 

such regulations as are necessary to 

carry out this function under [the 

CWA].’’ EPA generally has codified its 

test procedure regulations (including 

analysis and sampling requirements) for 

CWA programs at 40 CFR part 136, 

though some requirements are codified 

in other parts (e.g., 40 CFR Chapter I, 

Subchapters N and O). 

IV. Purpose and Summary of Proposed 

Rule 

The CWA requires EPA to promulgate 

test procedures (analytical methods) for 

analyses required in NPDES permit 

applications and for reports required 

under NPDES permits. EPA codifies 

these approved test procedures at 40 

CFR part 136. EPA regions, as well as 

authorized states, territories and tribes 

issue NPDES permits. These permits 

must include conditions designed to 

ensure compliance with the technologybased and water quality-based 

requirements of the CWA, including in 

many cases, restrictions on the quantity 

of specific pollutants that can be 

discharged as well as pollutant 

measurement and reporting 

requirements. Often, entities have a 

choice in deciding which approved test 

procedure they will use for a specific 

pollutant because EPA has approved the 

use of more than one.1

The procedures for the analysis of 

pollutants required by CWA section 

304(h) are a central element of the 

NPDES permit program. Examples of 

where these EPA analytical methods 

must be used include, among others, the 

following: (1) Applications for NPDES 

permits, (2) sampling or other reports 

required under NPDES permits, (3) 

other requests for quantitative or 

qualitative effluent data under the 

NPDES regulations, (4) State CWA 401 

certifications and (5) sampling and 

analysis required under EPA’s General 

Pre-Treatment Regulations for Existing 

and New Sources of Pollution 40 CFR 

136.1 and 40 CFR 403.12(b)(5)(v). 

Periodically, EPA proposes to update 

the approved methods in 40 CFR part 

136. In general, the changes in this 

proposed action fall into the following 

categories: new and revised EPA 

methods and new and revised methods 

adopted by VCSBs; methods EPA has 

reviewed under EPA’s national alternate 

test procedures (ATP) program and 

preliminarily concluded are appropriate 

for nationwide use; certain corrections 

to 40 CFR part 136; and amendments to 

the procedure for determination of the 

MDL primarily to address laboratory 

contamination and to better account for 

intra-laboratory variability. Collectively, 

EPA’s current understanding indicates 

that adoption of these proposed 

revisions would improve data quality, 

update methods to keep current with 

technology advances, provide additional 

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8958 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

clarity for ATPs, and provide the 

regulated community with greater 

flexibility. 

The following paragraphs provide 

details on the proposed revisions. 

A. Changes to 40 CFR 136.3 and 

Appendix A to Include New Versions of 

Previously Approved EPA Methods 

EPA proposes revisions to the 

approved EPA Methods 608, 624, and 

625 which it adopted in 1984, and 

proposes to make a minor correction to 

the parameter list in EPA Method 611. 

These four EPA methods are listed in 

Table IC at 40 CFR part 136. Methods 

608 and 625 also are listed in Tables ID 

and IG, and Methods 624 and 625 are 

listed in Table IF. EPA also proposes 

minor corrections to microbiological 

methods 1600, 1603, 1680, and 1682. 

These four EPA methods are listed in 

Table IA at 40 CFR part 136, and 

Methods 1600 and 1603 are listed in 

Table IH. 

1. Methods 608, 624, and 625 

The proposed revisions take 

advantage of improvements in analytical 

technology and allow greater flexibility 

in order to accommodate future 

improvements to the methods and 

generally obviate any need for 

additional revisions. EPA revised these 

methods in collaboration with other 

EPA offices, states, and environmental 

laboratory organizations. The revisions 

conform to the following principles: 

Updated Technology: EPA changed 

the GC columns from packed columns 

to capillary (open tubular) columns. 

Capillary columns provide greater 

resolution and decreased adsorption 

(loss) of the analytes and, therefore, 

result in a significant improvement in 

the accuracy (recovery) and precision of 

the results. 

Method Flexibility: The revised 

methods allow greater method 

flexibility so that the methods more 

closely align with 40 CFR 136.6. This 

flexibility would make it easier for 

laboratories to make in-house 

improvements and technology updates 

in the future that will not compromise 

the original quality control acceptance 

criteria of the methods. Consistent with 

40 CFR 136.6, EPA built into the 

methods procedures that will allow a 

laboratory to make limited changes to a 

method without applying for an ATP; 

however, the laboratory must document 

that the revisions produce results 

consistent with the QC acceptance 

criteria in the method in order to take 

advantage of the built-in flexibility. For 

example, the revised methods allow 

access to a greater list of compounds 

than the list of compounds determined 

by the original versions of these 

methods, provided that the laboratory 

can demonstrate acceptable accuracy 

and precision with these analytes in the 

specified matrices. The expanded list of 

compounds is an amalgamation of lists 

from Methods 1624, 1625, 1699 and 

other EPA methods that demonstrate the 

technology can be used to quantify these 

additional analytes. The revisions also 

allow more flexibility to adopt different 

extraction procedures, such as solid 

phase extraction. The revised methods 

include requirements for a laboratory to 

develop its own in-house QC acceptance 

criteria for tests of the laboratory control 

sample and tests of matrix spike and 

matrix spike duplicate samples, 

provided the LCS and MS/MSD meet 

minimum criteria specified in the 

method. The revisions also clarify that 

hydrogen can be used as a carrier gas for 

the methods. Some of the flexibility 

EPA proposes to add to the methods is 

currently specified in 40 CFR 

136.6(b)(4)(xvi). Because EPA proposes 

to incorporate that flexibility directly 

into the method, EPA proposes to delete 

the corresponding text from 40 CFR 

136.6. 

Method Harmonization: EPA updated 

these methods to make them more 

consistent with the most recent updates 

of similar methods from the Office of 

Ground Water and Drinking Water and 

the Office of Resource Conservation and 

Recovery. EPA revised the required QC 

frequencies and standards (internal 

standards and surrogates) to more 

closely match the methods from other 

EPA analytical method programs. 

Laboratories that run methods from 

multiple EPA programs will benefit 

from these revisions. 

2. Method 611 

EPA proposes a minor correction to a 

parameter name in the parameter list of 

of EPA Method 611 (‘‘Haloethers’’). As 

currently listed, the compound with the 

CAS Registry Number 108–60–1 is bis(2- 

chloroisopropyl)ether. EPA proposes to 

correct the analyte name to 2,2′- 

oxybis(1-chloropropane), which 

matches the CAS Number 108–60–1. 

The original analyte name bis(2- 

chloroisopropyl)ether has a CAS 

number of 39638–32–9. EPA is unaware 

that this chemical has ever been in 

industrial production, and is therefore 

unlikely to be a compound of 

monitoring concern. Furthermore, it is 

not possible to procure an analytical 

standard reference material for the 

compound with CAS number 39638– 

32–9. The compound in the parameter 

list should be 2,2′-oxybis(1- 

chloropropane), CAS number 108–60–1. 

3. Methods 1600, 1603, 1680, and 1682 

EPA proposes the following changes 

for EPA microbiological methods 1600, 

1603, 1680, and 1682. These changes 

correct typographical or other errors that 

EPA identified in the methods after 

publication. EPA proposes to revise all 

of these methods with new EPA 

document numbers and dates. 

a. EPA Method 1600 for Enterococci 

using membrane filtration: In Table 3 

Verification controls, EPA changed the 

negative control for brain heart infusion 

broth incubated at 45 °C from E. coli to 

Enterobacter aerogenes. E. coli is 

thermotolerant and E. aerogenes is not, 

so E. coli is not an appropriate negative 

control when heated. 

b. EPA Method 1603 for E. coli using 

membrane filtration: In Section 11.5, 

EPA changed the number of colonies on 

a countable plate from 20–60 to 20–80 

colonies. Sixty colonies was a 

typographical error. In addition the 

following sentence was inadvertently 

omitted and EPA included it: Sample 

volumes of 1–100 mL are normally 

tested at half-log intervals (e.g., 100, 30, 

10, and 3 mL). 

c. EPA Method 1680 for fecal 

coliforms using multiple tube 

fermentation: in Section 3.1 Definitions, 

the sentence ‘‘The predominant fecal 

coliform is E. coli.’’ should read ‘‘The 

predominant fecal coliform can be E. 

coli.’’ 

d. EPA Method 1682 for Salmonella 

by MSRV medium: (1) In Section 9.3, 

Table 2, the lab-prepared spike 

acceptance criteria should read 

‘‘Detect—254%’’ and ‘‘Detect—287%’’ 

and (2) in Section 14.5, Table 9, the 

spiked Salmonella for Example 2, 

Liquid should read ‘‘3.7x10 8 CFU/mL.’’ 

B. Methods Incorporated by Reference 

Currently, hundreds of methods and 

ATPs are incorporated by reference 

within 40 CFR part 136. In most cases, 

40 CFR part 136 contains multiple 

approved methods for a single pollutant 

and regulated entities often have a 

choice in the selected method. The 

proposed rule contains revisions to 

methods that will be incorporated by 

reference from two VCSBs: Standard 

Methods and ASTM. EPA proposed 

VCSB methods in compliance with the 

National Technology Transfer Act (see 

Section V.I below). The proposed VCSB 

methods are available on their 

respective VCSB Web sites to everyone 

at a cost determined by the VCSB, 

generally from $40 to $80. Both 

organizations also offer memberships or 

subscriptions that allow unlimited 

access to their methods. The cost of 

obtaining these methods is not a 

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significant financial burden for a 

discharger or environmental laboratory, 

making the methods reasonably 

available. The proposal also includes 

USGS methods and vendor ATPs that 

are incorporated by reference. The ATPs 

and USGS methods are available free of 

charge on the Web site for that 

organization. Therefore, EPA concludes 

that the proposed methods and ATPs 

incorporated by reference are reasonably 

available. The individual standards are 

discussed in greater detail below. 

C. Changes to 40 CFR 136.3 to Include 

New Versions of Approved Standard 

Methods 

EPA proposes to approve new 

versions of currently approved Standard 

Methods. The new versions of currently 

approved Standard Methods clarify or 

improve the instructions in the method, 

improve the QC instructions, or make 

editorial corrections. Consistent with 

the previous method update rule (77 FR 

29767–29768), EPA proposes to 

generally approve and include in 40 

CFR part 136 only the most recent 

version of a method published by the 

Standard Methods Committee by listing 

only one version of the method with the 

year of publication designated by the 

last four digits in the method number 

(e.g., SM 3111 B–2011). The date 

indicates the latest revision date of the 

method. This allows use of a specific 

method in any edition that includes a 

method with the same method number 

and year of publication. 

Most of the revisions that EPA 

proposes to Standard Methods 

previously approved in 40 CFR part 136 

do not contain any substantive changes. 

The following describes the proposed 

non-substantive changes related to 

Standard Methods in 40 CFR part 136. 

Each entry contains the proposed 

Standard Methods number and date, the 

parameter, and a brief description of the 

analytical technique. The methods 

listed below are organized according to 

the table at 40 CFR part 136 in which 

they appear. 

The following changes would apply to 

Table IA at 40 CFR part 136: 

1. SM 9221 (B,C,E,F)–2006, Coliform 

(fecal), Coliform (fecal) in presence of 

chlorine, Coliform (total), Coliform 

(total) in presence of chlorine, E. coli, 

most probable number (MPN), 5 tube 3 

dilution. 

2. SM 9223–2004, E. coli, multiple 

tube/multiple well. 

3. SM 9230 (B,C)–2007, Fecal 

Streptococci, Enterococci, most 

probable number (MPN), 5 tube 3 

dilution or membrane filtration. 

The following changes would apply to 

Table IB at 40 CFR part 136: 

1. SM 2120 B–2011, color, platinum 

cobalt method. 

2. SM 2130 B–2011, turbidity, 

nephelometric method. 

3. SM 2310 B–2011, acidity, titration 

using electrometric endpoint or 

phenolphthalein endpoint. 

4. SM 2320 B–2011, alkalinity, 

electrometric or colorimetric titration to 

pH 4.5. 

5. SM 2340 B–2011 and SM 2340 C– 

2011, hardness, by the calculation 

method or EDTA titration. 

6. SM 2510 B–2011, conductivity, 

Wheatstone bridge method. 

7. SM 2540 B–2011, SM 2540 C–2011, 

SM 2540 D–2011, SM 2540 E–2011, and 

SM 2540 F–2011, total, filterable, nonfilterable, volatile, and settleable residue 

(solids, listed in the same order as the 

method numbers), all by gravimetric 

methodologies. 

8. SM 2550 B–2010, temperature, 

thermometric. 

9. SM 3111 B–2011, SM 3111 C–2011, 

SM 3111 D–2011, and SM 3111 E–2011, 

metals, direct aspiration AA methods 

with different gas mixtures. Each 

method has a different list of metals; no 

changes are proposed to these lists. 

10. SM 3112 B–2011, metals, 

applicable to mercury, cold-vapor 

atomic absorption spectrometric 

method. 

11. SM 3114 B–2011 and SM 3114 C– 

2011, total arsenic and total selenium, 

hydride generation/atomic absorption 

spectrometric methods. Both analyze 

total arsenic and total selenium. 

12. SM 3120 B–2011, metals, ICP 

method; no changes are proposed for the 

approved list of metals. 

13. SM 3125 B–2011, metals, ICP/MS 

method; no changes are proposed for the 

approved list of metals. 

14. SM 3500-Al B–2011, aluminum, 

colorimetric method. 

15. SM 3500-As B–2011, arsenic, 

colorimetric method (SDDC). 

16. SM 3500-Ca B–2011, calcium, 

titrimetric method (EDTA). 

17. SM 3500-Cr B–2011 and SM 3500- 

Cr C–2011, chromium, the ‘‘B’’ method 

uses a colorimetric method (diphenylcarbazide) and is approved for total or 

dissolved chromium, the ‘‘C’’ method 

uses ion chromatography and is only 

approved for dissolved chromium. 

18. SM 3500-Cu B–2011 and SM 

3500-Cu C–2011, copper, both method 

sections use colorimetric methods, the 

‘‘B’’ method uses a neocuproine reagent 

and the ‘‘C’’ method uses a 

bathocuproine reagent. 

19. SM 3500-Fe B–2011, iron, 

colorimetric method (phenanthroline). 

20. SM 3500-K B–2011 and SM 3500– 

K C–2011, potassium, the ‘‘B’’ method is 

a flame photometric method and the 

‘‘C’’ method is an electrode method. 

21. SM 3500-Mn B–2011, manganese, 

colorimetric method (persulfate). 

22. SM 3500-Na B–2011, sodium, 

flame photometric method. 

23. SM 3500-Pb B–2011, lead, 

colorimetric method (dithizone). 

24. SM 3500-V B–2011, vanadium, 

colorimetric method (gallic acid). 

25. SM 3500-Zn B–2011, zinc, 

colorimetric method (zincon). 

26. SM 4110 (B–D)–2011, anions, ion 

chromatography; no changes are 

proposed for the approved analyte list. 

27. SM 4140 B–2011, inorganic 

anions, capillary ion electrophoresis 

with indirect UV detection: No changes 

are proposed for the approved analyte 

list. 

28. SM 4500-B B–2011, boron, 

spectrophotometer or filter photometer 

(curcumin). 

29. SM 4500-Cl¥ (B–E)–2011, 

chloride, titrimetric: (silver nitrate), 

(mercuric nitrate), automated 

(ferricyanide), potentiometric titration 

30. SM 4500-Cl (B–G)–2011, chlorine 

(residual), amperometric direct, 

amperometric direct (low level), 

iodometric direct, back titration ether 

end–point, titrimetric: N,N-diethyl-pphenylenediamine with ferrous 

ammonium sulfate (DPD-FAS), 

spectrophotometric (DPD). 

31. SM 4500-CN¥ (B–G)–2011, 

cyanide, manual distillation with MgCl2

followed by: Titrimetric, 

spectrophotometric, manual, ion 

selective electrode, cyanide amenable to 

chlorination (CATC); manual 

distillation with MgCl2, followed by: 

Titrimetric or spectrophotometric. 

32. SM 4500-F¥ (B–E)–2011, fluoride, 

manual distillation, followed by any of 

the following: Electrode, manual, 

colorimetric, fluoride dye reagent 

(SPADNS is the common name for the 

fluoride dye reagent which is a mixture 

of chemicals), automated complexone. 

33. SM 4500-H+ B–2011, hydrogen 

ion (pH), electrometric measurement. 

34. SM 4500-NH3 (B–H)–2011, 

ammonia (as nitrogen), manual 

distillation or gas diffusion (pH > 11), 

followed by any of the following: 

Titration, electrode, manual phenate, 

salicylate, or other substituted phenols 

in Berthelot reaction based methods; 

automated phenate, salicylate, or other 

substituted phenols in Berthelot 

reaction based methods. 

35. SM 4500-NO2

¥ B–2011, nitrite (as 

nitrogen), spectrophotometric: Manual. 

36. SM 4500-NO3

¥ D–2011, nitrate (as 

nitrogen), ion selective electrode. 

37. SM 4500-NO3

¥ (E,F, H)–2011, 

nitrate-nitrite (as nitrogen), colorimetric: 

Cadmium reduction-manual and 

automated, and colorimetric: Automated 

hydrazine. 

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38. SM 4500-NO3

¥ (E,F)–2011, nitrite 

(as nitrogen), colorimetric: Cadmium 

reduction-manual and automated. 

39. SM 4500-Norg (B–D)–2011, total 

Kjeldahl nitrogen (as nitrogen, organic), 

semi-automated block digester 

colorimetric (distillation not required). 

40. SM 4500-O (B–G), oxygen 

(dissolved), Winkler (azide 

modification), electrode. 

41. SM 4500-P (B (5), E–H)–2011, 

phosphorus and ortho-phosphate, 

persulfate digestion, digestion, followed 

by any of the following: Manual or 

automated ascorbic acid reduction. The 

‘‘B Part 5’’ method is the persulfate 

digestion procedure and is required 

prior to measurement of total 

phosphorus using SM 4500 P (E–H). The 

‘‘E’’ through ‘‘G’’ methods are approved 

for both total phosphorus and orthophosphate. The ‘‘H’’ method is only 

approved for total phosphorous. 

42. SM 4500-S2¥ (B–D, F,G)–2011, 

sulfide, sample pretreatment, titrimetric 

(iodine) analysis, colorimetric 

(methylene blue), ion selective 

electrode. 

43. SM 4500-SiO2 (C,E,F)–2011, silica, 

0.45-micron filtration followed by any 

of the following: Colorimetric, manual 

or automated (Molybdosilicate). 

44. SM 4500-SO3

2¥ B–2011, sulfite, 

titrimetric (iodine-iodate). 

45. SM 4500-SO4

2¥ (C–G)–2011, 

sulfate, automated colorimetric, 

gravimetric, and turbidimetric. 

46. SM 5210 B–2011, biochemical 

oxygen demand (BOD5), dissolved 

oxygen depletion. 

47. SM 5220 (B–D)–2011, chemical 

oxygen demand (COD), titrimetric; 

spectrophotometric, manual or 

automatic. 

48. SM 5310 (B-D)–2011, total organic 

carbon (TOC), combustion, heated 

persulfate or UV persulfate oxidation. 

49. SM 5520 (B,F)–2011, oil and 

grease, hexane extractable material 

(HEM): n-hexane extraction and 

gravimetry, silica gel treated HEM 

(SGT–HEM): Silica gel treatment and 

gravimetry. 

50. SM 5530 (B,D)–2010, phenols, 

manual distillation, followed by 

colorimetric (4AAP) manual. 

51. SM 5540 C–2011, surfactants, 

colorimetric (methylene blue). 

The following changes would apply to 

Table IC at 40 CFR part 136: 

1. SM 6200 (B,C)–2011, volatile 

organic compounds, purge and trap 

capillary-column gas chromatographic/

mass spectrometric (GC/MS), purge and 

trap capillary-column gas 

chromatographic (GC). 

2. SM 6440 B–2005, polynuclear 

aromatic hydrocarbons (PAHs), high 

performance liquid chromatography 

(HPLC). 

The following changes would apply to 

Table ID at 40 CFR part 136: 

1. SM 6630 (B, C)–2007, 

organochlorine pesticides, gas 

chromatography (GC). 

2. SM 6640 B–2006, acidic herbicide 

compounds, gas chromatography (GC). 

EPA also proposes revisions to certain 

Standard Methods approved in Part 136 

for which Standard Methods adopted 

updates that contain substantive 

changes. The following summarizes 

these changes for each method, 

organized by the table at 40 CFR part 

136 in which they appear. 

The following changes would apply to 

Table IA and/or Table IH at 40 CFR part 

136: 

1. EPA proposes that the membrane 

filtration method SM 9222 B–1997 be 

replaced with SM 9222 B–2006. This 

method analyzes Coliform (total) in the 

presence of chlorine. The newer method 

includes a number of technology 

updates that do not significantly change 

the procedure. In addition, the method: 

a. Modified the procedure to allow for 

the use of a humidified incubator if 

loose-lidded plates are used during 

incubation. 

b. Added a note that five typical and 

five atypical colonies per membrane 

need to be identified during coliform 

verification. 

c. Moved the definition of ‘‘Coliform’’ 

that was Section 4 of SM 9222, and 

renumbered the rest of the document, 

such that the ‘‘Procedure’’ is now 

Section 4, instead of Section 5. This is 

not a substantive change except that in 

Table IA, Parameter 4 ‘‘Coliform (total), 

in presence of chlorine, number per 100 

mL’’ the citation for ‘‘MF with 

enrichment’’ would be changed from 

‘‘9222 (B+B.5c)–1997’’ to ‘‘9222 

(B+B.4c)–2006.’’ 

2. EPA proposes that the membrane 

filtration method SM 9222 D–1997 be 

replaced with SM 9222 D–2006. This 

method analyzes Coliform (fecal) and 

Coliform (fecal) in the presence of 

chlorine. The new method allows use of 

a dry recirculating incubator as 

specified in the culture dishes section. 

In addition, EPA proposes to add the 

following footnote to Tables IA and IH 

regarding SM9222D–2006 for fecal 

coliform verification frequency: ‘‘The 

verification frequency is at least five 

typical and five atypical colonies per 

sampling site on the day of sample 

collection & analysis.’’ SM 9222 D–2006 

specifies that the fecal coliform colonies 

should be verified ‘‘at a frequency 

established by the laboratory,’’ which 

can be as low as zero. Colonies need be 

verified to prevent misidentification of 

results as false positive or false negative. 

3. EPA proposes that the membrane 

filtration method SM 9222 G–1997 be 

replaced with SM 9222 G–2006 in Table 

IH. These methods analyze for E. coli 

and Fecal Coliforms. The newer method 

includes a number of technology 

updates that do not significantly change 

the procedure. In addition, the method 

now has a modified composition of EC 

broth to include different quantities of 

KH2PO4 and 4-methylumbelliferyl-b-Dglucuronide. 

The following changes would apply to 

Table IB at 40 CFR part 136: 

EPA proposes SM 2120 F–2011 be 

added to Table IB for Color. EPA 

previously approved it as SM 2120 E– 

1993. It is also similar to the currently 

approved National Council for Air and 

Stream Improvement, Inc. method that 

uses American Dye Manufacturers 

Institute weighted–ordinate 

spectrophotometric parameters. 

1. EPA proposes that SM 3113 B– 

2004, a metals atomic absorption 

furnace method, be replaced with the 

revised version SM 3113 B–2010. The 

only substantive change would be a 

reduction in the required replicate 

analyses of each calibration standard 

from three to two. Similar EPA methods 

do not require replicates of each 

calibration standard. 

Finally, Standard Methods requested 

that EPA propose SM 6810 for the 

analysis of pharmaceutical and personal 

care products in water. EPA does not 

propose to add this method because no 

supporting data were received by the 

deadline to demonstrate that the method 

had undergone full inter-laboratory 

validation. 

D. Changes to 40 CFR 136.3 to Include 

New Versions of Approved ASTM 

Methods 

EPA proposes to approve new 

versions of currently approved ASTM 

methods, for the same reasons outlined 

in the first paragraph of Section IV.B 

above. Many of the changes EPA 

proposes to ASTM Methods approved in 

40 CFR part 136 do not contain any 

substantive changes. The following 

describes the proposed changes related 

to ASTM Methods in 40 CFR part 136. 

Each entry contains (in the following 

order): proposed ASTM method number 

and date, the parameter, a brief 

description of the analytical technique, 

and a brief description of any 

substantive changes in this revision 

from the last approved version of the 

method. The methods listed below are 

organized according to the table at 40 

CFR part 136 in which they appear. 

The following changes would apply to 

Table IB at 40 CFR part 136: 

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1. ASTM D 511–09 (A, B), calcium 

and magnesium, titrimetric (EDTA), AA 

direct aspiration; the modified method 

includes less specific calibration 

requirements for the part A titrimetric 

method than the previous version. 

However, the revised requirements are 

still more comprehensive than other 

approved methods. Therefore, EPA 

considers this revised method has 

adequate calibration criteria. 

2. ASTM D 516–11, sulfate ion, 

turbidimetric, no substantive changes. 

3. ASTM D 858–12 (A–C), manganese, 

atomic absorption (AA) direct 

aspiration, AA furnace; the modified 

method allows for pH adjustments in 

the laboratory, if the sample is returned 

within 14 days following sampling. The 

modified method also allows the use of 

block digestion systems for trace metal 

analysis, and quality control procedures 

now require the lab to analyze a 

continuing calibration blank and 

continuing calibration verification at a 

frequency of 10%. 

4. ASTM D 859–10, silica, 

colorimetric, manual; the modified 

method allows the use of direct reading 

spectrophotometer or filter photometer, 

which is common for most approved 

colorimetric methods. 

5. ASTM D 1067–11, acidity or 

alkalinity, electrometric endpoint or 

phenolphthalein endpoint; 

electrometric or colorimetric titration to 

pH 4.5, manual; no substantive changes 

6. ASTM D 1068–10 (A–C), iron, AA 

direct aspiration; AA furnace; 

Colorimetric (Phenanthroline); EPA 

originally approved Parts A–D, but 

ASTM discontinued Part B. EPA 

proposes that Parts C and D in the 

existing 40 CFR part 136 Table 1B, be 

shifted to Parts B and C to account for 

the discontinued Part B. Additionally, 

ASTM increased the frequency of 

quality control parameters for Test 

Method A—Atomic Absorption. The 

method now includes a method blank, 

a matrix spike sample and a control 

sample with every ten samples. 

7. ASTM D 1126–12, hardness, 

titrimetric (EDTA); no substantive 

changes. 

8. ASTM D 1179–10, fluoride ion, 

electrode, manual; colorimetric, 

(SPADNS); The revision removed 

calculation, precision and bias, and 

quality control procedures (method 

blank, matrix spike, LCS) previously 

included for Test Method B–Ion 

Selective Electrode. The method 

replaces those requirements with a lab 

duplicate and a reference sample 

analysis. This is similar to EPA 

approved SM 4500–F¥ (C, D) currently 

in 40 CFR part 136. The revision also 

removed the silver sulfate reagent used 

to remove chloride from the sample, as 

it is no longer considered a major 

interference. 

9. ASTM D 1246–10, bromide ion, 

electrode; no substantive changes. 

10. ASTM D 1687–12 (A–C), 

chromium (total) and dissolved 

hexavalent chromium, colorimetric 

(diphenyl-carbazide); AA direct 

aspiration; AA furnace; ASTM modified 

the method to allow the use of block 

digestion systems for trace metal 

analysis, and now allows for pH 

adjustments in the laboratory if the 

sample is returned within 14 days 

following sampling. 

11. ASTM D 1688–12 (A–C), copper, 

AA direct aspiration, AA furnace; 

ASTM modified the method to allow the 

use of block digestion systems for trace 

metal analysis, and now allows for pH 

adjustments in the laboratory if the 

sample is returned within 14 days 

following sampling. ASTM also requires 

analysis of a continuing calibration 

blank and continuing calibration 

verification at a 10% frequency. 

12. ASTM D 1691–12 (A, B), zinc, AA 

direct aspiration; ASTM modified the 

method to allow the use of block 

digestion systems for trace metal 

analysis, and now allows for pH 

adjustments in the laboratory if the 

sample is returned within 14 days 

following sampling. 

13. ASTM D 1976–12, dissolved, 

total-recoverable, or total elements, 

inductively coupled plasma/atomic 

emission spectroscopy (ICP/AES); 

ASTM modified the method to allow 

block digestion systems for trace metal 

analysis. 

14. ASTM D 3223–12, total mercury, 

cold vapor, manual; ASTM modified the 

method to allow the use of block 

digestion systems for trace metal 

analysis, and requires analysis of a 

continuing calibration blank and 

continuing calibration verification at a 

10% frequency. 

15. ASTM D 3373–12, vanadium, AA 

furnace; ASTM modified the method to 

allow the use of block digestion systems 

for trace metal analysis, and requires 

analysis of a continuing calibration 

blank and continuing calibration 

verification at a 10% frequency. ASTM 

now allows for pH adjustments in the 

laboratory if the sample is returned 

within 14 days following sampling. 

16. ASTM D 3557–12 (A–D), 

cadmium, AA direct aspiration, AA 

furnace, Voltammetry; ASTM modified 

the method to allow the use of block 

digestion systems for trace metal 

analysis, and requires analysis of a 

continuing calibration blank and 

continuing calibration verification at a 

10% frequency. ASTM now allows for 

pH adjustments in the laboratory if the 

sample is returned within 14 days 

following sampling. 

17. ASTM D 3590–11 (A, B), total 

Kjeldahl nitrogen, manual digestion and 

distillation or gas diffusion; semiautomated block digester colorimetric 

(distillation not required); ASTM 

revised the preservation method to 

allow storing samples at 2–6 °C, instead 

of the previous 4 °C. The method 

includes OI Analytical Flow Injection 

Analysis (FIA) performance data using 

an alternative copper sulfate catalyst in 

place of mercury (note: ‘‘OI Analytical’’ 

is a company name, not an acronym). 

18. ASTM D 4382–12, barium, AA 

furnace; ASTM modified the method to 

allow the use of block digestion systems 

for trace metal analysis, and requires 

analysis of a continuing calibration 

blank and continuing calibration 

verification at a 10% frequency. 

19. ASTM D 4658–09, sulfide ion, ion 

selective electrode; no substantive 

changes. 

20. ASTM D 5257–11, dissolved 

hexavalent chromium, ion 

chromatography; ASTM recommends 

buffering samples containing very high 

levels of anionic species to a pH of 9– 

9.5, then filtering the sample and storing 

it at <6 °C for a holding time of 28 days 

to prevent reduction of Cr(VI) to Cr(III). 

ASTM added an allowance for alternate 

holding times in Sections 1.3 and 9.2 if 

the user ‘‘demonstrates that holding 

time does not affect sample integrity per 

US EPA 40 CFR 136 . . .’’ 

21. ASTM D 5673–10, dissolved 

elements and total-recoverable 

elements, ICP/MS; no substantive 

changes. 

22. ASTM D 5907–13, filterable 

matter (total dissolved solids) and 

nonfilterable matter (total suspended 

solids), gravimetric, 180° gravimetric, 

103–105° post washing of residue; no 

substantive changes. 

23. ASTM D 6508–10, inorganic 

anions (fluoride, bromide, chloride, 

nitrite, nitrate, orthophosphate, and 

sulfate), capillary ion electrophoresis 

with indirect UV detection; no 

substantive changes. 

24. ASTM D 7284–13, total cyanide, 

manual distillation with MgCl2 followed 

by flow injection, gas diffusion 

amperometry; ASTM modified the 

method to include the use of a collector 

tube of the micro distillation apparatus 

with 1.5 ml of 1.0 M NaOH, and 

included information regarding the use 

of this collector tube in the procedure. 

ASTM also added information regarding 

the precision and bias associated with 

this method based on an interlaboratory 

study. 

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25. ASTM D 7511–12, total cyanide, 

segmented flow injection, in-line 

ultraviolet digestion, followed by gas 

diffusion amperometry; no substantive 

changes. 

The following changes would apply to 

Table IC at 40 CFR part 136: 

1. ASTM D 7065–11, nonylphenol, 

bisphenol A, p-tert-octylphenol, 

nonylphenol monoethoxylate, 

nonylphenol diethoxylate, gas 

chromatography/mass spectrometry 

(GC/MS); no substantive changes. 

E. Changes to 40 CFR 136.3 To Include 

New United States Geological Survey 

(USGS) Methods 

1. EPA proposes to add the USGS 

Methods I–2547–11 and I–2548–11 

titled ‘‘Colorimetric Determination of 

Nitrate Plus Nitrite in Water by 

Enzymatic Reduction, Automated 

Discrete Analyzer Methods,’’ to Table IB 

for the analytes nitrate, nitrite, and 

combined nitrate-nitrite. Method I– 

2548–11 is a low level (analytical range) 

version of Method I–2547–11. They are 

both included in the same method title. 

The method can be found in USGS 

Survey Techniques and Methods, Book 

5, Chapter B8. The method is available 

for free from the USGS Web site. This 

method follows the same procedure as 

in ATP Case No. N07–0003—Nitrate 

Elimination Company Inc.’s (NECi) 

Method N07–0003, Revision 9.0, March 

2014, ‘‘Method for Nitrate Reductase 

Nitrate-Nitrogen Analysis,’’ which EPA 

also proposes to approve. Additional 

details on the ATP study and multilaboratory validation can be found in 

Section E.1 below. 

F. Changes to 40 CFR 136.3 to Include 

ATPs 

To promote method innovation, EPA 

maintains a program that allows method 

developers to apply for EPA review of 

an alternative method to an existing 

approved method and potentially for 

EPA approval of that ATP. This ATP 

program is described for CWA 

applications at 40 CFR 136.4 and 136.5. 

EPA proposes for nationwide use six 

alternate test procedures. Based on 

EPA’s review, the performance of these 

ATPs is equally effective as other 

methods already approved for 

measurement. These proposed new 

methods include: NECi Method N07– 

0003, ‘‘Method for Nitrate Reductase 

Nitrate-Nitrogen Analysis;’’ Timberline 

Instruments, LLC Method Ammonia001, ‘‘Determination of Inorganic 

Ammonia by Continuous Flow Gas 

Diffusion and Conductivity Cell 

Analysis;’’ IDEXX Laboratories, Inc. 

Colilert®-18, ‘‘Coliform/E. coli Enzyme 

Substrate Test for fecal coliforms in 

Wastewater;’’ NCASI Method TNTP– 

W10900, ‘‘Total (Kjeldahl) Nitrogen and 

Total Phosphorus in Pulp and Paper 

Biologically Treated Effluent by 

Alkaline Persulfate Digestion;’’ Hach 

Company Method 10242, ‘‘Simplified 

Spectrophotometric Measurement of 

Total Kjeldahl Nitrogen in Water and 

Wastewater;’’ and Hach Company 

Method 10206, ‘‘Spectrophotometric 

Measurement of Nitrate in Water and 

Wastewater.’’ Descriptions of these new 

methods included for approval are as 

follows: 

1. The Nitrate Elimination Company 

Inc. (NECi) Method N07–0003, ‘‘Nitrate 

Reductase Nitrate-Nitrogen Analysis,’’ 

Revision 9.0, dated March 2014 (The 

Nitrate Elimination Company, Inc 

2014a). The analysis measures nitrate, 

nitrite, and combined nitrate-nitrite. 

NECi Method N07–0003 is a ‘‘green’’ 

alternative to the other approved 

methods which use cadmium, a known 

carcinogen for the reduction of nitrate to 

nitrite prior to analyses. NECi Method 

N07–003 uses automated discreet 

analysis and spectrophotometry to 

determine concentrations of nitrate and 

nitrite, combined or separately in 

wastewater. The method involves the 

following steps: 

• Enzymatic reduction of nitrate in a 

sample to nitrite using eukaryotic 

nitrate reductase; 

• Diazotizing the nitrite originally in 

the sample plus the reduced nitrate with 

sulfanilamide followed by coupling 

with N-(1-napthyl)ethylenediamine 

dihydrochloride under acidic 

conditions to form a highly colored azo 

dye; 

• Colorimetric determination in 

which the absorbance of color at 546 nm 

is directly proportional to the 

concentration of the nitrite plus the 

reduced nitrate in the sample; 

• Measurement of nitrite separately, if 

needed, by analysis of the sample while 

eliminating the reduction step; 

• Subtraction of the nitrite value from 

that of the combined nitrate-nitrite 

value to measure nitrate separately if 

needed. 

NECi Method N07–0003 can be 

obtained from The Nitrate Elimination 

Company, 334 Hecla Street, Lake 

Linden, Michigan, 49945. Telephone: 

906–370–1130. 

2. Timberline Instruments, LLC 

Method Ammonia-001, ‘‘Determination 

of Inorganic Ammonia by Continuous 

Flow Gas Diffusion and Conductivity 

Cell Analysis,’’ dated June 24, 2011 

(Timberline Instruments, LLC 2011a). 

Timberline Ammonia-001 is an 

automated method that uses a gas 

permeation cell and a conductivity 

detector to determine concentrations of 

ammonia in wastewater. The method 

involves the following steps: 

• An aqueous sample is combined 

with sodium hydroxide to a pH above 

11 producing ammonia in a non-ionized 

form in solution. 

• This solution is conveyed to a 

membrane assembly and the gaseous 

ammonia in the aqueous sample 

migrates through the hydrophobic 

membrane into a borate buffer 

absorption solution, which is then 

transported to a conductivity cell. 

• The measured changes in 

conductivity are used to quantitate 

ammonia in the sample using an 

external calibration. 

Timberline Instruments, LLC Method 

Ammonia-001 can be obtained from 

Timberline Instruments, LLC, 1880 

South Flatiron Court, Boulder, Colorado 

80301. Telephone: 303–440–8779. 

3. IDEXX Laboratories, Inc., Colilert®- 

18, ‘‘Coliform/E. coli Enzyme Substrate 

Test for fecal coliforms in Wastewater’’ 

(ATP Case No. N09–0004). The method 

is identical to the already approved E. 

coli Colilert®-18 method, with one 

exception. The current method was 

designed for total coliforms and E. coli, 

at an incubation temperature of 35 ± 

0.5°C for these organisms. The 

addendum to the IDEXX Colilert®-18 

method allows for incubation at 44.5 ± 

0.2°C for fecal coliforms. 

The Colilert®-18 Coliform/E. coli 

Enzyme Substrate Test can be obtained 

from IDEXX Laboratories Inc., One 

IDEXX Drive, Westbrook, ME 04092, 

Telephone: 1–800–321–0707. 

4. National Council for Air and 

Stream Improvement, Inc. (NCASI) 

Method TNTP–W10900, ‘‘Total 

(Kjeldahl) Nitrogen (TKN) and Total 

Phosphorus in Pulp and Paper 

Biologically Treated Effluent by 

Alkaline Persulfate Digestion,’’ dated 

June 2011 (National Council for Air and 

Stream Improvement, Inc. 2011a). 

Unlike the other ATPs in the proposed 

rule, this method is for measurements in 

pulp, paper and paperboard mill 

biologically treated effluent only. 

NCASI Method TNTP–W10900 uses an 

alkaline persulfate digestion procedure 

to convert inorganic and organic 

nitrogen containing compounds to 

nitrate and inorganic and organic 

phosphorus containing compounds to 

orthophosphate which are then 

measured using a spectrophotometer to 

determine the concentration of total 

Kjeldahl nitrogen and total phosphorus 

in a sample. 

The method involves the following 

steps: 

• Oxidation of the inorganic and 

organic nitrogen containing compounds 

to nitrate and the inorganic and organic 

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forms of phosphorus to orthophosphate 

by heating acidified, unfiltered samples 

in the presence of persulfate (a strong 

oxidizer) at 120°C and 15 psi positive 

pressure for 30 minutes. 

• Analysis of the digestate for 

measurement of nitrate and 

orthophosphate using the approved 

colorimetric procedures. 

NCASI Method TNTP–W10900 can be 

obtained from The National Council for 

Air and Stream Improvement, Inc., 

Publications Coordinator, P.O. Box 

13318, Research Triangle Park, NC 

27709–3318, Telephone: 919–941–6400. 

5. Hach Company Method 10242, 

‘‘Simplified Spectrophotometric 

Measurement of Total Kjeldahl Nitrogen 

in Water and Wastewater,’’ Revision 1.1, 

dated January 10, 2013 (Hach Company 

2013a). Hach Company Method 10242 is 

a simplified green chemistry alternative 

to the other approved methods for 

measuring TKN. The method uses less 

toxic reagents (e.g., eliminating the use 

of mercuric sulfate). Hach Company 

Method 10242 uses a spectrophotometer 

to measure the concentration of total 

Kjeldahl nitrogen in a sample. 

The method involves the following 

steps: 

• Oxidation of the inorganic and 

organic nitrogen containing compounds 

to nitrate by digestion with 

peroxodisulfate; 

• Reaction of nitrate with 2,6- 

dimethylphenol in a solution of sulfuric 

and phosphoric acid to form 

nitrodimethylphenol; 

• Spectrophotometric measurement 

of the nitrodimethylphenol in which the 

absorbance of color at 345 nm is directly 

proportional to the concentration of 

total nitrogen in the sample; 

• Measurement of oxidized forms of 

nitrogen (nitrite + nitrate) in the original 

sample in a second test vial; 

• Subtraction of the concentration of 

the oxidized forms of nitrogen from the 

total nitrogen concentration resulting in 

the concentration of total Kjeldahl 

nitrogen in the sample. 

Hach Company Method 10242 can be 

obtained from Hach Company, 5600 

Lindbergh Drive, Loveland, CO 80539. 

Telephone: 970–669–3050. 

6. Hach Company Method 10206, 

‘‘Spectrophotometric Measurement of 

Nitrate in Water and Wastewater,’’ 

Revision 2.1, dated January 10, 2013 

(Hach Company 2013b). Hach Company 

Method 1206 is a ‘‘green’’ alternative to 

the other approved methods which use 

cadmium, a known carcinogen for the 

reduction of nitrate to nitrite prior to 

analyses. Hach Company Method 10206 

uses a spectrophotometer to measure the 

concentration of nitrate or combined 

nitrate-nitrite in a sample. 

The method involves the following 

steps: 

• Reaction of nitrate with 2,6- 

dimethylphenol in a solution of sulfuric 

and phosphoric acid to form 

nitrodimethylphenol; 

• Spectrophotometric measurement 

of the nitrodimethylphenol in which the 

absorbance of color at 345 nm is directly 

proportional to the concentration of 

nitrate or, if the sample has been 

preserved with sulfuric acid, combined 

nitrate-nitrite in the sample. 

Hach Company Method 10206 can be 

obtained from Hach Company, 5600 

Lindbergh Drive, Loveland, CO 80539. 

Telephone: 970–669–3050. 

G. Changes to 40 CFR part 136 to Align 

With 40 CFR part 122 

The procedures approved in 40 CFR 

part 136 are often required as part of an 

application for a NPDES Permit NPDES, 

for reports required to be submitted 

under NPDES permits and/or for other 

requests for quantitative or qualitative 

effluent data under 40 CFR parts 122 

and 125. EPA is clarifying the language 

in 40 CFR 136.1, 136.2, and 136.3 so 

that the term ‘‘Director’’ as used in 40 

CFR part 136 parallels that in 40 CFR 

part 122. These sections use the terms 

‘‘Administrator’’ and ‘‘State having an 

authorized program’’ and define these 

terms in 136.3. EPA proposes to revise 

these provisions to substitute the single 

term ‘‘Director’’ and define ‘‘Director’’ 

in section 40 CFR 136.3(d) by crossreference to the definition of ‘‘Director’’ 

in the NPDES regulations at section 40 

CFR 122.2. 

EPA recently revised 40 CFR part 122 

to include a definition of ‘‘sufficiently 

sensitive.’’ The term is used to describe 

what approved methods are adequate 

for NPDES permits. 40 CFR part 

136.6(a)(2) uses the same term 

‘‘sufficiently sensitive’’ in a different 

context to describe how sensitive a 

modified method should be compared 

to the original method. 40 CFR 

136.6(a)(2) currently states that the 

modified method must be sufficiently 

sensitive and meet or exceed 

performance of the approved method(s) 

for the analyte(s) of interest, as 

documented by meeting the initial and 

ongoing quality control requirements in 

the method. 

EPA proposes to delete the words ‘‘be 

sufficiently sensitive and’’ from 40 CFR 

136.6(a)(2) to eliminate unnecessary 

confusion. It will not change the 

requirements of 40 CFR 136.6(a)(2). If a 

method modification meets or exceeds 

the performance of the approved 

method, this includes sensitivity. 

H. Corrections to 40 CFR Part 136 

These changes consist of 

typographical errors, updates that went 

unnoticed during the last update to 40 

CFR part 136 to methods from VCSBs, 

and technology updates to toxicity 

methods. 

1. EPA proposes to make a number of 

clarifications and corrections to its 

Whole Effluent Toxicity acute and 

chronic methods manuals (Methods for 

Measuring the Acute Toxicity of 

Effluents and Receiving Waters to 

Freshwater and Marine Organisms, 

EPA–821–R–02–012, October 2002; 

Short-term Methods for Estimating the 

Chronic Toxicity of Effluents and 

Receiving Waters to Freshwater 

Organisms, EPA/821/R–02/013, October 

2002; and Methods for Measuring the 

Chronic Toxicity of Effluents and 

Receiving Waters to Marine and 

Estuarine Organisms, EPA/821/R–02/

014, October 2002) listed in Table IA. 

Clarifications include testing all 

concentrations rather than only high 

and low concentrations, definition of 

terms (e.g., the acronym YCT—yeast, 

cereal leaves, and trout chow, is not 

defined), consistency corrections among 

the three manuals, notation that Cusum 

figure axes should be log scale, pH and 

temperature measurements should be 

done at the beginning of the test (rather 

than only at the end of the test), etc. 

Corrections also include deletion of 

unavailable products, typographical 

errors, etc. 

2. EPA proposes to change the 

Standard Method listed for E. coli most 

probable number (MPN) in Tables IA 

and IH. During a previous revision, 

Standard Methods added sampling as 

section 9221B.1. As a result, section 

9221B.1 in previously approved 

versions has become section 9221B.2. 

EPA proposes to change SM 9221B.1 to 

9221B.2 in Tables IA and IH for E. coli 

MPN. The related footnotes in Tables IA 

and IH (12, 14 and 11, 13, respectively) 

are accurate and EPA does not propose 

to change them. 

3. EPA proposes to change Table IA 

for Enterococci. EPA proposes to 

reinstate a line for Enterococci that was 

erroneously deleted in the 2012 

Methods Update Rule. The line ‘‘MPN, 

multiple tube’’ with Standard Method 

9230B–2007 should be added. 

4. EPA proposes to change one of the 

Table IB hardness entries that currently 

states ‘‘Ca plus Mg as their carbonates, 

by inductively coupled plasma or AA 

direct aspiration. (See Parameters 13 

and 33).’’ EPA proposes to revise the 

entry to ‘‘Ca plus Mg as their carbonates, 

by any approved method for Ca and Mg 

(See Parameters 13 and 33), provided 

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8964 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

that the sum of the lowest point of 

quantitation for Ca and Mg is below the 

NPDES permit requirement for 

Hardness.’’ The rationale behind this 

change is that if one calcium and 

magnesium method approved by EPA 

can be used to calculate hardness, then 

other approved EPA methods should 

also be permitted to do so. 

5. EPA proposes to edit Table IB, 

footnote 24. EPA proposes to delete ‘‘p 

14’’ from the footnote because the 

method is not on that page. 

6. EPA proposes to delete Method 

200.5, in Table IB from the cobalt, 

molybdenum and thallium entries. 

These analytes have not undergone 

formal testing by this method, and this 

method should not have been approved 

for these analytes. 

7. EPA proposes to remove the 

reference to costs in 40 CFR 136.3 

because costs are not included in the 

referenced documents. 

8. EPA proposes to remove the first 

instance of ‘‘are’’ in 40 CFR 136.3(e) 

because it is an error. 

I. Changes to Table II at 40 CFR 136.3(e) 

to Required Containers, Preservation 

Techniques, and Holding Times 

EPA proposes revisions to Table II at 

40 CFR 136.3(e) to amend some of the 

current requirements. 

1. EPA proposes to add rows to Table 

II that specify holding times for total/

fecal coliforms, and fecal streptococci in 

Table IH. Currently these bacterial tests 

are unspecified. EPA proposes the same 

holding time requirements as the other 

bacterial tests. 

2. EPA proposes to change the sodium 

thiosulfate concentrations in Table II for 

bacterial tests from 0.0008% sodium 

thiosulfate to 0.008%. EPA proposed 

this change in its last update to 40 CFR 

part 136 (75 FR 58066–58067), but 

inadvertently omitted it in the 

publication of the final rule. 

3. EPA proposes to re-insert language 

that was accidentally deleted from 

footnote 5 of Table II during the last 

update to 40 CFR part 136. Footnote 5 

currently reads ‘‘ASTM D7365–09a 

specifies treatment options for samples 

containing oxidants (e.g., chlorine). 

Also, Section 9060A of Standard 

Methods for the Examination of Water 

and Wastewater (20th and 21st editions) 

addresses dechlorination procedures.’’ 

EPA proposes to revise the footnote to 

read ‘‘ASTM D7365–09a specifies 

treatment options for samples 

containing oxidants (e.g., chlorine) for 

cyanide analysis. Also, Section 9060A 

of Standard Methods for the 

Examination of Water and Wastewater 

(20th and 21st editions) addresses 

dechlorination procedures for 

microbiological analyses.’’ The footnote 

needs to specify that treatment options 

for samples containing oxidants is 

specifically for cyanide analysis, and 

that the dechlorination procedures are 

specifically for microbiological 

analyses. 

4. EPA seeks comment on how to 

approve variances to sample 

preservation, containers or holding 

times listed in Table II for specific 

dischargers. Before the 2012 Final 

Method Update Rule (FR 77: 29758), the 

regulation required parties requesting a 

variance from Table II for specific 

dischargers to send the request to the 

appropriate EPA regional office for 

review, and then for the regional office 

to send the request to the National ATP 

Coordinator at EPA Headquarters for 

review and recommendation. Following 

receipt of such recommendation, the 

regional office could approve a variance. 

In the 2012 Final Method Update Rule, 

EPA changed the requirement so that 

either the Regional ATP Coordinator or 

the permitting authority could approve 

an exception to Table II for specific 

dischargers. The primary rationale for 

this change, as stated in the preamble of 

the 2010 Proposed Method Update Rule 

(FR 76: 77742) was: ‘‘EPA is revising the 

text at 136.3(e) to allow a party to 

explain, without a cumbersome waiver 

process, to their permitting or other 

authority their basis for an alternative 

approach.’’ Giving this authority to 

either the Regional ATP Coordinator or 

the permitting authority speeds up the 

approval process. Also, the permitting 

authority is more likely to know about 

special circumstances surrounding the 

local dischargers (e.g., unusual 

discharge matrices, remote locations, 

etc.). 

This change in the approval process 

resulted in the following potential 

complications and EPA is interested in 

public comment on them. First, it 

created a parallel authority to approve 

variances to Table II for specific 

dischargers. A discharger could make a 

request to both the Regional ATP 

Coordinator and the permitting 

authority, receive contradictory 

answers, and then choose the answer 

that the discharger prefers. Second, 

when there are different authorities 

approving a Table II variance for 

specific dischargers, there is potential 

for the data and documentation required 

by one authority to differ significantly 

from that required by the other 

authority. 

EPA seeks comment on potential 

paths forward that would eliminate 

these concerns, while streamlining the 

process so that approval can be granted 

within the EPA region or by the state 

permitting authority. One possibility is 

for the permitting authority and the 

Regional ATP Coordinator to approve 

Table II variances for specific 

dischargers collaboratively. The 

permitting authority could provide the 

initial review and approval, and then 

approved requests could be sent to the 

Regional ATP Coordinator for final 

review and approval. Both organizations 

would need to agree for specific 

dischargers to be allowed Table II 

variances. Another option is to give the 

Regional ATP Coordinator exclusive 

rights to approve Table II variances for 

specific dischargers. Another option is 

to give the permitting authority 

exclusive rights to approve Table II 

variances. Other options are also 

possible, such as leaving 40 CFR 

136.3(e) unchanged. 

EPA also seeks comment on what data 

should be submitted to support a 

request for a Table II variance for a 

specific discharger. 40 CFR 136.3(e) 

requires that data be included with any 

request to modify Table II requirements 

for a specific discharger. The data 

would need to prove that the variance 

does not compromise the analytical 

results. 

J. Clarifications/Corrections to ATP 

Procedures in 40 CFR 136.4, 136.5 and 

Allowed Modifications in 136.6 

40 CFR 136.4 and 136.5 describe EPA 

procedures for obtaining approval to use 

an alternate test procedures either on a 

national basis, or for limited use by 

dischargers or facilities specified in the 

approval. In the 2012 Method Update 

Rule, EPA made several clarifying 

changes to the language of these 

sections. At the same time, however, in 

many places in 40 CFR 136.4 and 136.5 

where the phrase ‘‘Regional Alternate 

Test Procedures Coordinator’’ or 

‘‘Regional ATP Coordinator’’ appears, 

EPA inadvertently also inserted the 

phrase ‘‘or permitting authority’’ 

following the phrase. This error resulted 

from the use of the ‘‘search and replace’’ 

function on the computer. The effect of 

the change was to inadvertently 

authorize State permitting authorities to 

approve ATPs for limited use within the 

State. EPA never intended this result as 

is demonstrated by two facts. First, in its 

proposal for the 2012 Update, EPA did 

not propose to authorize State NPDES 

permitting authorities to approve 

limited use ATPs. Second, the rule 

states that the approval may be 

restricted to specific dischargers or 

facilities, or to all dischargers or 

facilities ‘‘specified in the approval for 

the Region.’’ (emphasis added). This 

language evidences EPA’s intent that the 

Region—not the state—would be 

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authorized to issue any such limited use 

ATP approval. Finally, as further 

evidence of EPA’s intent, in several 

places, the text of the rule makes more 

sense if read to authorize only the 

Regional ATP Coordinator, and not the 

State permitting authority, to approve 

limited use ATPs. For example, 40 CFR 

136.5(d)(1) provides that after a review 

of the application by the Alternate Test 

Procedure Regional ATP Coordinator or 

permitting authority, the Regional ATP 

Coordinator or permitting authority 

notifies the applicant and the 

appropriate State agency of approval or 

rejection of the use of the alternate test 

procedure. 

As currently written, if the State is 

acting on a request for approval, the 

regulation would require the State to 

inform itself of its own action in 

approving or rejecting the ATP, a 

somewhat superfluous requirement. 

Consequently, EPA proposes to delete 

all instances of ‘‘or permitting 

authority’’ from 40 CFR 136.4 and 136.5 

to correct this error and revise the rule 

text to its original intent. Based on this 

revision, EPA and EPA alone would 

have the authority to approve limited 

use ATPs. 

EPA also proposes changes to 40 CFR 

136.4 and 136.5 to clarify the process for 

nationwide approval and the Regional 

ATP Coordinator’s role in limited use 

ATP approvals. These changes do not 

significantly change the process, the 

intent is to make wording simpler and 

clearer. 

Finally, EPA proposes to add 

language to 40 CFR 136.6(b)(1) to clarify 

that if a method user is uncertain 

whether or not a modification is 

allowed under 40 CFR 136.6, the user 

should contact either its Director or EPA 

Regional ATP Coordinator. 

K. Changes to Appendix B to 40 CFR 

part 136—Definition and Procedure for 

the Determination of the MDL 

EPA proposes revisions to the 

procedure for determination of the MDL 

primarily to address laboratory blank 

contamination and to better account for 

intra-laboratory variability. EPA’s 

consideration of revisions to the MDL 

procedure for this rulemaking is specific 

to these revisions, and other changes to 

the procedure are outside the scope of 

this action. The proposed changes 

originated from The National 

Environmental Laboratory Accreditation 

Conference Institute and also reflect 

review by EPA, states, and commercial 

laboratories. The proposed revisions 

address the following issues and would 

add new requirements. 

Background contamination: 

laboratories would be required to 

evaluate the MDL to account for 

background levels of contamination. As 

laboratory methods become more and 

more sensitive, background levels of 

contamination are more likely to 

contribute to the result. This 

modification would reduce false 

positive detects. 

MDLs that represent multiple 

instruments: if a laboratory uses MDL 

values that represent multiple 

instruments, then the laboratory would 

be required to calculate the MDL using 

spiked samples and blank samples from 

all of these instruments. Currently, 

laboratories can run all of their MDL 

samples on the most sensitive 

instrument, and then use that MDL for 

other instruments. This modification 

will make the MDL more representative 

of the laboratory’s actual capability. 

Ongoing MDL quarterly verification: 

laboratories would be required to check 

their MDL values once a quarter. 

Currently, laboratories can run MDL 

samples once a year under the most 

ideal circumstances (e.g., immediately 

after the instrument has been serviced 

or after an annual maintenance routine). 

Quarterly evaluation will determine if 

the detection limit has significantly 

drifted during the year. Laboratories 

would be exempt from running these 

samples for a method during quarters 

when no samples are run using that 

method. 

EPA requests comment on whether it 

should adopt these proposed changes, 

in part, or in whole. 

V. Statutory and Executive Order 

Reviews 

A. Executive Order 12866: Regulatory 

Planning and Review and Review and 

Executive Order 13563: Improving 

Regulation and Regulatory Review 

This rule is not a significant 

regulatory action and was therefore not 

submitted to the Office of Management 

and Budget for review. 

B. Paperwork Reduction Act 

This action does not impose an 

information collection burden under the 

PRA. This rule does not impose any 

information collection, reporting, or 

recordkeeping requirements. This 

proposal would merely add or revise 

CWA test procedures. 

C. Regulatory Flexibility Act 

I certify that this action would not 

have a significant economic impact on 

a substantial number of small entities 

under the RFA. This action will not 

impose any requirements on small 

entities. This action would approve new 

and revised versions of CWA testing 

procedures. Generally, these changes 

would have a positive impact on small 

entities by increasing method flexibility, 

thereby allowing entities to reduce costs 

by choosing more cost-effective 

methods. In general, EPA expects the 

proposed revisions would lead to few, if 

any, increased costs. As explained 

previously, most of the proposed 

changes clarify procedures for EPA 

approval of ATPs, clarify or improve the 

instructions in the method, update the 

technology used in the method, improve 

the QC instructions, make editorial 

corrections, or reflect the most recent 

approval year of an already approved 

method. In some cases, the proposal 

would add alternatives to currently 

approved methods for a particular 

analyte (e.g. Method N07–0003 for 

Nitrate Reductase Nitrate-Nitrogen 

Analysis). Because these methods 

would be alternatives rather than 

requirements, there are no direct costs 

associated with their proposal. EPA 

proposes methods that would be 

incorporated by reference. If a permittee 

elected to use these methods, they could 

incur a small cost associated with 

obtaining these methods. See Section 

IV.B. Finally, the proposed changes to 

the MDL procedure would lead to 

limited increased costs. In the vast 

majority of cases, laboratories already 

collect samples that could be used in 

the revised procedure and/or would 

simply adjust the time period of 

collection. The total number of MDL 

samples run annually would only 

increase to any appreciable extent for 

laboratories that own many instruments. 

EPA has not estimated costs for these 

cases, because such costs, if incurred, 

would be negligible in comparison to 

overall laboratory expenditures. 

D. Unfunded Mandates Reform Act 

This action does not contain any 

unfunded mandate as described in 

UMRA, 2 U.S.C. 1531–1538, and does 

not significantly or uniquely affect small 

governments. The action imposes no 

enforceable duty on any state, local or 

tribal governments or the private sector. 

E. Executive Order 13132: Federalism 

This proposed rule does not have 

federalism implications. It will not have 

substantial direct effects on the states, 

on the relationship between the national 

government and the states, or on the 

distribution of power and 

responsibilities among the various 

levels of government. 

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8966 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

F. Executive Order 13175: Consultation 

and Coordination with Indian Tribal 

Governments 

This proposed rule does not have 

tribal implications as specified in 

Executive Order 13175. This rule would 

merely approve new and revised 

versions of test procedures. EPA does 

not expect the proposal would lead to 

any costs to any tribal governments, and 

if incurred, projects they would be 

minimal. Thus, Executive Order 13175 

does not apply to this action. 

G. Executive Order 13045: Protection of 

Children from Environmental Health 

Risks and Safety Risks 

EPA interprets EO 13045 as applying 

only to those regulatory actions that 

concern environmental health or safety 

risks that the EPA has reason to believe 

may disproportionately affect children, 

per the definition of ‘‘covered regulatory 

action’’ in section 2–202 of the 

Executive Order. This action is not 

subject to Executive Order 13045 

because it does not concern an 

environmental health risk or safety risk. 

H. Executive Order 13211: Actions that 

Significantly Affect Energy Supply, 

Distribution, or Use 

This action is not subject to Executive 

Order 13211 because it is not a 

significant regulatory action under 

Executive Order 12866. 

I. National Technology Transfer and 

Advancement Act of 1995 

This action involved technical 

standards. The EPA proposes to approve 

the use of technical standards 

developed and recommended by the 

Standard Methods Committee and 

ASTM International for use in 

compliance monitoring where EPA 

determined that those standards meet 

the needs of CWA programs. As 

explained in Section IV.C, EPA does not 

propose to add one SM method because 

it did not receive data to demonstrate 

that the method had undergone full 

inter-laboratory validation. EPA 

proposes all other methods 

recommended by VCSBs in advance of 

the proposed rule. 

J. Executive Order 12898: Federal 

Actions To Address Environmental 

Justice in Minority Populations and 

Low-Income Populations 

The EPA believes the human health or 

environmental risk addressed by this 

action will not have potential 

disproportionately high and adverse 

human health or environmental effects 

on minority, low-income or indigenous 

populations. 

List of Subjects in 40 CFR Part 136 

Environmental protection, 

Incorporation by reference, Reporting 

and recordkeeping requirements, Test 

procedures, Water pollution control. 

Dated: February 5, 2015. 

Gina McCarthy, 

Administrator. 

For the reasons set out in the 

preamble, title 40, chapter I of the Code 

of Federal Regulations is proposed to be 

amended as follows: 

PART 136—GUIDELINES 

ESTABLISHING TEST PROCEDURES 

FOR THE ANALYSIS OF POLLUTANTS 

■ 1. The authority citation for part 136 

continues to read as follows: 

Authority: Secs. 301, 304(h), 307 and 

501(a), Pub. L. 95–217, 91 Stat. 1566, et seq. 

(33 U.S.C. 1251, et seq.) (the Federal 

Water Pollution Control Act 

Amendments of 1972 as amended by the 

Clean Water Act of 1977). 

■ 2. Section 136.1 is amended by 

revising paragraph (a) to read as follows: 

§ 136.1 Applicability. 

(a) The procedures prescribed herein 

shall, except as noted in §§ 136.4, 136.5, 

and 136.6, be used to perform the 

measurements indicated whenever the 

waste constituent specified is required 

to be measured for: 

(1) An application submitted to the 

Director and/or reports required to be 

submitted under NPDES permits or 

other requests for quantitative or 

qualitative effluent data under parts 122 

to 125 of this chapter; and 

(2) Reports required to be submitted 

by dischargers under the NPDES 

established by parts 124 and 125 of this 

chapter; and 

(3) Certifications issued by States 

pursuant to section 401 of the Clean 

Water Act (CWA), as amended. 

* * * * * 

■ 3. Section 136.2 is amended by 

revising paragraph (d) to read as 

follows: 

§ 136.2 Definitions. 

* * * * * 

(d) Director means the director as 

defined in 40 CFR 122.2. 

* * * * * 

■ 4. In § 136.3: 

■ a. Revise paragraph (a) introductory 

text and tables IA, IB, IC, ID, IF, IG, and 

IH. 

■ b. Revise paragraphs (b) introductory 

text, (b)(8)(iv), (b)(8)(v), (b)(8)(xiii), 

(b)(8)(xv), (b)(10)(viii), (b)(10)(x) through 

(lviii), (b)(10)(lxi) through (lxiii), 

(b)(10)(lxviii), (b)(15)(v), (b)(15)(viii) 

through (x), (b)(15)(xii), (b)(15)(xiii), 

(b)(15)(xv) through (xvii), (b)(15)(xxii) 

through (xxiv), (b)(15)(xxx), 

(b)(15)(xxxv), (b)(15)(xxxvii), 

(b)(15)(xxxix), (b)(15)(xlii), (b)(15)(l), 

(b)(15)(lii), (b)(15)(lv), (b)(15)(lviii), 

(b)(15)(lxi), (b)(15)(lxvi), and 

(b)(15)(lxviii). 

■ c. Redesignate paragraphs (b)(19)(vii) 

and (viii) as paragraphs (b)(19)(ix) and 

(x), respectively. 

■ d. Add paragraphs (b)(19)(vii) and 

(viii). 

■ e. Revise paragraphs (b)(20)(i) through 

(iv). 

■ f. Remove paragraph (b)(20)(v). 

■ g. Revise paragraph (b)(25). 

■ h. Redesignate paragraphs (b)(33) and 

(34) as paragraphs (b)(35) and (36), 

respectively, and redesignate paragraphs 

(b)(26) through (32) as paragraphs 

(b)(27) through (33), respectively. 

■ i. Add paragraph (b)(26). 

■ j. Add paragraph (b)(34). 

■ k. Revise newly redesignated 

paragraph (b)(35). 

■ l. Revise paragraph (c) and the table in 

paragraph (e). 

The revisions and additions read as 

follows: 

§ 136.3 Identification of test procedures. 

(a) Parameters or pollutants, for which 

methods are approved, are listed 

together with test procedure 

descriptions and references in Tables 

IA, IB, IC, ID, IE, IF, IG, and IH of this 

section. The methods listed in Tables 

IA, IB, IC, ID, IE, IF, IG, and IH are 

incorporated by reference, see paragraph 

(b) of this section, with the exception of 

EPA Methods 200.7, 601–613, 624.1, 

625.1, 1613, 1624, and 1625. The full 

texts of Methods 601–613, 624.1, 625.1, 

1613, 1624, and 1625 are printed in 

appendix A of this part, and the full text 

of Method 200.7 is printed in appendix 

C of this part. The full text for 

determining the method detection limit 

when using the test procedures is given 

in appendix B of this part. In the event 

of a conflict between the reporting 

requirements of 40 CFR parts 122 and 

125 and any reporting requirements 

associated with the methods listed in 

these tables, the provisions of 40 CFR 

parts 122 and 125 are controlling and 

will determine a permittee’s reporting 

requirements. The full text of the 

referenced test procedures are 

incorporated by reference into Tables 

IA, IB, IC, ID, IE, IF, IG, and IH. The date 

after the method number indicates the 

latest editorial change of the method. 

The discharge parameter values for 

which reports are required must be 

determined by one of the standard 

analytical test procedures incorporated 

by reference and described in Tables IA, 

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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 §§ 136.4 and 136.5. Under 

certain circumstances paragraph (c) of 

this section, § 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 mL 

or number per gram dry weight.

Most Probable Number 

(MPN), 5 tube, 3 dilution, or.

p. 132 31680 11 15 1681 11 20 9221 C E– 

2006 

Multiple tube/multiple well, 

or.

........................................... .................. Colilert18 ® 13 18 29

Membrane filter (MF) 2, 

single step.

p. 124 3 .............................. 9222 D– 

2006 30

B–0050– 

85 4.

2. Coliform (fecal) in presence of 

chlorine, number per 100 mL.

MPN, 5 tube, 3 dilution, or p. 132 3 .............................. 9221 C E– 

2006 

MF 2, single step 5 ............. p. 124 3 .............................. 9222 D– 

2006 30

3. Coliform (total), number per 100 

mL.

MPN, 5 tube, 3 dilution, or p. 114 3 .............................. 9221 B–2006 

MF 2, single step or two 

step.

p. 108 3 .............................. 9222 B–2006 B–0025– 

85 4.

4. Coliform (total), in presence of 

chlorine, number per 100 mL.

MPN, 5 tube, 3 dilution, or p. 114 3 .............................. 9221 B–2006 

MF 2 with enrichment 5 ...... p. 111 3 .............................. 9222 

B¥2006 

5. E. coli, number per 100 mL 21 ..... MPN 6 8 16 multiple tube, or ........................................... 9221B.2– 

2006/

9221F– 

2006 12 14

multiple tube/multiple well, 

or.

........................................... 9223 B– 

2004 13

991.15 10 .. Colilert® 13 18

Colilert18® 13 17 18

MF 2678 single step .......... 1603 22 .............................. .................. mColiBlue24 ® 19

6. Fecal streptococci, number per 

100 mL.

MPN, 5 tube, 3 dilution, or p. 139 3 .............................. 9230 B–2007 

MF 2, or ............................. p. 136 3 .............................. 9230 C–2007 B–0055– 

85 4.

Plate count ........................ p. 143 3.

7. Enterococci, number per 100 

mL 21.

MPN, 5 tube, 3 dilution, or p. 139 3 .............................. 9230 B–2007 

MPN 6 8, multiple tube/multiple well, or............................................ 9230 D–2007 D6503– 

99 9.

Enterolert ® 13 24

MF 2678 single step or ...... 1600 25 .............................. 9230 C–2007 

Plate count ........................ p. 143 3.

8. Salmonella, number per gram dry 

weight 11.

MPN multiple tube ............ 1682 23.

Aquatic Toxicity: 

9. Toxicity, acute, fresh water organisms, LC50, percent effluent.Ceriodaphnia dubia acute 2002.0 26.

Daphnia puplex and 

Daphnia magna acute.

2021.0 26.

Fathead Minnow, 

Pimephales promelas, 

and Bannerfin shiner, 

Cyprinella leedsi, acute.

2000.0 26.

Rainbow Trout, 

Oncorhynchus mykiss, 

and brook trout, 

Salvelinus fontinalis, 

acute.

2019.0 26.

10. Toxicity, acute, estuarine and 

marine organisms of the Atlantic 

Ocean and Gulf of Mexico, LC50, 

percent effluent.

Mysid, Mysidopsis bahia, 

acute.

2007.0 26.

Sheepshead Minnow, 

Cyprinodon variegatus, 

acute.

2004.0 26.

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TABLE IA—LIST OF APPROVED BIOLOGICAL METHODS FOR WASTEWATER AND SEWAGE SLUDGE—Continued 

Parameter and units Method 1 EPA Standard 

methods 

AOAC, 

ASTM, 

USGS 

Other 

Silverside, Menidia 

beryllina, Menidia 

menidia, and Menidia 

peninsulae, acute.

2006.0 26.

11. Toxicity, chronic, fresh water organisms, NOEC or IC25, percent 

effluent.

Fathead minnow, 

Pimephales promelas, 

larval survival and 

growth.

1000.0 27.

Fathead minnow, 

Pimephales promelas, 

embryo-larval survival 

and teratogenicity.

1001.0 27.

Daphnia, Ceriodaphnia 

dubia, survival and reproduction.

1002.0 27.

Green alga, Selenastrum 

capricornutum, growth.

1003.0 27.

12. Toxicity, chronic, estuarine and 

marine organisms of the Atlantic 

Ocean and Gulf of Mexico, NOEC 

or IC25, percent effluent.

Sheepshead minnow, 

Cyprinodon variegatus, 

larval survival and 

growth.

1004.0 28.

Sheepshead minnow, 

Cyprinodon variegatus, 

embryo-larval survival 

and teratogenicity.

1005.0 28.

Inland silverside, Menidia 

beryllina, larval survival 

and growth.

1006.0 28.

Mysid, Mysidopsis bahia, 

survival, growth, and fecundity.

1007.0 28.

Sea urchin, Arbacia 

punctulata, fertilization.

1008.0 28.

Table IA notes: 

1The method must be specified when results are reported. 

2A 0.45-μm membrane filter (MF) or other pore size certified by the manufacturer to fully retain organisms to be cultivated and to be free of 

extractables which could interfere with their growth. 3 Microbiological Methods for Monitoring the Environment, Water, and Wastes, EPA/600/8–78/017. 1978. US EPA. 

4 U.S. Geological Survey Techniques of Water-Resource Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and 

Analysis of Aquatic Biological and Microbiological Samples. 1989. USGS. 5Because the MF technique usually yields low and variable recovery from chlorinated wastewaters, the Most Probable Number method will be 

required to resolve any controversies. 6Tests 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. 7When 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. 8To 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. 9Annual Book of ASTM Standards-Water and Environmental Technology, Section 11.02. 2000, 1999, 1996. ASTM International. 

10Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998. AOAC International. 11 Recommended for enumeration of target organism in sewage sludge. 12The 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. 13These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is used to detect the enzyme b-glucuronidase produced by E. coli. 14After 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 μg/mL of MUG may be used. 15 Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using Lauryl-Tryptose Broth (LTB) and EC Medium, EPA–821–R–14–009. September 2014. U.S. EPA. 16Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube 

and dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert® may be enumerated with the multiple-well procedures, Quanti-Tray® and the MPN calculated from the table provided by the manufacturer. 17 Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms and E. coli that provides results within 18 h of 

incubation at 35°C rather than the 24 h required for the Colilert® test and is recommended for marine water samples. 18 Descriptions of the Colilert®, Colilert-18®, and Quanti-Tray® may be obtained from IDEXX Laboratories, Inc. 19A description of the mColiBlue24® test, is available from Hach Company. 20 Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation using A–1 Medium, EPA–821–R–06–013. July 

2006. U.S. EPA. 21 Recommended for enumeration of target organism in wastewater effluent. 

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22 Method 1603: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar 

(modified mTEC), EPA–821–R–14–010. September 2014. U.S. EPA. 23 Method 1682: Salmonella in Sewage Sludge (Biosolids) by Modified Semisolid Rappaport-Vassiliadis (MSRV) Medium, EPA–821–R–14–012. 

July 2014. U.S. EPA. 24A description of the Enterolert® test may be obtained from IDEXX Laboratories Inc. 25 Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-b-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. 27Short-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. 28Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms, EPA–821–R– 

02–014. Third Edition, October 2002. U.S. EPA. 29 Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms and E. coli that has been adapted to detect 

fecal coliforms. To use Colilert-18® to assay for fecal coliforms, the incubation temperature is 44.5 + 0.2°C. This test is recommended for wastewater samples. 30The verification frequency is at least five typical and five atypical colonies per sampling site on the day of sample collection and analysis. 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

1. Acidity, as CaCO3, mg/

L.

Electrometric endpoint 

or phenolphthalein 

endpoint.

.......................... 2310 B–2011 ................. D1067–11 ........ I–1020–85. 2

2. Alkalinity, as CaCO3, 

mg/L.

Electrometric or Colorimetric titration to pH 

4.5, Manual.

.......................... 2320 B–1997 ................. D1067–11 ........ 973.43 3, I–1030–85. 2

Automatic ...................... 310.2 (Rev. 

1974) 1.

........................................ .......................... I–2030–85. 2

3. Aluminum—Total, 4 mg/

L.

Digestion 4, followed by 

any of the following: 

AA direct aspiration 36........................... 3111 D–2011 or 3111 

E–2011.

.......................... I–3051–85. 2

AA furnace ............. .......................... 3113 B–2010.

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev 4.2 

(2003) 68; 

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 ........ 993.143, I–4471–97. 50

Direct Current Plasma 

(DCP) 36.

.......................... ........................................ D4190–08 ........ See footnote. 34

Colorimetric (Eriochrome 

cyanine R).

.......................... 3500–Al B–2011.

4. Ammonia (as N), mg/L Manual distillation 6 or 

gas diffusion (pH > 

11), followed by any 

of the following: 

350.1, Rev. 2.0 

(1993).

4500–NH3 B–2011 ........ .......................... 973.49. 3

Nesslerization ................ .......................... ........................................ D1426–08 (A) .. 973.49 3, I–3520–85. 2

Titration ......................... .......................... 4500–NH3 C–2011.

Electrode ....................... .......................... 4500–NH3 D–2011 or 

E–2011.

D1426–08 (B).

Manual phenate, salicylate, or other substituted phenols in 

Berthelot reaction 

based methods.

.......................... 4500–NH3 F–2011 ........ .......................... See footnote. 60

Automated phenate, salicylate, or other substituted phenols in 

Berthelot reaction 

based methods.

350.1 30, Rev. 

2.0 (1993).

4500–NH3 G–2011 ........

4500–NH3 H–2011 

.......................... I–4523–85. 2

Automated electrode ..... .......................... ........................................ .......................... See footnote. 7

Ion Chromatography ..... .......................... ........................................ D6919–09.

Automated gas diffusion, 

followed by conductivity cell analysis.

.......................... ........................................ .......................... Timberline Ammonia– 

001 74

5. Antimony—Total, 4 mg/

L.

Digestion 4, followed by 

any of the following: 

AA direct aspiration 36........................... 3111 B–2011.

AA furnace ............. .......................... 3113 B–2010.

STGFAA ................. 200.9, Rev. 2.2 

(1994).

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

ICP/AES36 ............. 200.5, Rev 4.2 

(2003) 68; 

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

6. Arsenic-Total, 4 mg/L ... Digestion 4, followed by 

any of the following: 

206.5 (Issued 

1978) 1.

AA gaseous hydride .......................... 3114 B–2011 or ............

3114 C–2011 .................

D2972–08 (B) .. I–3062–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D2972–08 (C) .. I–4063–98. 49

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev 4.2 

(2003) 68; 

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–4020–05. 70

Colorimetric 

(SDDC).

.......................... 3500–As B–2011 ........... D2972–08 (A) .. I–3060–85. 2

7. Barium-Total, 4 mg/L .... Digestion4, followed by 

any of the following: 

AA direct aspiration 36........................... 3111 D–2011 ................. .......................... I–3084–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D4382–12.

ICP/AES36 ............. 200.5, Rev 4.2 

(2003) 68; 

200.7, Rev. 

4.4 (1994).

3120 B–2011 ................. .......................... I–4471–97. 50

ICP/MS ................... 200.8, Rev. 5.4 

(1994).

3125 B–2011 ................. D5673–10 ........ 993.143, I–4471–97. 50

DCP36 .................... .......................... ........................................ .......................... 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–2011.

D3645–08 (A) .. I–3095–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D3645–08 (B).

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES ................. 200.5, Rev 4.2 

(2003) 68; 

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 ........................ .......................... ........................................ D4190–08 ........ See footnote. 34

Colorimetric 

(aluminon).

.......................... See footnote. 61

9. Biochemical oxygen 

demand (BOD5), mg/L.

Dissolved Oxygen Depletion........................... 5210 B–2011 ................. .......................... 973.44 3, p. 17 9, I– 

1578–78 8, See footnote. 10, 63

10. Boron—Total, 37 mg/L Colorimetric (curcumin) .......................... 4500–B B–2011 ............ .......................... I–3112–85. 2

ICP/AES ........................ 200.5, Rev 4.2 

(2003) 68; 

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 ............................... .......................... ........................................ D4190–08 ........ See footnote. 34

11. Bromide, mg/L ........... Electrode ....................... .......................... ........................................ D1246–10 ........ I–1125–85. 2

Ion Chromatography ..... 300.0, Rev 2.1 

(1993) and 

300.1–1, Rev 

1.0 (1997).

4110 B–2011, C–2011, 

D–2011.

D4327–03 ........ 993.30. 3

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: 

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

AA direct aspiration 36........................... 3111 B–2011 .................

or 3111 C–2011 ............

D3557–12 (A or 

B).

974.27 3, p. 37 9, I– 

3135–85 2 or I–3136– 

85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D3557–12 (D) .. I–4138–89. 51

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev 4.2 

(2003) 68; 

200.7, Rev. 

4.4 (1994).

3120 B–2011 ................. D1976–12 ........ I–1472–85 2 or I–4471– 

97. 50

ICP/MS ................... 200.8, Rev. 5.4 

(1994).

3125 B–2011 ................. D5673–10 ........ 993.14 3, I–4471–97. 50

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

Voltametry 11 .......... .......................... ........................................ D3557–12 (C).

Colorimetric (Dithizone)........................... 3500–Cd–D–1990.

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) 68; 

200.7, Rev. 

4.4 (1994).

3120 B–2011 ................. .......................... I–4471–97. 50

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 demand (CBOD5), mg/L 12.Dissolved Oxygen Depletion with nitrification inhibitor........................... 5210 B–2011 ................. .......................... See footnote. 35, 63

15. Chemical oxygen demand (COD), mg/L.Titrimetric ....................... 410.3 (Rev. 

1978) 1.

5220 B–2011 .................

or C–2011 .....................

D1252–06 (A) .. 973.46 3, p. 17 9, I– 

3560–85. 2

Spectrophotometric, 

manual or automatic.

410.4, Rev. 2.0 

(1993).

5220 D–2011 ................. D1252–06 (B) .. See footnotes. 13, 14, I– 

3561–85. 2

16. Chloride, mg/L ........... Titrimetric: (silver nitrate) .......................... 4500–Cl ¥ B–2011 ......... D512–04 (B) .... I–1183–85. 2

(Mercuric nitrate) .... .......................... 4500–Cl ¥ C–2011 ........ D512–04 (A) .... 973.51 3, I–1184–85. 2

Colorimetric: manual........................... ........................................ .......................... I–1187–85. 2

Automated (ferricyanide)........................... 4500–Cl ¥ E–2011 ......... .......................... I–2187–85. 2

Potentiometric Titration........................... 4500–Cl ¥ D–2011.

Ion Selective Electrode........................... ........................................ D512–04 (C).

Ion Chromatography.300.0, Rev 2.1 

(1993) and 

300.1–1, Rev 

1.0 (1997).

4110 B–2011 or 4110 

C–2011.

D4327–03 ........ 993.30 3, I–2057–90. 51

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 

(low level).

.......................... 4500–Cl E–2011.

Iodometric direct .... .......................... 4500–Cl B–2011.

Back titration ether 

end-point 15.

.......................... 4500–Cl C–2011.

DPD–FAS ............... .......................... 4500–Cl F–2011.

Spectrophotometric, 

DPD.

.......................... 4500–Cl G–2011.

Electrode ................ .......................... ........................................ .......................... See footnote. 16

17A. Chlorine-Free Available, mg/L.Amperometric direct ...... .......................... 4500–Cl D–2011 ........... D1253–08.

Amperometric direct 

(low level).

.......................... 4500–Cl E–2011.

DPD–FAS ............... .......................... 4500–Cl F–2011.

Spectrophotometric, 

DPD.

.......................... 4500–Cl G–2011.

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

18. Chromium VI dissolved, mg/L.0.45-micron filtration followed by any of the 

following: 

AA chelation-extraction........................... 3111 C–2011 ................. .......................... I–1232–85. 2

Ion Chromatography.218.6, Rev. 3.3 

(1994).

3500–Cr C–2011 ........... D5257–11 ........ 993.23. 

Colorimetric (diphenyl-carbazide)........................... 3500–Cr B–2011 ........... D1687–12 (A) .. I–1230–85. 2

19. Chromium— 

Total, 4 mg/L.

Digestion 4, followed by 

any of the following: 

AA direct aspiration 36........................... 3111 B–2011 ................. D1687–12 (B) .. 974.27 3, I–3236–85. 2

AA chelation-extraction........................... 3111 C–2011.

AA furnace ............. .......................... 3113 B–2010 ................. D1687–12 (C) .. I–3233–93. 46

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev 4.2 

(2003) 68, 

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

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

Colorimetric (diphenyl-carbazide)........................... 3500–Cr B–2011.

20. Cobalt—Total, 4 mg/L Digestion 4, followed by 

any of the following: 

AA direct aspiration .......................... 3111 B–2011 or 3111 

C–2011.

D3558–08 (A or 

B).

p. 37 9, I–3239–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D3558–08 (C) .. I–4243–89. 51

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 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 dominant wavelength, hue, luminance 

purity.

Colorimetric (ADMI) ....... .......................... 2120 F–2011 ................. .......................... See footnote. 18

(Platinum cobalt) 

Spectrophotometric.

.......................... 2120 B–2011 ................. .......................... I–1250–85. 2

22. Copper—Total, 4 mg/L Digestion 4, followed by 

any of the following: 

AA direct aspiration 36........................... 3111 B–2011 or ............

3111 C–2011 .................

D1688–12 (A or 

B).

974.27 3, p. 37 9, I– 

3270–85 2 or I–3271– 

85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D1688–12 (C) .. I–4274–89. 51

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev 4.2 

(2003) 68; 

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

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

Colorimetric 

(Neocuproine).

.......................... 3500–Cu B–2011.

Colorimetric 

(Bathocuproine).

.......................... 3500–Cu C–2011 .......... .......................... See footnote. 19

23. Cyanide—Total, mg/L Automated UV digestion/distillation and 

Colorimetry.

.......................... ........................................ .......................... Kelada–01. 55

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

Segmented Flow Injection, In-Line 

Ultraviolet Digestion, followed by 

gas diffusion amperometry.

.......................... ........................................ D7511–12.

Manual distillation 

with MgCl2, followed by any of 

the following: 

335.4, Rev. 1.0 

(1993) 57.

4500–CN ¥ B–2011 and 

C–2011.

D2036–09(A), 

D7284–13.

10–204–00–1–X. 56

Flow Injection, gas 

diffusion amperometry.

.......................... ........................................ D2036–09(A) 

D7284–13.

Titrimetric ............... .......................... 4500–CN ¥ D–2011 ....... D2036–09(A) .... p. 22. 9

Spectrophotometric, 

manual.

.......................... 4500–CN ¥ E–2011 ....... D2036–09(A) .... I–3300–85. 2

Semi-Automated 20 335.4, Rev. 1.0 

(1993) 57.

........................................ .......................... 10–204–00–1–X56, I– 

4302–85. 2

Ion Chromatography........................... ........................................ D2036–09(A).

Ion Selective Electrode........................... 4500–CN ¥ F–2011 ....... D2036–09(A).

24. Cyanide-Available, 

mg/L.

Cyanide Amenable to 

Chlorination (CATC); 

Manual distillation with 

MgCl2, followed by 

Titrimetric or 

Spectrophotometric.

.......................... 4500–CN ¥ G–2011 ...... D2036–09(B).

Flow injection and 

ligand exchange, 

followed by gas 

diffusion amperometry 59.

.......................... ........................................ D6888–09 ........ OIA–1677–09. 44

Automated Distillation and Colorimetry (no UV digestion)........................... ........................................ .......................... Kelada–01. 55

24.A Cyanide-Free, mg/L Flow Injection, followed 

by gas diffusion amperometry.

.......................... ........................................ D7237–10 ........ OIA–1677–09. 44

Manual micro-diffusion and colorimetry........................... ........................................ D4282–02.

25. Fluoride—Total, mg/L Manual distillation 6, followed by any of the 

following: 

.......................... 4500–F ¥ B–2011.

Electrode, manual .. .......................... 4500–F ¥ C–2011 .......... D1179–10 (B).

Electrode, automated........................... ........................................ .......................... I–4327–85. 2

Colorimetric, 

(SPADNS).

.......................... 4500–F ¥ D–2011 .......... D1179–10 (A).

Automated 

complexone.

.......................... 4500–F ¥ E–2011.

Ion Chromatography.300.0, Rev 2.1 

(1993) and 

300.1–1, Rev 

1.0 (1997).

4110 B–2011 or C–2011 D4327–03 ........ 993.30. 3

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) 1.

3113 B–2010.

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 ........ 973.52B3, I–1338–85. 2

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

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.

.......................... 2340 B–2011.

28. Hydrogen ion (pH), 

pH units.

Electrometric measurement........................... 4500–H +B–2011 .......... D1293–99 (A or 

B).

973.41 3, I–1586–85. 2

Automated electrode.150.2 (Dec. 

1982) 1.

........................................ .......................... See footnote 21, I–2587– 

85. 2

29. Iridium—Total, 4 mg/L Digestion 4, followed by 

any of the following: 

AA direct aspiration .......................... 3111 B–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 36........................... 3111 B–2011 or ............

3111 C–2011 .................

D1068–10 (A) .. 974.27 3, I–3381–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D1068–10 (B).

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev. 4.2 

(2003) 68; 

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

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

Colorimetric (Phenanthroline)........................... 3500–Fe–2011 .............. D1068–10 (C) .. See footnote. 22

31. Kjeldahl Nitrogen 5— 

Total, (as N), mg/L.

Manual digestion 20 and 

distillation or gas diffusion, followed by any 

of the following: 

.......................... 4500–Norg B–2011 or 

C–2011 and 4500– 

NH3 B–2011.

D3590–11 (A) .. I–4515–91. 45

Titration .................. .......................... 4500–NH3 C–2011 ........ .......................... 973.48. 3

Nesslerization ......... .......................... ........................................ D1426–08 (A).

Electrode ................ .......................... 4500–NH3 D–2011 or 

E–2011.

D1426–08 (B).

Semi-automated 

phenate.

350.1, Rev. 2.0 

(1993).

4500–NH3 G–2011 ........

4500–NH3 H–2011.

Manual phenate, 

salicylate, or 

other substituted 

phenols in 

Berthelot reaction 

based methods.

.......................... 4500–NH3 F–2011 ........ .......................... See footnote. 60

Automated Methods for TKN that do not require manual distillation. 

Automated phenate, 

salicylate, or 

other substituted 

phenols in 

Berthelot reaction 

based methods 

colorimetric (auto 

digestion and distillation).

351.1 (Rev. 

1978) 1.

........................................ .......................... I–4551–78. 8

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

Semi-automated 

block digestor 

colorimetric (distillation not required).

351.2, Rev. 2.0 

(1993).

4500–Norg D–2011 ........ D3590–11 (B) .. I–4515–91 45

Block digester, followed by Auto 

distillation and Titration.

.......................... ........................................ .......................... See footnote. 39

Block digester, followed by Auto 

distillation and 

Nesslerization.

.......................... ........................................ .......................... See footnote. 40

Block Digester, followed by Flow injection gas diffusion (distillation 

not required).

.......................... ........................................ .......................... See footnote. 41

Digestion with 

peroxdisulfate, 

followed by 

Spectrophotometric (2,6-dimethyl 

phenol).

.......................... ........................................ .......................... Hach 10242. 75

Digestion with 

persulfate, followed by Colorimetric.

.......................... ........................................ .......................... NCASI TNTP 

W10900. 77

32. Lead—Total, 4 mg/L ... Digestion 4, followed by 

any of the following: 

AA direct aspiration 36........................... 3111 B–2011 or 3111 

C–2011..

D3559–08 (A or 

B).

974.27 3, I–3399–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D3559–08 (D) .. I–4403–89. 51

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev. 4.2 

(2003) 68; 

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

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

Voltametry 11 .......... .......................... ........................................ D3559–08 (C).

Colorimetric (Dithizone)........................... 3500–Pb B–2011.

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 

(2003) 68; 

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

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 36........................... 3111 B–2011 ................. D858–12 (A or 

B).

974.27 3, I–3454–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D858–12 (C).

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev. 4.2 

(2003) 68; 

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

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

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8976 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

Colorimetric 

(Persulfate).

.......................... 3500–Mn B–2011 .......... .......................... 920.203. 3

Colorimetric 

(Periodate).

.......................... ........................................ .......................... See footnote. 23

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 

fluorescence 

spectrometry 

(CVAFS).

245.7 Rev. 2.0 

(2005) 17.

........................................ .......................... I–4464–01. 71

Purge and Trap 

CVAFS.

1631E43.

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/AES36 ............. 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 36........................... 3111 B–2011 or ............

3111 C–2011 .................

D1886–08 (A or 

B).

I–3499–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. D1886–08 (C) .. I–4503–89. 51

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES36 ............. 200.5, Rev. 4.2 

(2003) 68; 

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

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

38. Nitrate (as N), mg/L .. Ion Chromatography ..... 300.0, Rev. 2.1 

(1993) and 

300.1–1, Rev. 

1.0 (1997).

4110 B–2011 or C–2011 D4327–03 ........ 993.30. 3

CIE/UV ................... .......................... 4140 B–2011 ................. D6508–10, 

D6508, Rev. 

2 54.

Ion Selective Electrode........................... 4500–NO3 ¥ D–2011.

Colorimetric (Brucine sulfate).352.1 (Issued 

1971) 1.

........................................ .......................... 973.50 3, 419D 1,7, p. 

28. 9

Spectrophotometric 

(2,6– 

dimethylphenol).

.......................... ........................................ .......................... Hach 10206. 75

Nitrate-nitrite N 

minus Nitrite N 

(See parameters 

39 and 40).

.......................... ........................................ .......................... See footnote. 62

Enzymatic reduction, followed by 

automated colorimetric determination.

.......................... ........................................ .......................... I–2547–11. 72

I–2548–11. 72

N07–0003. 73

39. Nitrate-nitrite (as N), 

mg/L.

Cadmium reduction, 

Manual.

.......................... 4500–NO3 ¥ E–2011 ..... D3867–04 (B).

Cadmium reduction, 

Automated.

353.2, Rev. 2.0 

(1993).

4500–NO3 ¥ F–2011 ..... D3867–04 (A) .. I–2545–90. 51

Automated hydrazine........................... 4500–NO3 ¥ H–2011.

Reduction/Colorimetric........................... ........................................ .......................... See footnote. 62

Ion Chromatography.300.0, Rev. 2.1 

(1993) and 

300.1–1, Rev. 

1.0 (1997).

4110 B–2011 or C–2011 D4327–03 ........ 993.30. 3

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

CIE/UV ................... .......................... 4140 B–2011 ................. D6508–10 ........ D6508, Rev. 2. 54

Enzymatic reduction, followed by 

automated colorimetric determination.

.......................... ........................................ .......................... I–2547–11. 72

I–2548–11. 72

N07–0003. 73

Spectrophotometric 

(2,6- 

dimethylphenol).

.......................... ........................................ .......................... Hach 10206. 75

40. Nitrite (as N), mg/L .... Spectrophotometric: 

Manual.

.......................... 4500–NO2 ¥ B–2011 ..... .......................... See footnote. 25

Automated 

(Diazotization).

.......................... ........................................ .......................... I–4540–85 2, See footnote. 62

Automated (*bypass 

cadmium reduction).

353.2, Rev. 2.0 

(1993).

4500–NO3 ¥ F–2011 ..... D3867–04 (A) .. I–4545–85. 2

Manual (*bypass 

cadmium reduction).

.......................... 4500–NO3 ¥ E–2011 ..... D3867–04 (B).

Ion Chromatography.300.0, Rev. 2.1 

(1993) and 

300.1–1, Rev. 

1.0 (1997).

4110 B–2011 or C–2011 D4327–03 ........ 993.30. 3

CIE/UV ................... .......................... 4140 B–2011 ................. D6508–10, 

D6508, Rev. 

2 54.

Enzymatic reduction, followed by 

automated colorimetric determination.

.......................... ........................................ .......................... I–2547–11. 72

I–2548–11. 72

N07–0003. 73

41. Oil and grease—Total 

recoverable, mg/L.

Hexane extractable material (HEM): nHexane extraction and 

gravimetry.

1664 Rev. A; 

1664 Rev. 

B42.

5520 B–2011 38.

Silica gel treated 

HEM (SGT– 

HEM): Silica gel 

treatment and 

gravimetry.

1664 Rev. A; 

1664 Rev. 

B42.

5520 B–2011 38 and 

5520 F–2011 38.

42. Organic carbon— 

Total (TOC), mg/L.

Combustion ................... .......................... 5310 B–2011 ................. D7573–09 ........ 973.47 3, p. 14. 24

Heated persulfate 

or UV persulfate 

oxidation.

.......................... 5310 C–2011 .................

5310 D–2011 .................

D4839–03 ........ 973.47 3,, p. 14. 24

43. Organic nitrogen (as 

N), mg/L.

Total Kjeldahl N (Parameter 31) minus ammonia N (Parameter 4).

44. Ortho-phosphate (as 

P), mg/L.

Ascorbic acid method: 

Automated .............. 365.1, Rev. 2.0 

(1993).

4500–P F–2011 or G– 

2011.

.......................... 973.56 3, I–4601–85. 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) and 

300.1–1, Rev. 

1.0 (1997).

4110 B–2011 or C–2000 D4327–03 ........ 993.30. 3

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 modification)........................... 4500–O (B–F)–2011 ..... D888–09 (A) .... 973.45B3, I–1575–78. 8

Electrode ................ .......................... 4500–O G–2011 ............ D888–09 (B) .... I–1576–78. 8

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

Luminescence 

Based Sensor.

.......................... ........................................ D888–09 (C) .... See footnote. 63

See 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 distillation 26, followed by any of the 

following: 

420.1 (Rev. 

1978) 1.

5530 B–2010 ................. D1783–01.

Colorimetric (4AAP) 

manual.

420.1 (Rev. 

1978) 1.

5530 D–2010 27 ............. D1783–01 (A or 

B).

Automated colorimetric (4AAP).420.4 Rev. 1.0 

(1993).

49. Phosphorus (elemental), mg/L.Gas-liquid chromatography........................... ........................................ .......................... See footnote. 28

50. Phosphorus—Total, 

mg/L.

Digestion 20, followed by 

any of the following: 

.......................... 4500–P B(5)–2011 ........ .......................... 973.55. 3

Manual ................... 365.3 (Issued 

1978) 1.

4500–P E–2011 ............ D515–88 (A).

Automated ascorbic 

acid reduction.

365.1 Rev. 2.0 

(1993).

4500–P (F–H)–2011 ...... .......................... 973.56 3, I–4600–85. 2

ICP/AES4, 36 .......... 200.7, Rev. 4.4 

(1994).

3120 B–2011 ................. .......................... I–4471–97. 50

Semi-automated 

block digestor 

(TKP digestion).

365.4 (Issued 

1974) 1.

........................................ D515–88 (B) .... I–4610–91. 48

Digestion with 

persulfate, followed by Colorimetric.

.......................... ........................................ .......................... NCASI TNTP 

W10900. 77

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, 103–105° .. .......................... 2540 B–2011 ................. .......................... I–3750–85. 2

54. Residue—filterable, 

mg/L.

Gravimetric, 180° .......... .......................... 2540 C–2011 ................. D5907–13 ........ I–1750–85. 2

55. Residue—non-filterable (TSS), mg/L.Gravimetric, 103–105° 

post washing of residue.

.......................... 2540 D–2011 ................. D5907–13 ........ I–3765–85. 2

56. Residue—settleable, 

mg/L.

Volumetric, (Imhoff 

cone), or gravimetric.

.......................... 2540 F–2011.

57. Residue—Volatile, 

mg/L.

Gravimetric, 550° .......... 160.4 (Issued 

1971) 1.

2540–E–2011 ................ .......................... I–3753–85. 2

58. Rhodium—Total, 4 mg/

L.

Digestion 4, followed by 

any of the following: 

AA direct aspiration, 

or.

.......................... 3111 B–2011.

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, 

or.

.......................... 3111 B–2011.

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

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/AES36 ............. 200.5, Rev 4.2 

(2003) 68; 

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–4020–05. 70

AA gaseous hydride .......................... 3114 B–2011, or 3114 

C–2011.

D3859–08 (A) .. I–3667–85. 2

61. Silica—Dissolved, 37 mg/L.0.45-micron filtration followed by any of the 

following: 

Colorimetric, Manual........................... 4500–SiO 2 C–2011 ....... D859–10 .......... I–1700–85. 2

Automated 

(Molybdosilicate).

.......................... 4500–SiO 2 E–2011 or 

F–2011.

.......................... I–2700–85. 2

ICP/AES ................. 200.5, Rev. 4.2 

(2003) 68; 

200.7, Rev. 

4.4 (1994).

3120 B–2011 ................. .......................... I–4471–97. 50

ICP/MS ................... 200.8, Rev. 5.4 

(1994).

3125 B–2011 ................. D5673–10 ........ 993.14. 3

62. Silver—Total, 4 31 mg/L Digestion4, 29, followed 

by any of the following: 

AA direct aspiration .......................... 3111 B–2011 or ............

3111 C–2011 .................

.......................... 974.27 3, p. 37 9, I– 

3720–85. 2

AA furnace ............. .......................... 3113 B–2010 ................. .......................... I–4724–89. 51

STGFAA ................. 200.9, Rev. 2.2 

(1994).

ICP/AES ................. 200.5, Rev. 4.2 

(2003) 68; 

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

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) 68; 

200.7, Rev. 

4.4 (1994).

3120 B–2011 ................. .......................... I–4471–97. 50

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/cm at 25 °C.

Wheatstone bridge ........ 120.1 (Rev. 

1982) 1.

2510 B–2011 ................. D1125–95(99) 

(A).

973.40 3, I–2781–85. 2

65. Sulfate (as SO4), mg/

L.

Automated colorimetric 375.2, Rev. 2.0 

(1993).

4500–SO 4 2·F–2011 or 

G–2011.

Gravimetric ............. .......................... 4500–SO4 2¥ C–2011 or 

D–2011.

.......................... 925.54. 3

Turbidimetric .......... .......................... 4500–SO4 2¥ E–2011 .... D516–11.

Ion Chromatography.300.0, Rev. 2.1 

(1993) and 

300.1–1, Rev. 

1.0 (1997).

4110 B–2011 or C–2011 D4327–03 ........ 993.30 3, I–4020–05. 70

CIE/UV ................... .......................... 4140 B–2011 ................. D6508–1010 .... D6508, Rev. 2. 54

66. Sulfide (as S), mg/L .. Sample Pretreatment .... .......................... 4500–S 2¥>B, C–2011.

Titrimetric (iodine) .. .......................... 4500–S2¥ F–2011 ........ .......................... I–3840–85. 2

Colorimetric (methylene blue)........................... 4500–S2¥ D–2011.

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8980 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

Ion Selective Electrode........................... 4500–S2¥ G–2011 ........ D4658–09.

67. Sulfite (as SO3), mg/L Titrimetric (iodine-iodate) .......................... 4500–SO3 2¥ B–2011.

68. Surfactants, mg/L ...... Colorimetric (methylene 

blue).

.......................... 5540 C–2011 ................. D2330–02.

69. Temperature, °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) 1.

3113 B–2010.

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 

(2003) 68; 

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

Colorimetric (Gallic 

Acid).

.......................... 3500–V B–2011.

75. Zinc—Total 4, mg/L .... Digestion 4, followed by 

any of the following: 

AA direct aspiration 36........................... 3111 B–2011 or 3111 

C–2011.

D1691–12 (A or 

B).

974.27 3, p. 37 9, I– 

3900–85. 2

AA furnace ............. 289.2 (Issued 

1978) 1.

ICP/AES36 ............. 200.5, Rev. 4.2 

(2003) 68; 

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

DCP36 .................... .......................... ........................................ D4190–08 ........ See footnote. 34

Colorimetric 

(Zincon).

.......................... 3500 Zn B–2011 ........... .......................... See footnote. 33

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Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 8981 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

Parameter Methodology 58 EPA52 Standard methods ASTM USGS/AOAC/Other 

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. 3Official Methods of Analysis of the Association of Official Analytical Chemists, Methods Manual, Sixteenth Edition, 4th Revision, 1998. AOAC 

International. 4For the determination of total metals (which are equivalent to total recoverable metals) the sample is not filtered before processing. A digestion procedure is required to solubilize analytes in suspended material and to break down organic-metal complexes (to convert the analyte to a 

detectable form for colorimetric analysis). For non-platform graphite furnace atomic absorption determinations a digestion using nitric acid (as 

specified in Section 4.1.3 of Methods for the Chemical Analysis of Water and Wastes) is required prior to analysis. The procedure used should 

subject the sample to gentle, acid refluxing and at no time should the sample be taken to dryness. For direct aspiration flame atomic absorption 

determinations (FLAA) a combination acid (nitric and hydrochloric acids) digestion is preferred prior to analysis. The approved total recoverable 

digestion is described as Method 200.2 in Supplement I of ‘‘Methods for the Determination of Metals in Environmental Samples’’ EPA/600R–94/

111, May, 1994, and is reproduced in EPA Methods 200.7, 200.8, and 200.9 from the same Supplement. However, when using the gaseous hydride technique or for the determination of certain elements such as antimony, arsenic, selenium, silver, and tin by non-EPA graphite furnace 

atomic absorption methods, mercury by cold vapor atomic absorption, the noble metals and titanium by FLAA, a specific or modified sample digestion procedure may be required and in all cases the referenced method write-up should be consulted for specific instruction and/or cautions. 

For analyses using inductively coupled plasma-atomic emission spectrometry (ICP–AES), the direct current plasma (DCP) technique or EPA 

spectrochemical techniques (platform furnace AA, ICP–AES, and ICP–MS) use EPA Method 200.2 or an approved alternate procedure (e.g., 

CEM microwave digestion, which may be used with certain analytes as indicated in Table IB); the total recoverable digestion procedures in EPA 

Methods 200.7, 200.8, and 200.9 may be used for those respective methods. Regardless of the digestion procedure, the results of the analysis 

after digestion procedure are reported as ‘‘total’’ metals. 5 Copper sulfate or other catalysts that have been found suitable may be used in place of mercuric sulfate. 

6 Manual distillation is not required if comparability data on representative effluent samples are on file to show that this preliminary distillation 

step is not necessary: however, manual distillation will be required to resolve any controversies. In general, the analytical method should be consulted regarding the need for distillation. If the method is not clear, the laboratory may compare a minimum of 9 different sample matrices to 

evaluate the need for distillation. For each matrix, a matrix spike and matrix spike duplicate are analyzed both with and without the distillation 

step. (A total of 36 samples, assuming 9 matrices). If results are comparable, the laboratory may dispense with the distillation step for future 

analysis. Comparable is defined as < 20% RPD for all tested matrices). Alternatively the two populations of spike recovery percentages may be 

compared using a recognized statistical test. 7 Industrial Method Number 379–75 WE Ammonia, Automated Electrode Method, Technicon Auto Analyzer II. February 19, 1976. Bran & 

Luebbe Analyzing Technologies Inc. 8The 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. 9American 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. 11The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable. 12 Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test method which measures ‘‘total 

BOD.’’ The addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD5 parameter. A discharger 

whose permit requires reporting the traditional BOD5 may not use a nitrification inhibitor in the procedure for reporting the results. Only when a 

discharger’s permit specifically states CBOD5 is required can the permittee report data using a nitrification inhibitor. 13OIC Chemical Oxygen Demand Method. 1978. Oceanography International Corporation. 14 Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company. 15The back titration method will be used to resolve controversy. 16Orion Research Instruction Manual, Residual Chlorine Electrode Model 97–70. 1977. Orion Research Incorporated. The calibration graph for 

the Orion residual chlorine method must be derived using a reagent blank and three standard solutions, containing 0.2, 1.0, and 5.0 mL 0.00281 

N potassium iodate/100 mL solution, respectively. 17 Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry, EPA–821–R–05–001. Revision 2.0, February 2005. US 

EPA. 18 National Council of the Paper Industry for Air and Stream Improvement (NCASI) Technical Bulletin 803, May 2000. 19 Method 8506, Biocinchoninate Method for Copper, Hach Handbook of Water Analysis. 1979. Hach Company. 20When 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. 27The colorimetric reaction must be conducted at a pH of 10.0 ± 0.2. 28Addison, R.F., and R.G. Ackman. 1970. Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography, Journal of Chromatography, 47(3):421–426. 29Approved methods for the analysis of silver in industrial wastewaters at concentrations of 1 mg/L and above are inadequate where silver exists as an inorganic halide. Silver halides such as the bromide and chloride are relatively insoluble in reagents such as nitric acid but are readily 

soluble in an aqueous buffer of sodium thiosulfate and sodium hydroxide to pH of 12. Therefore, for levels of silver above 1 mg/L, 20 mL of sample should be diluted to 100 mL by adding 40 mL each of 2 M Na2S2O3 and NaOH. Standards should be prepared in the same manner. For levels of silver below 1 mg/L the approved method is satisfactory. 30The 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. 31For 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. 

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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 37When determining boron and silica, only plastic, PTFE, or quartz laboratory ware may be used from start until completion of analysis. 38Only 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. 45Open 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. 46Open 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. 47Open 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. 48Open 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. 49Open 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. 50Open 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. 51Open File Report 93–125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. USGS. 52 Unless otherwise indicated, all EPA methods, excluding EPA Method 300.1–1, are published in U.S. EPA. May 1994. Methods for the Determination of Metals in Environmental Samples, Supplement I, EPA/600/R–94/111; or U.S. EPA. August 1993. Methods for the Determination of 

Inorganic Substances in Environmental Samples, EPA/600/R–93/100. EPA Method 300.1 is US EPA. Revision 1.0, 1997, including errata cover 

sheet April 27, 1999. Determination of Inorganic Ions in Drinking Water by Ion Chromatography. 53Styrene divinyl benzene beads (e.g., AMCO–AEPA–1 or equivalent) and stabilized formazin (e.g., Hach StablCalTM 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. 55Kelada-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. 56QuikChem 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. 57When 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. 59Samples 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. 60Analysts 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. 62Easy (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. 67Orion Method AQ4500, Determination of Turbidity by Nephelometry. Revision 5, March 12, 2009. Thermo Scientific. 68EPA 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. 

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70Techniques 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. 71Water-Resources Investigations Report 01–4132, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory— 

Determination of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural Water with Cold Vapor-Atomic Fluorescence Spectrometry, 

2001. USGS. 72 USGS Techniques and Methods 5–B8, Chapter 8, Section B, Methods of the National Water Quality Laboratory Book 5, Laboratory Analysis, 2011 USGS. 73 NECi Method N07–0003, Revision 9.0, March 2014, Method for Nitrate Reductase Nitrate-Nitrogen Analysis, The Nitrate Elimination Co., 

Inc. 74Timberline Instruments, LLC Method Ammonia-001, Timberline Instruments, LLC. 75 Hach Company Method 10206, Hach Company. 76 Hach Company Method 10242, Hach Company. 77 National Council for Air and Stream Improvement (NCASI) Method TNTP–W10900, Total (Kjeldahl) Nitrogen and Total Phosphorus in Pulp 

and Paper Biologically Treated Effluent by Alkaline Persulfate Digestion. June 2011. 

TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS

Parameter 1 Method EPA2 7 Standard 

methods ASTM Other 

1. Acenaphthene .................................................... GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

2. Acenaphthylene ................................................. GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

3. Acrolein .............................................................. GC .................... 603 

GC/MS ............. 624.1 4,1624B 

4. Acrylonitrile ........................................................ GC .................... 603 

GC/MS ............. 624.1 4,1624B 

5. Anthracene ........................................................ GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440B–2005 D4657–92 (98) 

6. Benzene ............................................................. GC .................... 602 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

7. Benzidine ........................................................... Spectro-photometric.See footnote 3, 

p.1. 

GC/MS ............. 625.1 5, 1625B 6410 B–2000 

HPLC ............... 605 

8. Benzo(a)anthracene .......................................... GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

9. Benzo(a)pyrene ................................................. GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

10. Benzo(b)fluoranthene ...................................... GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

11. Benzo(g,h,i)perylene ........................................ GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

12. Benzo(k)fluoranthene ....................................... GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

13. Benzyl chloride ................................................ GC .................... See footnote 3, 

p. 130. 

GC/MS ............. See footnote 6, 

p. S102. 

14. Butyl benzyl phthalate ..................................... GC .................... 606 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

15. bis(2-Chloroethoxy) methane .......................... GC .................... 611 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

16. bis(2-Chloroethyl) ether ................................... GC .................... 611 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

17. bis(2-Ethylhexyl) phthalate .............................. GC .................... 606 

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TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued 

Parameter 1 Method EPA2 7 Standard 

methods ASTM Other 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

18. Bromodichloromethane .................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

19. Bromoform ....................................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

20. Bromomethane ................................................ GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

21. 4-Bromophenyl phenyl ether ........................... GC .................... 611 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

22. Carbon tetrachloride ........................................ GC .................... 601 6200 C–2011 See footnote 3, 

p. 130. 

GC/MS ............. 624.1, 1624B 6200 B–2011 

23. 4-Chloro-3-methyl phenol ................................ GC .................... 604 6420 B–2000 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

24. Chlorobenzene ................................................. GC .................... 601, 602 6200 C–2011 See footnote 3, 

p. 130. 

GC/MS ............. 624.1, 1624B 6200 B–2011 

25. Chloroethane ................................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

26. 2-Chloroethylvinyl ether ................................... GC .................... 601 

GC/MS ............. 624.1, 1624B 

27. Chloroform ....................................................... GC .................... 601 6200 C–2011 See footnote 3, 

p. 130. 

GC/MS ............. 624.1, 1624B 6200 B–2011 

28. Chloromethane ................................................ GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

29. 2-Chloronaphthalene ....................................... GC .................... 612 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

30. 2-Chlorophenol ................................................ GC .................... 604 6420 B–2000 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

31. 4-Chlorophenyl phenyl ether ........................... GC .................... 611 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

32. Chrysene .......................................................... GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

33. Dibenzo(a,h)anthracene .................................. GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

34. Dibromochloromethane .................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

35. 1,2-Dichlorobenzene ........................................ GC .................... 601, 602 6200 C–2011 

GC/MS ............. 625.1, 1625B 6200 B–2011 See footnote 9, 

p. 27. 

36. 1,3-Dichlorobenzene ........................................ GC .................... 601, 602 6200 C–2011 

GC/MS ............. 624.1, 1625B 6200 B–2011 See footnote 9, 

p. 27. 

37. 1,4-Dichlorobenzene ........................................ GC .................... 601, 602 6200 C–2011 

GC/MS ............. 624.1, 1625B 6200 B–2011 See footnote 9, 

p. 27. 

38. 3,3′-Dichlorobenzidine ..................................... GC/MS ............. 625.1, 1625B 6410 B–2000 

HPLC ............... 605 

39. Dichlorodifluoromethane .................................. GC .................... 601 

GC/MS ............. 6200 C–2011 

40. 1,1-Dichloroethane ........................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

41. 1,2-Dichloroethane ........................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

42. 1,1-Dichloroethene ........................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

43. trans-1,2-Dichloroethene ................................. GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

44. 2,4-Dichlorophenol ........................................... GC .................... 604 6420 B–2000 

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TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued 

Parameter 1 Method EPA2 7 Standard 

methods ASTM Other 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

45. 1,2-Dichloropropane ........................................ GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

46. cis-1,3-Dichloropropene ................................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

47. trans-1,3-Dichloropropene ............................... GC .................... 601 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

48. Diethyl phthalate .............................................. GC .................... 606 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

49. 2,4-Dimethylphenol .......................................... GC .................... 604 6420 B–2000 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

50. Dimethyl phthalate ........................................... GC .................... 606 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

51. Di-n-butyl phthalate .......................................... GC .................... 606 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

52. Di-n-octyl phthalate .......................................... GC .................... 606 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

53. 2, 4-Dinitrophenol ............................................ GC .................... 604 6420 B–2000 See footnote 9, 

p. 27. 

GC/MS ............. 625.1, 1625B 6410 B–2000 

54. 2,4-Dinitrotoluene ............................................. GC .................... 609 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

55. 2,6-Dinitrotoluene ............................................. GC .................... 609 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

56. Epichlorohydrin ................................................ GC .................... See footnote 3, 

p. 130. 

GC/MS ............. See footnote 6, 

p. S102. 

57. Ethylbenzene ................................................... GC .................... 602 6200 C–2011 

GC/MS ............. 624.1, 1624B 6200 B–2011 

58. Fluoranthene .................................................... GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

59. Fluorene ........................................................... GC .................... 610 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

HPLC ............... 610 6440 B–2005 D4657–92 (98) 

60. 1,2,3,4,6,7,8-Heptachloro-dibenzofuran .......... GC/MS ............. 1613B 

61. 1,2,3,4,7,8,9-Heptachloro-dibenzofuran .......... GC/MS ............. 1613B 

62. 1,2,3,4,6,7,8- Heptachloro-dibenzo-p-dioxin .... GC/MS ............. 1613B 

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-dibenzofuran ............... GC/MS ............. 1613B 

67. 1,2,3,6,7,8-Hexachloro-dibenzofuran ............... GC/MS ............. 1613B 

68. 1,2,3,7,8,9-Hexachloro-dibenzofuran ............... GC/MS ............. 1613B 

69. 2,3,4,6,7,8-Hexachloro-dibenzofuran ............... GC/MS ............. 1613B 

70. 1,2,3,4,7,8-Hexachloro-dibenzo-p-dioxin ......... GC/MS ............. 1613B 

71. 1,2,3,6,7,8-Hexachloro-dibenzo-p-dioxin ......... GC/MS ............. 1613B 

72. 1,2,3,7,8,9-Hexachloro-dibenzo-p-dioxin ......... GC/MS ............. 1613B 

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. 

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TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued 

Parameter 1 Method EPA2 7 Standard 

methods ASTM Other 

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) 12 [also known 

as bis(2-Chloro-1-methylethyl) ether].

GC .................... 611 

GC/MS ............. 625.1, 1625B 6410 B–2000 See footnote 9, 

p. 27. 

88. PCB–1016 ........................................................ GC .................... 608.3 See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625.1 6410 B–2000 

89. PCB–1221 ........................................................ GC .................... 608.3 See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625.1 6410 B–2000 

90. PCB–1232 ........................................................ GC .................... 608.3 See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625.1 6410 B–2000 

91. PCB–1242 ........................................................ GC .................... 608.3 See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625.1 6410 B–2000 

92. PCB–1248 ........................................................ GC .................... 608.3 See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625.1 6410 B–2000 

93. PCB–1254 ........................................................ GC .................... 608.3 See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625.1 6410 B–2000 

94. PCB–1260 ........................................................ GC .................... 608.3 See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625.1 6410 B–2000 

95. 1,2,3,7,8-Pentachloro-dibenzofuran ................. GC/MS ............. 1613B 

96. 2,3,4,7,8-Pentachloro-dibenzofuran ................. GC/MS ............. 1613B 

97. 1,2,3,7,8,-Pentachloro-dibenzo-p-dioxin .......... GC/MS ............. 1613B 

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TABLE IC—LIST OF APPROVED TEST PROCEDURES FOR NON-PESTICIDE ORGANIC COMPOUNDS—Continued 

Parameter 1 Method EPA2 7 Standard 

methods ASTM Other 

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-dibenzofuran ................... GC/MS ............. 1613B 10

103. 2,3,7,8-Tetrachloro-dibenzo-p-dioxin ............. GC/MS ............. 613, 625.1 5a, 

1613B 

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 (NP1EO) ......... GC/MS ............. D7065–11 

118. Nonylphenol Diethoxylate (NP2EO) .............. GC/MS ............. D7065–11 

119. Adsorbable Organic Halides (AOX) ............... Adsorption and 

Coulometric 

Titration.

1650 11

120. Chlorinated Phenolics .................................... In Situ 

Acetylation 

and GC/MS.

1653 11

Table IC notes: 

1All parameters are expressed in micrograms per liter (μg/L) except for Method 1613B, in which the parameters are expressed in picograms 

per liter (pg/L). 2The full text of Methods 601–613, 1613B, 1624B, and 1625B are provided at Appendix A, Test Procedures for Analysis of Organic Pollutants, 

of this Part 136. The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at 

Appendix B, Definition and Procedure for the Determination of the Method Detection Limit, of this Part 136. Methods 608.3, 624.1, and 625.1 are 

available at: water.epa.gov/scitech/methods/cwa/methods_index.cfm. 3 Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. 

EPA. 4 Method 624.1 may be used for quantitative determination of acrolein and acrylonitrile, provided that the laboratory has documentation to substantiate the ability to detect and quantify these analytes at levels necessary to comply with any associated regulations. In addition, the use of 

sample introduction techniques other than simple purge-and-trap may be required. QC acceptance criteria from Method 603 should be used 

when analyzing samples for acrolein and acrylonitrile in the absence of such criteria in Method 624.1. 5 Method 625.1 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, N-nitrosodi-n-propylamine, and Nnitrosodiphenylamine. However, when they are known to be present, Methods 605, 607, and 612, or Method 1625B, are preferred methods for 

these compounds. 5a Method 625.1 screening only. 

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8988 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

6Selected 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). 7Each 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 ongoing basis must spike and analyze 10% (5% for Methods 624.1 and 625.1 and 100% for methods 1624B and 1625B) of all samples to monitor 

and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect. The results should be reported, but cannot 

be used to demonstrate regulatory compliance. These quality control requirements also apply to the Standard Methods, ASTM Methods, and 

other methods cited. 8Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk. Revised October 28, 1994. 3M Corporation. 9 Method O–3116–87 is in Open File Report 93–125, Methods of Analysis by U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. USGS. 10Analysts may use Fluid Management Systems, Inc. Power-Prep system in place of manual cleanup provided the analyst meets the requirements of Method 1613B (as specified in Section 9 of the method) and permitting authorities. Method 1613, Revision B, Tetra- through OctaChlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS. Revision B, 1994. U.S. EPA. The full text of this method is provided in Appendix A to 40 CFR part 136 and at http://water.epa.gov/scitech/methods/cwa/index.cfm. 11 Method 1650, Adsorbable Organic Halides by Adsorption and Coulometric Titration. Revision C, 1997 U.S. EPA. Method 1653, Chlorinated 

Phenolics in Wastewater by In Situ Acetylation and GCMS. Revision A, 1997 U.S. EPA. The full text for both of these methods is provided at Appendix A in part 430, The Pulp, Paper, and Paperboard Point Source Category. 12The 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 EPA2 7 10 Standard 

methods ASTM Other 

1. Aldrin ...................................... GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96 (02).

See footnote,3 p. 7; See 

footnote,4 O–3104–83; 

See footnote, 8

3M0222. 

GC/MS ............. 625.1 ...................... 6410 B–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. a-BHC .................................... GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 7; See 

footnote,8 3M0222. 

GC/MS ............. 625.1 5 ................... 6410 B–2000 ........ ............................... See footnote,11 O–1126– 

95. 

9. b-BHC ..................................... GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,8 3M0222. 

GC/MS ............. 625.1 ...................... 6410 B–2000.

10. d-BHC ................................... GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,8 3M0222. 

GC/MS ............. 625.1 ...................... 6410 B–2000.

11. g-BHC (Lindane) ................... GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 7; See 

footnote,4 O–3104–83; 

See footnote,8

3M0222. 

GC/MS ............. 625.1 5 ................... 6410 B–2000 ........ ............................... See footnote,11 O–1126– 

95. 

12. Captan .................................. GC ................... 617, 608.3 ............. 6630 B–2007 ........ D3086–90, 

D5812–96(02).

See footnote,3 p. 7. 

13. Carbaryl ................................ TLC .................. ................................ ............................... ............................... See footnote,3 p. 94, See 

footnote,6 p. S60. 

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TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued 

Parameter Method EPA2 7 10 Standard 

methods ASTM Other 

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, 

D5812–96(02).

See footnote,3 p. 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, 

D5812–96(02).

See footnote,3 p. 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, 

D5812–96(02).

See footnote,3 p. 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, 

D5812–96(02).

See footnote,3 p. 7; See 

footnote,4 O–3104–83; 

See footnote,8

3M0222. 

GC/MS ............. 625.1 ...................... 6410 B–2000.

21. Demeton-O ........................... GC ................... 614, 622 ................ ............................... ............................... See footnote,3 p. 25; See 

footnote,6 p. S51. 

GC/MS ............. 625.1.

22. Demeton-S ........................... GC ................... 614, 622 ................ ............................... ............................... See footnote,3 p. 25; See 

footnote,6 p. S51. 

GC/MS ............. 625.1.

23. Diazinon ............................... GC ................... 507, 614, 622, 

1657.

............................... ............................... See footnote,3 p. 25; See 

footnote,4 O–3104–83; 

See footnote,6 p. S51. 

GC/MS ............. 525.2, 625.1 .......... ............................... ............................... See footnote,11 O–1126– 

95. 

24. Dicamba ............................... GC ................... 615 ......................... ............................... ............................... See footnote,3 p. 115. 

HPLC/MS ........ ................................ ............................... ............................... See footnote,12 O–2060– 

01. 

25. Dichlofenthion ....................... GC ................... 622.1 ...................... ............................... ............................... See footnote,4 page 27; 

See footnote,6 p. S73. 

26. Dichloran .............................. GC ................... 608.2, 617, 608.3 .. 6630 B–2007 ........ ............................... See footnote,3 p. 7; 

27. Dicofol .................................. GC ................... 617, 608.3 ............. ............................... ............................... See footnote,4 O–3104– 

83. 

28. Dieldrin ................................. GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 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. 

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8990 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued 

Parameter Method EPA2 7 10 Standard 

methods ASTM Other 

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, 

D5812–96(02).

See footnote,3 p. 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, 

D5812–96(02).

See footnote,3 p. 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, 608.3.

6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 7; See 

footnote,4 O–3104–83; 

See footnote,8

3M0222. 

GC/MS ............. 525.1, 525.2, 

625.1 5.

6410 B–2000.

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, 608.3.

6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 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, 

D5812–96(02).

See footnote,3 p. 7; See 

footnote,4 O–3104–83; 

See footnote,6 p. S73; 

See footnote,8

3M0222. 

GC/MS ............. 625.1 ...................... 6410 B–2000.

42. Isodrin ................................... GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

............................... See footnote,4 O–3104– 

83; See footnote,6 p. 

S73. 

GC/MS ............. 625.1.

43. Linuron ................................. GC ................... ................................ ............................... ............................... See footnote,3 p. 104; 

See footnote,6 p. S64. 

HPLC ............... 632.

HPLC/MS ........ 553 ......................... ............................... ............................... See footnote,12 O–2060– 

01. 

GC/MS ............. ................................ ............................... ............................... Seeootnote,11 O–1126– 

95. 

44. Malathion .............................. GC ................... 614, 1657 .............. 6630 B–2007 ........ ............................... See footnote,3 p. 25; See 

footnote,6 p. S51. 

GC/MS ............. 625.1 ...................... ............................... ............................... See footnote,11 O–1126– 

95. 

45. Methiocarb ............................ TLC .................. ................................ ............................... ............................... See footnote,3 p. 94; See 

footnote,6 p. S60. 

HPLC ............... 632.

HPLC/MS ........ ................................ ............................... ............................... See footnote,12 O–2060– 

01. 

46. Methoxychlor ........................ GC ................... 505, 508, 608.2, 

617, 1656, 608.3.

6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 7; See 

footnote,4 O–3104–83; 

See footnote,8

3M0222. 

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TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued 

Parameter Method EPA2 7 10 Standard 

methods ASTM Other 

GC/MS ............. 525.1, 525.2, 625.1 ............................... ............................... See footnote,11 O–1126– 

95. 

47. Mexacarbate ......................... TLC .................. ................................ ............................... ............................... See footnote,3 p. 94; See 

footnote,6 p. S60. 

HPLC ............... 632.

GC/MS ............. 625.1.

48. Mirex ..................................... GC ................... 617, 608.3 ............. 6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 7; See 

footnote,4 O–3104–83. 

GC/MS ............. 625.1.

49. Monuron ............................... TLC .................. ................................ ............................... ............................... See footnote,3 p. 104; 

See footnote,6 p. S64. 

HPLC ............... 632.

50. Monuron-TCA ....................... TLC .................. ................................ ............................... ............................... See footnote,3 p. 104; 

See footnote,6 p. S64. 

HPLC ............... 632.

51. Neburon ................................ TLC .................. ................................ ............................... ............................... See footnote,3 p. 104; 

See footnote,6 p. S64. 

HPLC ............... 632.

HPLC/MS ........ ................................ ............................... ............................... See footnote,12 O–2060– 

01. 

52. Parathion methyl .................. GC ................... 614, 622, 1657 ...... 6630 B–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, 

D5812–96(02).

See footnote,3 p. 7. 

55. Perthane ............................... GC ................... 617, 608.3 ............. ............................... D3086–90,

D5812–96(02).

See footnote,4 O–3104– 

83. 

56. Prometon .............................. GC ................... 507, 619 ................ ............................... ............................... See footnote,3 p. 83; See 

footnote,6 p. S68; See 

footnote,9 O–3106–93. 

GC/MS ............. 525.2, 625.1 .......... ............................... ............................... See footnote,11 O–1126– 

95. 

57. Prometryn ............................. GC ................... 507, 619 ................ ............................... ............................... See footnote,3 p. 83; See 

footnote,6 p. S68; See 

footnote,9 O–3106–93. 

GC/MS ............. 525.1, 525.2, 625.1 ............................... ............................... See footnote,13 O–2002– 

01. 

58. Propazine ............................. GC ................... 507, 619, 1656, 

608.3.

............................... ............................... See footnote,3 p. 83; See 

footnote,6 p. S68; See 

footnote,9 O–3106–93. 

GC/MS ............. 525.1, 525.2, 625.1.

59. Propham ............................... TLC .................. ................................ ............................... ............................... See footnote,3 p. 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, 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 ............................... ............................... 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. 

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TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1—Continued 

Parameter Method EPA2 7 10 Standard 

methods ASTM Other 

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, 608.3.

6630 B–2007 & C– 

2007.

D3086–90, 

D5812–96(02).

See footnote,3 p. 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, 608.3.

6630 B–2007 ........ ............................... See footnote,3 p. 7; See 

footnote,9 O–3106–93. 

GC/MS ............. 525.2, 625.1 .......... ............................... ............................... See footnote,11 O–1126– 

95. 

Table ID notes: 

1Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides may be found under Table IC, 

where entries are listed by chemical name. 2The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at Appendix B, 

Definition and Procedure for the Determination of the Method Detection Limit, of this Part 136. 3 Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. 

EPA. This EPA publication includes thin-layer chromatography (TLC) methods. 4 Methods for the Determination of Organic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the 

U.S. Geological Survey, Book 5, Chapter A3. 1987. USGS. 5The method may be extended to include a-BHC, g-BHC, endosulfan I, endosulfan II, and endrin. However, when they are known to exist, 

Method 608.3 is the preferred method. 6Selected 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). 7Each 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. 8Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk. Revised October 28, 1994. 3M Corporation. 9 Method O–3106–93 is in Open File Report 94–37, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory— 

Determination of Triazine and Other Nitrogen-Containing Compounds by Gas Chromatography With Nitrogen Phosphorus Detectors. 1994. 

USGS. 10EPA Methods 608.1, 608.2, 614, 614.1, 615, 617, 619, 622, 622.1, 627, and 632 are found in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, EPA 821–R–92–002, April 1992, U.S. EPA. EPA Methods 505, 507, 508, 525.1, 531.1 

and 553 are in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume II, EPA 821–R–93– 

010B, 1993, U.S. EPA. EPA Method 525.2 is in Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary 

Column Gas Chromatography/Mass Spectrometry, Revision 2.0, 1995, U.S. EPA. EPA methods 1656 and 1657 are in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume I, EPA 821–R–93–010A, 1993, U.S. EPA. Methods 

608.3 and 625.1 are available at: http://water.epa.gov/scitech/methods/cwa/methods_index.cfm (this is a placeholder for now). 11 Method O–1126–95 is in Open-File Report 95–181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory— 

Determination of pesticides in water by C–18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selectedion monitoring. 1995. USGS. 12 Method O–2060–01 is in Water-Resources Investigations Report 01–4134, Methods of Analysis by the U.S. Geological Survey National 

Water Quality Laboratory—Determination of Pesticides in Water by Graphitized Carbon-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass Spectrometry. 2001. USGS. 13 Method O–2002–01 is in Water-Resources Investigations Report 01–4098, Methods of Analysis by the U.S. Geological Survey National 

Water Quality Laboratory—Determination of moderate-use pesticides in water by C–18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry. 2001. USGS. 14 Method O–1121–91 is in Open-File Report 91–519, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory— 

Determination of organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with 

selected-ion monitoring. 1992. USGS. 

* * * * * 

TABLE 1F—LIST OF APPROVED METHODS FOR PHARMACEUTICAL POLLUTANTS

Pharmaceuticals pollutants CAS Registry 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. 

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TABLE 1F—LIST OF APPROVED METHODS FOR PHARMACEUTICAL POLLUTANTS—Continued 

Pharmaceuticals pollutants CAS Registry No. Analytical method number 

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 ® (2-Methoxy ethanol) ........................................ 109–86–4 1666/1671. 

Methylene chloride ........................................................................... 75–09–2 502.2/524.2/624.1. 

Methyl formate ................................................................................. 107–31–3 1666. 

4-Methyl-2-pentanone (MIBK) .......................................................... 108–10–1 1624C/1666/D3695/D4763/524.2/624.1. 

Phenol .............................................................................................. 108–95–2 D4763. 

n-Propanol ........................................................................................ 71–23–8 1666/1671/D3695/624.1. 

2-Propanone (Acetone) .................................................................... 67–64–1 D3695/D4763/524.2/624.1. 

Tetrahydrofuran ................................................................................ 109–99–9 1666/524.2/624.1. 

Toluene ............................................................................................ 108–88–3 D3695/D4763/502.2/524.2/624.1. 

Triethlyamine .................................................................................... 121–44–8 1666/1671. 

Xylenes ............................................................................................. (Note 1) 1624C/1666/624.1. 

Table 1F note: 

1 1624C: m-xylene 108–38–3, o,p-xylene, E–14095 (Not a CAS number; this is the number provided in the Environmental Monitoring Methods 

Index [EMMI] database.); 1666: m,p-xylene 136777–61–2, o-xylene 95–47–6. 

TABLE 1G—TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS (40 CFR PART 455) 

EPA survey 

code Pesticide name CAS No. EPA analytical method No.(s) 3

8 ...................... Triadimefon ..................................................... 43121–43–3 507/633/525.1/525.2/1656/625.1. 

12 .................... Dichlorvos ....................................................... 62–73–7 1657/507/622/525.1/525.2/625.1. 

16 .................... 2,4–D; 2,4–D Salts and Esters [2,4-Dichlorophenoxyacetic acid].94–75–7 1658/515.1/615/515.2/555. 

17 .................... 2,4–DB; 2,4–DB Salts and Esters [2,4- 

Dichlorophenoxybutyric acid].

94–82–6 1658/515.1/615/515.2/555. 

22 .................... Mevinphos ....................................................... 7786–34–7 1657/507/622/525.1/525.2/625.1.

25 .................... Cyanazine ....................................................... 21725–46–2 629/507/608.3/625.1. 

26 .................... Propachlor ....................................................... 1918–16–7 1656/508/608.1/525.1/525.2/608.3/625.1. 

27 .................... MCPA; MCPA Salts and Esters [2-Methyl-4- 

chlorophenoxyacetic acid].

94–74–6 1658/615/555. 

30 .................... Dichlorprop; Dichlorprop Salts and Esters [2- 

(2,4-Dichlorophenoxy) propionic acid].

120–36–5 1658/515.1/615/515.2/555. 

31 .................... MCPP; MCPP Salts and Esters [2-(2-Methyl4-chlorophenoxy) propionic acid].93–65–2 1658/615/555. 

35 .................... TCMTB [2-(Thiocyanomethylthio) benzo-thiazole].21564–17–0 637. 

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 ....................................................... 21087–64–9 507/633/525.1/525.2/1656/608.3/6 625.1. 

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 ........................................................... 1912–24–9 505/507/619/525.1/525.2/1656/6 608.3/625.1. 

62 .................... Benomyl .......................................................... 17804–35–2 631. 

68 .................... Bromacil; Bromacil Salts and Esters .............. 314–40–9 507/633/525.1/525.2/1656/608.3/6 625.1. 

69 .................... Bromoxynil ...................................................... 1689–84–5 1625/1661/625.1. 

69 .................... Bromoxynil octanoate ..................................... 1689–99–2 1656/608.3. 

70 .................... Butachlor ......................................................... 23184–66–9 507/645/525.1/525.2/1656/608.3/625.1. 

73 .................... Captafol ........................................................... 2425–06–1 1656/608.3/625.1. 

75 .................... Carbaryl [Sevin] .............................................. 63–25–2 531.1/632/553/625.1. 

76 .................... Carbofuran ...................................................... 1563–66–2 531.1/632/625.1. 

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TABLE 1G—TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS (40 CFR PART 455)—Continued 

EPA survey 

code Pesticide name CAS No. EPA analytical method No.(s) 3

80 .................... Chloroneb ....................................................... 2675–77–6 1656/508/608.1/525.1/525.2/608.3/625.1. 

82 .................... Chlorothalonil .................................................. 1897–45–6 508/608.2/525.1/525.2/1656/608.3/625.1. 

84 .................... Stirofos ............................................................ 961–11–5 1657/507/622/525.1/525.2/625.1. 

86 .................... Chlorpyrifos ..................................................... 2921–88–2 1657/508/622/625.1. 

90 .................... Fenvalerate ..................................................... 51630–58–1 1660. 

103 .................. Diazinon .......................................................... 333–41–5 1657/507/614/622/525.2/625.1. 

107 .................. Parathion methyl ............................................. 298–00–0 1657/614/622/625.1. 

110 .................. DCPA [Dimethyl 2,3,5,6-tetrachloroterephthalate].1861–32–1 508/608.2/525.1/525.2/515.1 2/515.2 2/1656/

608.3/625.1. 

112 .................. Dinoseb ........................................................... 88–85–7 1658/515.1/615/515.2/555/625.1. 

113 .................. Dioxathion ....................................................... 78–34–2 1657/614.1. 

118 .................. Nabonate [Disodium cyanodithioimidocarbonate].138–93–2 630.1. 

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-(Phosphonomethyl) glycine] ... 1071–83–6 547. 

140 .................. Heptachlor ....................................................... 76–44–8 1656/505/508/617/525.1/525.2/608.3/625.1. 

144 .................. Isopropalin ...................................................... 33820–53–0 1656/627/608.3. 

148 .................. Linuron ............................................................ 330–55–2 553/632. 

150 .................. Malathion ........................................................ 121–75–5 1657/614/625.1. 

154 .................. Methamidophos .............................................. 10265–92–6 1657. 

156 .................. Methomyl ........................................................ 16752–77–5 531.1/632. 

158 .................. Methoxychlor ................................................... 72–43–5 1656/505/508/608.2/617/525.1/525.2/608.3/

625.1. 

172 .................. Nabam ............................................................ 142–59–6 630/630.1. 

173 .................. Naled ............................................................... 300–76–5 1657/622/625.1. 

175 .................. Norflurazon ..................................................... 27314–13–2 507/645/525.1/525.2/1656/608.3/625.1. 

178 .................. Benfluralin ....................................................... 1861–40–1 1656/627/608.3 See footnote 1.

182 .................. Fensulfothion .................................................. 115–90–2 1657/622/625.1. 

183 .................. Disulfoton ........................................................ 298–04–4 1657/507/614/622/525.2/625.1. 

185 .................. Phosmet .......................................................... 732–11–6 1657/622.1/625.1. 

186 .................. Azinphos Methyl ............................................. 86–50–0 1657/614/622/625.1. 

192 .................. Organo-tin pesticides ...................................... 12379–54–3 Ind-01/200.7/200.9. 

197 .................. Bolstar ............................................................. 35400–43–2 1657/622. 

203 .................. Parathion ......................................................... 56–38–2 1657/614/625.1. 

204 .................. Pendimethalin ................................................. 40487–42–1 1656. 

205 .................. Pentachloronitrobenzene ................................ 82–68–8 1656/608.1/617/608.3/625.1. 

206 .................. Pentachlorophenol .......................................... 87–86–5 1625/515.2/555/515.1/525.1/525.2/625.1.

208 .................. Permethrin ...................................................... 52645–53–1 608.2/508/525.1/525.2/1656/1660/608.3 4/

625.1 4. 

212 .................. Phorate ........................................................... 298–02–2 1657/622/625.1. 

218 .................. Busan 85 [Potassium 

dimethyldithiocarbamate].

128–03–0 630/630.1. 

219 .................. Busan 40 [Potassium N-hydroxymethyl-Nmethyldithiocarbamate].51026–28–9 630/630.1. 

220 .................. KN Methyl [Potassium N-methyldithiocarbamate].137–41–7 630/630.1. 

223 .................. Prometon ........................................................ 1610–18–0 507/619/525.2/625.1. 

224 .................. Prometryn ....................................................... 7287–19–6 507/619/525.1/525.2/625.1. 

226 .................. Propazine ........................................................ 139–40–2 507/619/525.1/525.2/1656/608.3/625.1. 

230 .................. Pyrethrin I ....................................................... 121–21–1 1660. 

232 .................. Pyrethrin II ...................................................... 121–29–9 1660. 

236 .................. DEF [S,S,S-Tributyl phosphorotrithioate] ....... 78–48–8 1657. 

239 .................. Simazine ......................................................... 122–34–9 505/507/619/525.1/525.2/1656/608.3/625.1. 

241 .................. Carbam-S [Sodium dimethyldithio-carbamate] 128–04–1 630/630.1. 

243 .................. Vapam [Sodium methyldithiocarbamate] ........ 137–42–8 630/630.1. 

252 .................. Tebuthiuron ..................................................... 34014–18–1 507/525.1/525.2/625.1. 

254 .................. Terbacil ........................................................... 5902–51–2 507/633/525.1/525.2/1656/608.3/625.1. 

255 .................. Terbufos .......................................................... 13071–79–9 1657/507/614.1/525.1/525.2/625.1. 

256 .................. Terbuthylazine ................................................ 5915–41–3 619/1656/608.3. 

257 .................. Terbutryn ......................................................... 886–50–0 507/619/525.1/525.2/625.1. 

259 .................. Dazomet .......................................................... 533–74–4 630/630.1/1659. 

262 .................. Toxaphene ...................................................... 8001–35–2 1656/505/508/617/525.1/525.2/608.3/625.1. 

263 .................. Merphos [Tributyl phosphorotrithioate] ........... 150–50–5 1657/507/525.1/525.2/622/625.1. 

264 .................. Trifluralin 1 ....................................................... 1582–09–8 1656/508/617/627/525.2/608.3/625.1. 

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TABLE 1G—TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS (40 CFR PART 455)—Continued 

EPA survey 

code Pesticide name CAS No. EPA analytical method No.(s) 3

268 .................. Ziram [Zinc dimethyldithiocarbamate] ............. 137–30–4 630/630.1. 

Table 1G notes: 

1 Monitor and report as total Trifluralin. 

2Applicable to the analysis of DCPA degradates. 

3EPA Methods 608.1 through 645, 1645 through 1661, and Ind-01 are available in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume I, EPA 821–R–93–010A, Revision I, August 1993, U.S. EPA. EPA Methods 200.9 and 

505 through 555 are available in Methods for the Determination of Nonconventional Pesticides in Municipal and Industrial Wastewater, Volume II, 

EPA 821–R–93–010B, August 1993, U.S. EPA. The full text of Methods 608.3, 625.1, and 1625 are provided at Appendix A of this part 136. The 

full text of Method 200.7 is provided at Appendix C of this part 136. Methods 608.3 and 625.1 are available at: http://water.epa.gov/scitech/methods/cwa/methods_index.cfm (this is a placeholder for now). 4Permethrin is not listed within methods 608.3 and 625.1; however, cis-permethrin and trans-permethrin are listed. Permethrin can be calculated by adding the results of cis and trans-permethrin. 

TABLE 1H—LIST OF APPROVED MICROBIOLOGICAL METHODS FOR AMBIENT WATER

Parameter and units Method 1 EPA Standard 

methods 

AOAC, 

ASTM, 

USGS 

Other 

Bacteria: 

1. Coliform (fecal), number per 100 mL or 

number per gram dry weight.

Most Probable Number 

(MPN), 5 tube, 3 dilution, 

or.

p. 132 3 .......... 9221 C E– 

2006 

Membrane filter (MF),2 single 

step.

p. 124 3 .......... 9222 D– 

2006 27

B–0050–85 4

2. Coliform (fecal) in presence of chlorine, 

number per 100 mL.

MPN, 5 tube, 3 dilution, or .... p. 132 3 .......... 9221 C E– 

2006 

MF 2, single step 5 .................. p. 124 3 .......... 9222 D– 

2006 27

3. Coliform (total), number per 100 mL ......... MPN, 5 tube, 3 dilution, or .... p. 114 3 .......... 9221 B–2006 

MF 2, single step or two step p. 108 3 .......... 9222 B–2006 B–0025–85 4

4. Coliform (total), in presence of chlorine, 

number per 100 mL.

MPN, 5 tube, 3 dilution, or .... p. 114 3 .......... 9221 B–2006 

MF 2 with enrichment ............. p. 111 3 .......... 9222 B–2006 

5.E. coli, number per 100 mL ........................ MPN,6 8 14 multiple tube, or .... ........................ 9221 B.2– 

2006/9221 

F–2006 11 13

Multiple tube/multiple well, or ........................ 9223 B– 

2004 12

991.15 10 Colilert® 12 16, 

Colilert-

® 12 15 16

MF 25678, two step, or .......... 1103.1 19 ........ 9222 B–2006/

9222 G– 

2006,18

9213 D– 

2007 

D5392–93 9

Single step ............................. 1603 20, 

1604 21.

mColiBlue– 

24® 17

6. Fecal streptococci, number per 100 mL .... MPN, 5 tube, 3 dilution, or .... p. 139 3 .......... 9230 B–2007 

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,6 8 multiple tube/multiple 

well, or.

........................ 9230 D–2007 D6503–99 9 Enterolert® 12 22

MF 25678 two step, or ........... 1106.1 23 ........ 9230 C–2007 D5259–92 9

Single step, or ....................... 1600 24 ........... 9230 C–2007 

Plate count ............................ p. 143 3.

Protozoa:.

8.Cryptosporidium .......................................... Filtration/IMS/FA .................... 1622 25, 

1623 26.

9.Giardia ......................................................... Filtration/IMS/FA .................... 1623 26.

Table 1H notes: 

1The method must be specified when results are reported. 

2A 0.45-μm membrane filter (MF) or other pore size certified by the manufacturer to fully retain organisms to be cultivated and to be free of 

extractables which could interfere with their growth. 3 Microbiological Methods for Monitoring the Environment, Water, and Wastes. EPA/600/8–78/017. 1978. US EPA. 

4 U.S. Geological Survey Techniques of Water-Resource Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and 

Analysis of Aquatic Biological and Microbiological Samples. 1989. USGS. 5Because the MF technique usually yields low and variable recovery from chlorinated wastewaters, the Most Probable Number method will be 

required to resolve any controversies. 6Tests 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. 

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8996 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

7When 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. 8To 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. 9Annual Book of ASTM Standards—Water and Environmental Technology. Section 11.02. 2000, 1999, 1996. ASTM International. 

10Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. 1995. AOAC International. 11The 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. 12These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is used to detect the enzyme b-glucuronidase produced by E. coli. 13After 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 μg/mL of MUG may be used. 14Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube 

and dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert® may be enumerated with the multiple-well procedures, Quanti-Tray® or Quanti-Tray®/2000, and the MPN calculated from the table provided by the manufacturer. 15 Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms and E. coli that provides results within 18 h of 

incubation at 35 °C, rather than the 24 h required for the Colilert® test, and is recommended for marine water samples. 16 Descriptions of the Colilert®, Colilert-18®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories Inc. 17A description of the mColiBlue24® test may be obtained from Hach Company. 18Subject total coliform positive samples determined by 9222B–1997 or other membrane filter procedure to 9222G–1997 using NA–MUG 

media. 19 Method 1103.1: Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC), 

EPA–821–R–10–002. March 2010. US EPA. 20 Method 1603: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar 

(Modified mTEC), EPA–821–R–14–010. September 2014. US EPA. 21Preparation and use of MI agar with a standard membrane filter procedure is set forth in the article, Brenner et al. 1993. New Medium for 

the Simultaneous Detection of Total Coliform and Escherichia coli in Water. Appl. Environ. Microbiol. 59:3534–3544 and in Method 1604: Total 

Coliforms and Escherichia coli (E. coli) in Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI Medium), EPA 821– 

R–02–024, September 2002, US EPA. 22A description of the Enterolert® test may be obtained from IDEXX Laboratories Inc. 23 Method 1106.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE–EIA), EPA–821–R–09– 

015. December 2009. US EPA. 24 Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-b-D-Glucoside Agar (mEI), EPA–821–R– 

14–011. September 2014. US EPA. 25 Method 1622 uses a filtration, concentration, immunomagnetic separation of oocysts from captured material, immunofluorescence assay to 

determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the detection of 

Cryptosporidium. Method 1622: Cryptosporidium in Water by Filtration/IMS/FA, EPA–821–R–05–001. December 2005. US EPA. 26 Method 1623 uses a filtration, concentration, immunomagnetic separation of oocysts and cysts from captured material, immunofluorescence 

assay to determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the simultaneous detection of Cryptosporidium and Giardia oocysts and cysts. Method 1623: Cryptosporidium and Giardia in Water by Filtration/IMS/FA. 

EPA–821–R–05–002. December 2005. US EPA. 27The verification frequency is at least five typical and five atypical colonies per sampling site on the day of sample collection and analysis. 

(b) The documents required in this 

section are incorporated by reference 

into this section in accordance with 5 

U.S.C. 552(a) and 1 CFR part 51. Copies 

of the documents may be obtained from 

the sources listed in paragraph (b) of 

this section. Documents may be 

inspected at EPA’s Water Docket, EPA 

West, 1301 Constitution Avenue NW., 

Room 3334, Washington, DC 20004, 

(Telephone: 202–566–2426); or at the 

National Archives and Records 

Administration (NARA). For 

information on the availability of this 

material at NARA, call 202–741–6030, 

or go to: http://www.archives.gov/

federal_register/code_of_federal_

regulations/ibr_locations.html. These 

test procedures are incorporated as they 

exist on the day of approval and a notice 

of any change in these test procedures 

will be published in the Federal 

Register. The full texts of the methods 

from the following references which are 

cited in Tables IA, IB, IC, ID, IE, IF, IG 

and IH of this section are incorporated 

by reference into this regulation and 

may be obtained from the source 

identified. 

* * * * * 

(8) * * * 

* * * * * 

(iv) Method 1600: Enterococci in 

Water by Membrane Filtration Using 

membrane-Enterococcus Indoxyl-b-DGlucoside 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 membraneThermotolerant 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 MultipleTube Fermentation using Lauryl 

Tryptose Broth (LTB) and EC Medium. 

September 2014. EPA–821–R–14–009. 

Table IA, Note 15. 

* * * * * 

(xv) Method 1682: Salmonella in 

Sewage Sludge (Biosolids) by Modified 

Semisolid Rappaport-Vassiliadis 

(MSRV) Medium. September 2014. EPA 

821–R–14–012. Table IA, Note 23. 

* * * * * 

(10) * * * 

* * * * * 

(viii) 2120, Color. 2011. Table IB. 

* * * * * 

(x) 2310, Acidity. 2011. Table IB. 

(xi) 2320, Alkalinity. 2011. Table IB. 

(xii) 2340, Hardness. 2011. Table IB. 

(xiii) 2510, Conductivity. 2011. Table 

IB. 

(xiv) 2540, Solids. 2011. Table IB. 

(xv) 2550, Temperature. 2011. Table 

IB. 

(xvi) 3111, Metals by Flame Atomic 

Absorption Spectrometry. 2011. Table 

IB. 

(xvii) 3112, Metals by Cold-Vapor 

Atomic Absorption Spectrometry. 2011. 

Table IB. 

(xviii) 3113, Metals by Electrothermal 

Atomic Absorption Spectrometry. 2010. 

Table IB. 

(xix) 3114, Arsenic and Selenium by 

Hydride Generation/Atomic Absorption 

Spectrometry. 2011. Table IB. 

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(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-SO3

2·, Sulfite. 2011. Table 

IB. 

(li) 4500-SO4

2·, Sulfate. 2011. Table 

IB. 

(lii) 5210, Biochemical Oxygen 

Demand (BOD). 2011. Table IB. 

(liii) 5220, Chemical Oxygen Demand 

(COD). 2011. Table IB. 

(liv) 5310, Total Organic Carbon 

(TOC). 2011. Table IB. 

(lv) 5520, Oil and Grease. 2011. Table 

IB. 

(lvi) 5530, Phenols. 2010. Table IB. 

(lvii) 5540, Surfactants. 2011. Table 

IB. 

(lviii) 6200, Volatile Organic 

Compounds. 2011. Table IC. 

* * * * * 

(lxi) 6440, Polynuclear Aromatic 

Hydrocarbons. 2005. Table IC. 

(lxii) 6630, Organochlorine Pesticides. 

2007. Table ID. 

(lxiii) 6640, Acidic Herbicide 

Compounds. 2006. Table ID. 

* * * * * 

(lxviii) 9222, Membrane Filter 

Technique for Members of the Coliform 

Group. 2006. Table IA; Table IH, Note 

18. 

* * * * * 

(15) * * * 

* * * * * 

(v) ASTM D511–09, Standard Test 

Methods for Calcium and Magnesium in 

Water. May 2009. Table IB. 

* * * * * 

(viii) ASTM D516–11, Standard Test 

Method for Sulfate Ion in Water, 

September 2011. Table IB. 

(ix) ASTM D858–12, Standard Test 

Methods for Manganese in Water. 

September 2012. Table IB. 

(x) ASTM D859–10, Standard Test 

Method for Silica in Water. July 2010. 

Table IB. 

* * * * * 

(xii) ASTM D1067–11, Standard Test 

Methods for Acidity or Alkalinity of 

Water. April 2011. Table IB. 

(xiii) ASTM D1068–10, Standard Test 

Methods for Iron in Water. October 

2010. Table IB. 

* * * * * 

(xv) ASTM D1126–12, Standard Test 

Method for Hardness in Water. March 

2012. Table IB. 

(xvi) ASTM D1179–10, Standard Test 

Methods for Fluoride Ion in Water. July 

2010. Table IB. 

(xvii) ASTM D1246–10, Standard Test 

Method for Bromide Ion in Water. July 

2010. Table IB. 

* * * * * 

(xxii) ASTM D1687–12 (Approved 

September 1, 2012), Standard Test 

Methods for Chromium in Water. 

August 2007. Table IB. 

(xxiii) ASTM D1688–12, Standard 

Test Methods for Copper in Water. 

September 2012. Table IB. 

(xxiv) ASTM D1691–12, Standard 

Test Methods for Zinc in Water. 

September 2012. Table IB. 

* * * * * 

(xxx) ASTM D1976–12, Standard Test 

Method for Elements in Water by 

Inductively-Coupled Argon Plasma 

Atomic Emission Spectroscopy. March 

2012. Table IB. 

* * * * * 

(xxxv) ASTM D3223–12, Standard 

Test Method for Total Mercury in Water. 

September 2012. Table IB. 

* * * * * 

(xxxvii) ASTM D3373–12, Standard 

Test Method for Vanadium in Water. 

September 2012. Table IB. 

* * * * * 

(xxxix) ASTM D3557–12, Standard 

Test Method for Cadmium in Water. 

September 2012. Table IB. 

* * * * * 

(xlii) ASTM D3590–11, Standard Test 

Methods for Total Kjeldahl Nitrogen in 

Water. April 2011. Table IB. 

* * * * * 

(l) ASTM D4382–12, Standard Test 

Method for Barium in Water, Atomic 

Absorption Spectrophotometry, 

Graphite Furnace. September 2012. 

Table IB. 

* * * * * 

(lii) ASTM D4658–09, Standard Test 

Method for Sulfide Ion in Water. May 

2009. Table IB. 

* * * * * 

(lv) ASTM D5257–11, Standard Test 

Method for Dissolved Hexavalent 

Chromium in Water by Ion 

Chromatography. April 2011. Table IB. 

* * * * * 

(lviii) ASTM D5673–10, Standard Test 

Method for Elements in Water by 

Inductively Coupled Plasma—Mass 

Spectrometry. September 2010. Table 

IB. 

(lix) ASTM D5907–13, Standard Test 

Method for Filterable and Nonfilterable 

Matter in Water. July 2013. Table IB. 

* * * * * 

(lxi) ASTM. D6508–10, Standard Test 

Method for Determination of Dissolved 

Inorganic Anions in Aqueous Matrices 

Using Capillary Ion Electrophoresis and 

Chromate Electrolyte. October 2010. 

Table IB, Note 54. 

* * * * * 

(lxvi) ASTM. D7284–13, Standard 

Test Method for Total Cyanide in Water 

by Micro Distillation followed by Flow 

Injection Analysis with Gas Diffusion 

Separation and Amperometric 

Detection. July 2013. Table IB. 

* * * * * 

(lxviii) ASTM. D7511–12, Standard 

Test Method for Total Cyanide by 

Segmented Flow Injection Analysis, InLine Ultraviolet Digestion and 

Amperometric Detection. January 2012. 

Table IB. 

* * * * * 

(19) * * * 

* * * * * 

(vii) Method 10206, TNTplus 835–836 

Nitrate Method, Spectrophotometric 

Measurement of Nitrate in Water and 

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8998 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

Wastewater. Revision 2.1, January 10, 

2013. Table IB, Note 75. 

(viii) Method 10242, TNTplus 880 

Total Kjeldahl Nitrogen Method, 

Simplified Spectrophotometric 

Measurement of Total Kjeldahl Nitrogen 

in Water and Wastewater. Revision 1.1, 

January 10, 2013. Table IB, Note 75. 

* * * * * 

(20) * * * 

(i) Colilert®. 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®. 2013. Table IA, 

Note 18; Table IH, Notes 14 and 16. 

* * * * * 

(25) National Council of the Paper 

Industry for Air and Stream 

Improvements, Inc. (NCASI), 260 

Madison Avenue, New York NY 10016. 

(i) NCASI Methods TNTP–W10900 as 

an Alternative Testing Procedure to EPA 

Method 351.2 and EPA Method 365.4. 

June 2011. Table IB, Note 77. 

(ii) NCASI Technical Bulletin No. 

253, An Investigation of Improved 

Procedures for Measurement of Mill 

Effluent and Receiving Water Color. 

December 1971. Table IB, Note 18. 

(iii) NCASI Technical Bulletin No. 

803, An Update of Procedures for the 

Measurement of Color in Pulp Mill 

Wastewaters. May 2000. Table IB, Note 

18. 

(26) The Nitrate Elimination Co., Inc. 

(NECi), 334 Hecla St., Lake Linden NI 

49945. 

(i) NECi Method N07–0003, Method 

for Nitrate Reductase Nitrate-Nitrogen 

Analysis. Revision 9.0. March 2014. 

Table IB, Note 73. 

(ii) [Reserved] 

* * * * * 

(34) Timberline Instruments, LLC, 

1880 South Flatiron Ct., Unit I, Boulder 

CO 80301. 

(i) Determination of Inorganic 

Ammonia by Continuous Flow Gas 

Diffusion and Conductivity Cell 

Analysis. June 24, 2011. Table IB, Note 

74. 

(ii) [Reserved] 

(35) U.S. Geological Survey (USGS), 

U.S. Department of the Interior, Reston, 

Virginia. Available from USGS Books 

and Open-File Reports (OFR) Section, 

Federal Center, Box 25425, Denver, CO 

80225. 

(i) Colorimetric determination of 

nitrate plus nitrite in water by 

enzymatic reduction, automated 

discrete analyzer methods. U.S. 

Geological Survey Techniques and 

Methods, Book 5, Chapter B8. 2011. 

Table IB, Note 72. 

(ii) Methods for Determination of 

Inorganic Substances in Water and 

Fluvial Sediments, editors, Techniques 

of Water-Resources Investigations of the 

U.S. Geological Survey, Book 5, Chapter 

A1. 1979. Table IB, Note 8. 

(iii) Methods for Determination of 

Inorganic Substances in Water and 

Fluvial Sediments, Techniques of 

Water-Resources Investigations of the 

U.S. Geological Survey, Book 5, Chapter 

A1. 1989. Table IB, Note 2. 

(iv) Methods for the Determination of 

Organic Substances in Water and 

Fluvial Sediments. Techniques of 

Water-Resources Investigations of the 

U.S. Geological Survey, Book 5, Chapter 

A3. 1987. Table IB, Note 24; Table ID, 

Note 4. 

(v) OFR 76–177, Selected Methods of 

the U.S. Geological Survey of Analysis 

of Wastewaters. 1976. Table IE, Note 2. 

(vi) OFR 91–519, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Organonitrogen 

Herbicides in Water by Solid-Phase 

Extraction and Capillary-Column Gas 

Chromatography/Mass Spectrometry 

With Selected-Ion Monitoring. 1992. 

Table ID, Note 14. 

(vii) OFR 92–146, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Total Phosphorus by a 

Kjeldahl Digestion Method and an 

Automated Colorimetric Finish That 

Includes Dialysis. 1992. Table IB, Note 

48. 

(viii) OFR 93–125, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Inorganic and Organic 

Constituents in Water and Fluvial 

Sediments. 1993. Table IB, Note 51; 

Table IC, Note 9. 

(ix) OFR 93–449, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Chromium in Water by 

Graphite Furnace Atomic Absorption 

Spectrophotometry. 1993. Table IB, 

Note 46. 

(x) OFR 94–37, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Triazine and Other 

Nitrogen-containing Compounds by Gas 

Chromatography with Nitrogen 

Phosphorus Detectors. 1994. Table ID, 

Note 9. 

(xi) OFR 95–181, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Pesticides in Water by 

C–18 Solid-Phase Extraction and 

Capillary-Column Gas Chromatography/ 

Mass Spectrometry With Selected-Ion 

Monitoring. 1995. Table ID, Note 11. 

(xii) OFR 97–198, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Molybdenum in Water 

by Graphite Furnace Atomic Absorption 

Spectrophotometry. 1997. Table IB, 

Note 47. 

(xiii) OFR 98–165, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Elements in WholeWater Digests Using Inductively 

Coupled Plasma-Optical Emission 

Spectrometry and Inductively Coupled 

Plasma-Mass Spectrometry. 1998. Table 

IB, Note 50. 

(xiv) OFR 98–639, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Arsenic and Selenium 

in Water and Sediment by Graphite 

Furnace—Atomic Absorption 

Spectrometry. 1999. Table IB, Note 49. 

(xv) OFR 00–170, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Ammonium Plus 

Organic Nitrogen by a Kjeldahl 

Digestion Method and an Automated 

Photometric Finish that Includes Digest 

Cleanup by Gas Diffusion. 2000. Table 

IB, Note 45. 

(xvi) Techniques and Methods Book 

5–B1, Determination of Elements in 

Natural-Water, Biota, Sediment and Soil 

Samples Using Collision/Reaction Cell 

Inductively Coupled Plasma-Mass 

Spectrometry. Chapter 1, Section B, 

Methods of the National Water Quality 

Laboratory, Book 5, Laboratory 

Analysis. 2006. Table IB, Note 70. 

(xvii) U.S. Geological Survey 

Techniques of Water-Resources 

Investigations, Book 5, Laboratory 

Analysis, Chapter A4, Methods for 

Collection and Analysis of Aquatic 

Biological and Microbiological Samples. 

1989. Table IA, Note 4; Table IH, Note 

4. 

(xviii) Water-Resources Investigation 

Report 01–4098, Methods of Analysis by 

the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Moderate-Use 

Pesticides and Selected Degradates in 

Water by C–18 Solid-Phase Extraction 

and Gas Chromatography/Mass 

Spectrometry. 2001. Table ID, Note 13. 

(xix) Water-Resources Investigations 

Report 01–4132, Methods of Analysis by 

the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Organic Plus Inorganic 

Mercury in Filtered and Unfiltered 

Natural Water With Cold Vapor-Atomic 

Fluorescence Spectrometry. 2001. Table 

IB, Note 71. 

(xx) Water-Resources Investigation 

Report 01–4134, Methods of Analysis by 

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the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Pesticides in Water by 

Graphitized Carbon-Based Solid-Phase 

Extraction and High-Performance Liquid 

Chromatography/Mass Spectrometry. 

2001. Table ID, Note 12. 

(xxi) Water Temperature—Influential 

Factors, Field Measurement and Data 

Presentation, Techniques of WaterResources 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

Parameter number/name Container 1 Preservation 2 3 Maximum holding time 4

Table IA—Bacterial Tests: 

1–5. Coliform, total, fecal, and E. coli ....................................... PA, G ............. Cool, <10 °C, 0.008% 

Na2S2O3

5.

8 hours 22 23. 

6. Fecal streptococci ................................................................. PA, G ............. Cool, <10 °C, 0.008% 

Na2S2O3

5.

8 hours 22. 

7. Enterococci ........................................................................... PA, G ............. Cool, <10 °C, 0.008% 

Na2S2O3

5.

8 hours 22. 

8. Salmonella ............................................................................ PA, G ............. Cool, <10 °C, 0.008% 

Na2S2O3

5.

8 hours 22. 

Table IA—Aquatic Toxicity Tests: 

9–12. Toxicity, acute and chronic ............................................. P, FP, G ......... Cool, ≤6 °C 16 ......................... 36 hours. 

Table IB—Inorganic Tests: 

1. Acidity .................................................................................... P, FP, G ......... Cool, ≤6 °C 18 ......................... 14 days. 

2. Alkalinity ................................................................................ P, FP, G ......... Cool, ≤6 °C 18 ......................... 14 days. 

4. Ammonia ............................................................................... P, FP, G ......... Cool, ≤6 °C 18, H2SO4 to pH 

<2.

28 days. 

9. Biochemical oxygen demand ................................................ P, FP, G ......... Cool, ≤6 °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, carbonaceous ..................... P, FP G .......... Cool, ≤6 °C 18 ......................... 48 hours. 

15. Chemical oxygen demand .................................................. P, FP, G ......... Cool, ≤6 °C 18, H2SO4 to pH 

<2.

28 days. 

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 °C 18 ......................... 48 hours. 

23–24. Cyanide, total or available (or CATC) and free ............ P, FP, G ......... Cool, ≤6 °C 18, NaOH to pH 

>10 5 6, reducing agent if 

oxidizer present.

14 days. 

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 °C 18, H2SO4 to pH 

<2.

28 days. 

Table IB—Metals: 7

18. Chromium VI ....................................................................... P, FP, G ......... Cool, ≤6 °C 18, pH = 9.3– 

9.7 20.

28 days. 

35. Mercury (CVAA) .................................................................. P, FP, G ......... HNO3 to pH <2 ....................... 28 days. 

35. Mercury (CVAFS) ................................................................ FP, G; and 

FP-lined 

cap 17.

5 mL/L 12N HCl or 5 mL/L 

BrCl 17.

90 days 17. 

3, 5–8, 12, 13, 19, 20, 22, 26, 29, 30, 32–34, 36, 37, 45, 47, 

51, 52, 58–60, 62, 63, 70–72, 74, 75. Metals, except boron, 

chromium VI, and mercury.

P, FP, G ......... HNO3 to pH <2, or at least 24 

hours prior to analysis 19.

6 months. 

38. Nitrate .................................................................................. P, FP, G ......... Cool, ≤6 °C 18 ......................... 48 hours. 

39. Nitrate-nitrite ........................................................................ P, FP, G ......... Cool, ≤6 °C 18, H2SO4 to pH 

<2.

28 days. 

40. Nitrite ................................................................................... P, FP, G ......... Cool, ≤6 °C 18 ......................... 48 hours. 

41. Oil and grease .................................................................... G .................... Cool to ≤6 °C 18, HCl or 

H2SO4 to pH <2.

28 days. 

42. Organic Carbon ................................................................... P, FP, G ......... Cool to ≤6 °C 18, HCl, H2SO4, 

or H3PO4 to pH <2.

28 days. 

44. Orthophosphate .................................................................. P, FP, G ......... Cool, to ≤6 °C 18 24 ................. Filter within 15 minutes; Analyze within 48 hours. 

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TABLE II—REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES—Continued 

Parameter number/name Container 1 Preservation 2 3 Maximum holding time 4

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 in dark .. 8 hours. 

48. Phenols ............................................................................... G .................... Cool, ≤6 °C 18, H2SO4 to pH 

<2.

28 days. 

49. Phosphorous (elemental) .................................................... G .................... Cool, ≤6 °C 18 ......................... 48 hours. 

50. Phosphorous, total .............................................................. P, FP, G ......... Cool, ≤6 °C 18, H2SO4 to pH 

<2.

28 days. 

53. Residue, total ...................................................................... P, FP, G ......... Cool, ≤6 °C 18 ......................... 7 days. 

54. Residue, Filterable .............................................................. P, FP, G ......... Cool, ≤6 °C 18 ......................... 7 days. 

55. Residue, Nonfilterable (TSS) .............................................. P, FP, G ......... Cool, ≤6 °C 18 ......................... 7 days. 

56. Residue, Settleable ............................................................. P, FP, G ......... Cool, ≤6 °C 18 ......................... 48 hours. 

57. Residue, Volatile ................................................................. P, FP, G ......... Cool, ≤6 °C 18 ......................... 7 days. 

61. Silica .................................................................................... P or Quartz .... Cool, ≤6 °C 18 ......................... 28 days. 

64. Specific conductance .......................................................... P, FP, G ......... Cool, ≤6 °C 18 ......................... 28 days. 

65. Sulfate ................................................................................. P, FP, G ......... Cool, ≤6 °C 18 ......................... 28 days. 

66. Sulfide ................................................................................. P, FP, G ......... Cool, ≤6 °C 18, add zinc acetate plus sodium hydroxide 

to pH >9.

7 days. 

67. Sulfite .................................................................................. P, FP, G ......... None required ......................... Analyze within 15 minutes. 

68. Surfactants .......................................................................... P, FP, G ......... Cool, ≤6 °C 18 ......................... 48 hours. 

69. Temperature ........................................................................ P, FP, G ......... None required ......................... Analyze. 

73. Turbidity .............................................................................. P, FP, G ......... Cool, ≤6 °C 18 ......................... 48 hours. 

Table IC—Organic Tests: 8

13, 18–20, 22, 24–28, 34–37, 39–43, 45–47, 56, 76, 104, 

105, 108–111, 113. Purgeable Halocarbons.

G, FP-lined 

septum.

Cool, ≤6 °C 18, 0.008% 

Na2S2O3

5.

14 days. 

6, 57, 106. Purgeable aromatic hydrocarbons .......................... G, FP-lined 

septum.

Cool, ≤6 °C 18, 0.008% 

Na2S2O3

5, HCl to pH 2 9.

14 days 9. 

3, 4. Acrolein and acrylonitrile ................................................... G, FP-lined 

septum.

Cool, ≤6 °C 18, 0.008% 

Na2S2O3, pH to 4–5 10.

14 days 10. 

23, 30, 44, 49, 53, 77, 80, 81, 98, 100, 112. Phenols 11 .......... G, FP-lined 

cap.

Cool, ≤6 °C 18, 0.008% 

Na2S2O3.

7 days until extraction, 40 

days after extraction. 

7, 38. Benzidines 11 12 ............................................................... G, FP-lined 

cap.

Cool, ≤6 °C 18, 0.008% 

Na2S2O3

5.

7 days until extraction 13. 

14, 17, 48, 50–52. Phthalate esters 11 ...................................... G, FP-lined 

cap.

Cool, ≤6 °C 18 ......................... 7 days until extraction, 40 

days after extraction. 

82–84. Nitrosamines 11 14 .......................................................... G, FP-lined 

cap.

Cool, ≤6 °C 18, store in dark, 

0.008% Na2S2O3

5.

7 days until extraction, 40 

days after extraction. 

88–94. PCBs 11 ......................................................................... G, FP-lined 

cap.

Cool, ≤6 °C 18 ......................... 1 year until extraction, 1 year 

after extraction. 

54, 55, 75, 79. Nitroaromatics and isophorone 11 ..................... G, FP-lined 

cap.

Cool, ≤6 °C 18, store in dark, 

0.008% Na2S2O3 5.

7 days until extraction, 40 

days after extraction. 

1, 2, 5, 8–12, 32, 33, 58, 59, 74, 78, 99, 101. Polynuclear aromatic hydrocarbons 11.G, FP-lined 

cap.

Cool, ≤6 °C 18, store in dark, 

0.008% Na2S2O3

5.

7 days until extraction, 40 

days after extraction. 

15, 16, 21, 31, 87. Haloethers 11 .............................................. G, FP-lined 

cap.

Cool, ≤6 °C 18, 0.008% 

Na2S2O3

5.

7 days until extraction, 40 

days after extraction. 

29, 35–37, 63–65, 107. Chlorinated hydrocarbons 11 ............... G, FP-lined 

cap.

Cool, ≤6 °C 18 ......................... 7 days until extraction, 40 

days after extraction. 

60–62, 66–72, 85, 86, 95–97, 102, 103. CDDs/CDFs 11 .......... G .................... See footnote 11 ...................... See footnote 11. 

Aqueous Samples: Field and Lab Preservation ................ G .................... Cool, ≤6 °C 18, 0.008% 

Na2S2O3

5, pH <9.

1 year. 

Solids and Mixed-Phase Samples: Field Preservation ...... G .................... Cool, ≤6 °C 18 ......................... 7 days. 

Tissue Samples: Field Preservation .................................. G .................... Cool, ≤6 °C 18 ......................... 24 hours. 

Solids, Mixed-Phase, and Tissue Samples: Lab Preservation.G .................... Freeze, ≤ ¥10 °C .................. 1 year. 

114–118. Alkylated phenols ...................................................... G .................... Cool, <6 °C, H2SO4 to pH <2 28 days until extraction, 40 

days after extraction. 

119. Adsorbable Organic Halides (AOX) .................................. G .................... Cool, <6 °C, 0.008% 

Na2S2O3, HNO3 to pH <2.

Hold at least 3 days, but not 

more than 6 months. 

120. Chlorinated Phenolics ....................................................... G, FP-lined 

cap.

Cool, <6 °C, 0.008% 

Na2S2O3, H2SO4 to pH <2.

30 days until acetylation, 30 

days after acetylation. 

Table ID—Pesticides Tests: 

1–70. Pesticides 11 .................................................................... G, FP-lined 

cap.

Cool, ≤6 °C 18, pH 5–9 15 ....... 7 days until extraction, 40 

days after extraction. 

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TABLE II—REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES—Continued 

Parameter number/name Container 1 Preservation 2 3 Maximum holding time 4

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 °C, 0.008% 

Na2S2O3

5.

8 hours 22 23. 

5. E. coli .................................................................................... PA, G ............. Cool, <10 °C, 0.008% 

Na2S2O3

5.

8 hours 22. 

6. Fecal streptococci ................................................................. PA, G ............. Cool, <10 °C, 0.008% 

Na2S2O3

5.

8 hours 22. 

7. Enterococci ........................................................................... PA, G ............. Cool, <10 °C, 0.008% 

Na2S2O3

5.

8 hours 22. 

Table IH—Protozoan Tests: 

8. Cryptosporidium .................................................................... LDPE; field filtration.1–10 °C .................................. 96 hours 21. 

9. Giardia ................................................................................... LDPE; field filtration.1–10 °C .................................. 96 hours 21. 

1 ‘‘P’’ is for polyethylene; ‘‘FP’’ is fluoropolymer (polytetrafluoroethylene (PTFE); Teflon®), 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. 2Except 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 °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 °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). 3When 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). 4Samples 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 § 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 § 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 

°C, with minimum head space. 

5ASTM 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. 6Sampling, 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. 7For 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. 8Guidance 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. 

10The 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. 

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11When 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 °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. 13Extracts may be stored up to 30 days at < 0 °C. 14For the analysis of diphenylnitrosamine, add 0.008% Na2S2O3 and adjust pH to 7–10 with NaOH within 24 hours of sampling. 15The 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. 16Place 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 °C prior to test initiation. 17Samples 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. 18Aqueous samples must be preserved at ≤ 6 °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 ‘‘≤ °C’’ is used in place of the ‘‘4 °C’’ and ‘‘< 4 °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 °C may not be used to meet the ≤6 °C requirement. The preservation temperature does not apply to samples that are analyzed immediately (less than 15 minutes). 19An 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. 20To 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. 22Sample analysis should begin as soon as possible after receipt; sample incubation must be started no later than 8 hours from time of collection. 23For 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. 24The 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). 

■ 5. Section 136.4 is amended by 

revising paragraphs (a) introductory 

text, (b), and (c) to read as follows: 

§ 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 § 136.3. EPA shall make 

available for review all the factual bases 

for its proposal, including the method, 

any performance data submitted by the 

applicant and any available EPA 

analysis of those data. 

(4) Following public comment, EPA 

shall publish in the Federal Register a 

final decision on whether to amend this 

part to include the alternate test 

procedure as an approved analytical 

method for nationwide use. 

(5) Whenever the National 

Coordinator has recommended approval 

of an applicant’s ATP request for 

nationwide use, any person may request 

an approval of the method for limited 

use under § 136.5 from the EPA Region. 

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■ 6. Section 136.5 is amended by 

revising paragraphs (a), (b), (c)(1), and 

(d) to read as follows: 

§ 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. 

■ 7. In § 136.6: 

■ a. Revise paragraphs (b)(1) and (2) 

introductory text. 

■ b. Remove paragraph (b)(4)(xvi). 

■ c. Redesignate paragraphs (b)(4)(xvii) 

through (xxii) as paragraphs (b)(4)(xvi) 

through (xxi), respectively. 

■ d. Add paragraph (c). 

The revision and addition read as 

follows: 

§ 136.6 Method modifications and 

analytical requirements. 

* * * * * 

(b) Method modifications. (1) If the 

underlying chemistry and determinative 

technique in a modified method are 

essentially the same as an approved part 

136 method, then the modified method 

is an equivalent and acceptable 

alternative to the approved method 

provided the requirements of this 

section are met. However, those who 

develop or use a modification to an 

approved (part 136) method must 

document that the performance of the 

modified method, in the matrix to 

which the modified method will be 

applied, is equivalent to the 

performance of the approved method. If 

such a demonstration cannot be made 

and documented, then the modified 

method is not an acceptable alternative 

to the approved method. Supporting 

documentation must, if applicable, 

include the routine initial 

demonstration of capability and ongoing 

QC including determination of precision 

and accuracy, detection limits, and 

matrix spike recoveries. Initial 

demonstration of capability typically 

includes analysis of four replicates of a 

mid-level standard and a method 

detection limit study. Ongoing quality 

control typically includes method 

blanks, mid-level laboratory control 

samples, and matrix spikes (QC is as 

specified in the method). The method is 

considered equivalent if the quality 

control requirements in the reference 

method are achieved. The method user’s 

Standard Operating Procedure (SOP) 

must clearly document the 

modifications made to the reference 

method. Examples of allowed method 

modifications are listed in this section. 

If the method user is uncertain whether 

a method modification is allowed, the 

Regional ATP Coordinator or Director 

should be contacted for approval prior 

to implementing the modification. The 

method user should also complete 

necessary performance checks to verify 

that acceptable performance is achieved 

with the method modification prior to 

analyses of compliance samples. 

(2) Requirements. The modified 

method must meet or exceed 

performance of the approved method(s) 

for the analyte(s) of interest, as 

documented by meeting the initial and 

ongoing quality control requirements in 

the method. 

* * * * * 

(c) The permittee must notify their 

permitting authority of the intent to use 

a modified method. Such notification 

should be of the form ‘‘Method xxx has 

been modified within the flexibility 

allowed in 40 CFR 136.6.’’ The 

permittee may indicate the specific 

paragraph of § 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. 

■ 8. In Appendix A to part 136: 

■ a. Revise Method 608. 

■ b. Revise Method 611, section 1.1. 

■ c. Revise Method 624. 

■ d. Revise Method 625. 

The revisions read as follows: 

Appendix A to Part 136—Methods for 

Organic Chemical Analysis of 

Municipal and Industrial Wastewater 

* * * * * 

Method 608.3—Organochlorine 

Pesticides And PCBs By GC/HSD 

1. Scope and Application 

1.1 This method is for determination 

of organochlorine pesticides and 

polychlorinated biphenyls (PCBs) in 

industrial discharges and other 

environmental samples by gas 

chromatography (GC) combined with a 

halogen-specific detector (HSD; e.g., 

electron capture, electrolytic 

conductivity), as provided under 40 

CFR 136.1. This revision is based on a 

previous protocol (Reference 1), on the 

revision promulgated October 26, 1984 

(49 FR 43234), on an inter-laboratory 

method validation study (Reference 2), 

and on EPA Method 1656 (Reference 

16). The analytes that may be 

qualitatively and quantitatively 

determined using this method and their 

CAS Registry numbers are listed in 

Table 1. 

1.2 This method may be extended to 

determine the analytes listed in Table 2. 

However, extraction or gas 

chromatography challenges for some of 

these analytes may make quantitative 

determination difficult. 

1.3 When this method is used to 

analyze unfamiliar samples for an 

analyte listed in Table 1 or Table 2, 

analyte identification must be supported 

by at least one additional qualitative 

technique. This method gives analytical 

conditions for a second GC column that 

can be used to confirm and quantify 

measurements. 

Additionally, Method 625 provides 

gas chromatograph/mass spectrometer 

(GC/MS) conditions appropriate for the 

qualitative confirmation of results for 

the analytes listed in Tables 1 and 2 

using the extract produced by this 

method, and Method 1699 (Reference 

18) provides high resolution GC/MS 

conditions for qualitative confirmation 

of results using the original sample. 

When such methods are used to confirm 

the identifications of the target analytes, 

the quantitative results should be 

derived from the procedure with the 

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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 alphaand gamma-isomers in Table 1. 

Reporting may be by the individual 

isomers, or as the sum of the 

concentrations of these isomers, as 

requested or required by a regulatory/

control authority or in a permit. 

Technical Chlordane is listed in Table 2 

and may be used in cases where 

historical reporting has only been the 

Technical Chlordane. Toxaphene and 

the PCBs have been moved from Table 

1 to Table 2 (Additional Analytes) to 

distinguish these analytes from the 

analytes required in quality control tests 

(Table 1). QC acceptance criteria for 

Toxaphene and the PCBs have been 

retained in Table 4 and may continue to 

be applied if desired, or if these analytes 

are requested or required by a 

regulatory/control authority or in a 

permit. Method 1668C (Reference 17) 

may be useful for determination of PCBs 

as individual chlorinated biphenyl 

congeners, and Method 1699 (Reference 

18) may be useful for determination of 

the pesticides listed in this method. 

However, at the time of writing of this 

revision, Methods 1668C and 1699 had 

not been approved for use at 40 CFR 

part 136. 

1.6 Method detection limits (MDLs; 

Reference 3) for the analytes in Tables 

1 and some of the analytes in Table 2 

are listed in those tables. These MDLs 

were determined in reagent water 

(Reference 3). Advances in analytical 

technology, particularly the use of 

capillary (open-tubular) columns, 

allowed laboratories to routinely 

achieve MDLs for the analytes in this 

method that are 2–10 times lower than 

those in the version promulgated in 

1984 (40 FR 43234). The MDL for an 

analyte in a specific wastewater may 

differ from those listed, depending upon 

the nature of interferences in the sample 

matrix. 

1.6.1 EPA has promulgated this 

method at 40 CFR part 136 for use in 

wastewater compliance monitoring 

under the National Pollutant Discharge 

Elimination System (NPDES). The data 

reporting practices described in Section 

15.2 are focused on such monitoring 

needs and may not be relevant to other 

uses of the method. 

1.6.2 This method includes 

‘‘reporting limits’’ based on EPA’s 

‘‘minimum level’’ (ML) concept (see the 

glossary in Section 23). Tables 1 and 2 

contain MDL values and ML values for 

many of the analytes. The MDL for an 

analyte in a specific wastewater may 

differ from those listed in Tables 1 or 2, 

depending upon the nature of 

interferences in the sample matrix. 

1.7 The separatory funnel and 

continuous liquid-liquid sample 

extraction and concentration steps in 

this method are essentially the same as 

those steps in Methods 606, 609, 611, 

and 612. Thus, a single sample may be 

extracted to measure the analytes 

included in the scope of each of these 

methods. Samples may also be extracted 

using a disk-based solid-phase 

extraction (SPE) procedure developed 

by the 3M Corporation and approved by 

EPA as an Alternate Test Procedure 

(ATP) for wastewater analyses in 1995 

(Reference 20). 

1.8 This method is performancebased. 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®, alumina, a C18 solidphase cleanup, and an elemental sulfur 

cleanup procedure are provided to aid 

in elimination of interferences that may 

be encountered. Other cleanup 

procedures may be used if demonstrated 

to be effective for the analytes in a 

wastewater matrix. 

3. Contamination and Interferences 

3.1 Solvents, reagents, glassware, 

and other sample processing lab ware 

may yield artifacts, elevated baselines, 

or matrix interferences causing 

misinterpretation of chromatograms. All 

materials used in the analysis must be 

demonstrated free from contamination 

and interferences by running blanks 

initially and with each extraction batch 

(samples started through the extraction 

process in a given 24-hour period, to a 

maximum of 20 samples). Specific 

selection of reagents and purification of 

solvents by distillation in all-glass 

systems may be required. Where 

possible, lab ware is cleaned by 

extraction or solvent rinse, or baking in 

a kiln or oven. All materials used must 

be routinely demonstrated to be free 

from interferences under the conditions 

of the analysis by running blanks as 

described in Section 8.5. 

3.2 Glassware must be scrupulously 

cleaned (Reference 4). Clean all 

glassware as soon as possible after use 

by rinsing with the last solvent used in 

it. Solvent rinsing should be followed 

by detergent washing with hot water, 

and rinses with tap water and reagent 

water. The glassware should then be 

drained dry, and heated at 400 °C for 

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15–30 minutes. Some thermally stable 

materials, such as PCBs, may require 

higher temperatures and longer baking 

times for removal. Solvent rinses with 

pesticide quality acetone, hexane, or 

other solvents may be substituted for 

heating. Volumetric lab ware should not 

be heated excessively or for long periods 

of time. After drying and cooling, 

glassware should be sealed and stored 

in a clean environment to prevent 

accumulation of dust or other 

contaminants. Store inverted or capped 

with aluminum foil. 

3.3 Interferences by phthalate esters 

can pose a major problem in pesticide 

analysis when using the electron 

capture detector. The phthalate esters 

generally appear in the chromatogram as 

large late eluting peaks, especially in the 

15 and 50% fractions from Florisil®. 

Common flexible plastics contain 

varying amounts of phthalates that may 

be extracted or leached from such 

materials during laboratory operations. 

Cross contamination of clean glassware 

routinely occurs when plastics are 

handled during extraction steps, 

especially when solvent-wetted surfaces 

are handled. Interferences from 

phthalates can best be minimized by 

avoiding use of non-fluoropolymer 

plastics in the laboratory. Exhaustive 

cleanup of reagents and glassware may 

be required to eliminate background 

phthalate contamination (References 5 

and 6). Interferences from phthalate 

esters can be avoided by using a 

microcoulometric or electrolytic 

conductivity detector. 

3.4 Matrix interferences may be 

caused by contaminants co-extracted 

from the sample. The extent of matrix 

interferences will vary considerably 

from source to source, depending upon 

the nature and diversity of the industrial 

complex or municipality being sampled. 

Interferences extracted from samples 

high in total organic carbon (TOC) may 

result in elevated baselines, or by 

enhancing or suppressing a signal at or 

near the retention time of an analyte of 

interest. Analyses of the matrix spike 

and duplicate (Section 8.3) may be 

useful in identifying matrix 

interferences, and the cleanup 

procedures in Section 11 may aid in 

eliminating these interferences. EPA has 

provided guidance that may aid in 

overcoming matrix interferences 

(Reference 7); however, unique samples 

may require additional cleanup 

approaches to achieve the MDLs listed 

in Table 3. 

4. Safety 

4.1 The toxicity or carcinogenicity of 

each reagent used in this method has 

not been precisely defined; however, 

each chemical compound should be 

treated as a potential health hazard. 

From this viewpoint, exposure to these 

chemicals must be reduced to the lowest 

possible level by whatever means 

available. The laboratory is responsible 

for maintaining a current awareness file 

of OSHA regulations regarding the safe 

handling of the chemicals specified in 

this method. A reference file of safety 

data sheets (SDSs, OSHA, 29 CFR 

1910.1200(g)) should also be made 

available to all personnel involved in 

sample handling and chemical analysis. 

Additional references to laboratory 

safety are available and have been 

identified (References 8 and 9) for the 

information of the analyst. 

4.2 The following analytes covered 

by this method have been tentatively 

classified as known or suspected human 

or mammalian carcinogens: 4,4′-DDT, 

4,4′-DDD, the BHCs, and the PCBs. 

Primary standards of these toxic 

analytes should be prepared in a 

chemical fume hood, and a NIOSH/

MESA approved toxic gas respirator 

should be worn when high 

concentrations are handled. 

4.3 This method allows the use of 

hydrogen as a carrier gas in place of 

helium (Section 5.8.2). The laboratory 

should take the necessary precautions in 

dealing with hydrogen, and should limit 

hydrogen flow at the source to prevent 

buildup of an explosive mixture of 

hydrogen in air. 

5. Apparatus and Materials 

Note: Brand names and suppliers are for 

illustration purposes only. No endorsement 

is implied. Equivalent performance may be 

achieved using equipment and materials 

other than those specified here. 

Demonstrating that the equipment and 

supplies used in the laboratory achieve the 

required performance is the responsibility of 

the laboratory. Suppliers for equipment and 

materials in this method may be found 

through an on-line search. Please do not 

contact EPA for supplier information. 

5.1 Sampling equipment, for 

discrete or composite sampling 

5.1.1 Grab sample bottle—amber 

glass bottle large enough to contain the 

necessary sample volume (nominally 1 

L), fitted with a fluoropolymer-lined 

screw cap. Foil may be substituted for 

fluoropolymer if the sample is not 

corrosive. If amber bottles are not 

available, protect samples from light. 

Unless pre-cleaned, the bottle and cap 

liner must be washed, rinsed with 

acetone or methylene chloride, and 

dried before use to minimize 

contamination. 

5.1.2 Automatic sampler 

(optional)—the sampler must use a glass 

or fluoropolymer container and tubing 

for sample collection. If the sampler 

uses a peristaltic pump, a minimum 

length of compressible silicone rubber 

tubing may be used. Before use, 

however, the compressible tubing 

should be thoroughly rinsed with 

methanol, followed by repeated rinsing 

with reagent water to minimize the 

potential for sample contamination. An 

integrating flow meter is required to 

collect flow proportional composites. 

The sample container must be kept 

refrigerated at <6 °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 multiposition manifold 

5.2.1.4.1 Vacuum system—Capable 

of achieving 0.1 bar (25 inch) Hg (house 

vacuum, vacuum pump, or water 

aspirator), equipped with shutoff valve 

and vacuum gauge 

5.2.1.4.2 Vacuum trap—Made from 

500-mL sidearm flask fitted with singlehole rubber stopper and glass tubing 

Note: The approved ATP for solid-phase 

extraction is limited to disk-based extraction 

media and associated peripheral equipment. 

5.2.2 Filtration 

5.2.2.1 Glass powder funnel, 125- to 

250-mL 

5.2.2.2 Filter paper for above, 

Whatman 41, or equivalent 

5.2.2.3 Prefiltering aids—90-mm 1- 

mm glass fiber filter or Empore® Filter 

Aid 400 

5.2.3 Drying column 

5.2.3.1 Chromatographic column— 

approximately 400 mm long × 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 

°C for 1 hour minimum 

5.2.4 Column for Florisil® or 

alumina cleanup—approximately 300 

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mm long × 10 mm ID, with 

fluoropolymer stopcock. (This column 

is not required if cartridges containing 

Florisil® 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 groundglass stopper is used to prevent 

evaporation of extracts. 

5.2.5.1.2 Evaporative flask, KudernaDanish—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 °C), installed in 

a hood using appropriate engineering 

controls to limit exposure to solvent 

vapors. 

5.2.5.2 Nitrogen evaporation 

device—Equipped with heated bath that 

can be maintained at an appropriate 

temperature for the solvent and 

analytes. (N-Evap, Organomation 

Associates, Inc., or equivalent) 

5.2.5.3 Rotary evaporator—Buchi/

Brinkman-American Scientific or 

equivalent, equipped with a variable 

temperature water bath, vacuum source 

with shutoff valve at the evaporator, and 

vacuum gauge. 

5.2.5.2.1 A recirculating water pump 

and chiller are recommended, as use of 

tap water for cooling the evaporator 

wastes large volumes of water and can 

lead to inconsistent performance as 

water temperatures and pressures vary. 

5.2.5.2.2 Round-bottom flask—100- 

mL and 500-mL or larger, with groundglass 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 °C for 30 

minutes, or solvent rinse or Soxhlet 

extract with methylene chloride. 

5.2.5 Solid-phase extraction disks— 

90-mm extraction disks containing 2 g 

of 8-mm octadecyl (C18) bonded silica 

uniformly enmeshed in a matrix of inert 

PTFE fibrils (3M Empore® or 

equivalent). The disks should not 

contain any organic compounds, either 

from the PTFE or the bonded silica, 

which will leach into the methylene 

chloride eluant. One liter of reagent 

water should pass through the disks in 

2–5 minutes, using a vacuum of at least 

25 inches of mercury. 

Note: Extraction disks from other 

manufacturers may be used in this 

procedure, provided that they use the same 

solid phase materials (i.e., octadecyl bonded 

silica). Disks of other diameters also may be 

used, but may adversely affect the flow rate 

of the sample through the disk. 

5.3 Vials 

5.3.1 Extract storage—10- to 15-mL, 

amber glass, with fluoropolymer-lined 

screw cap 

5.3.2 GC autosampler—1- to 5-mL, 

amber glass, with fluoropolymer-lined 

screw- or crimp-cap, to fit GC 

autosampler 

5.4 Balances 

5.4.1 Analytical—capable of 

accurately weighing 0.1 mg 

5.4.2 Top loading—capable of 

weighing 10 mg 

5.5 Sample cleanup 

5.5.1 Oven—For baking and storage 

of adsorbents, capable of maintaining a 

constant temperature (± 5 °C) in the 

range of 105–250 °C. 

5.5.2 Muffle furnace—Capable of 

cleaning glassware or baking sodium 

sulfate in the range of 400–450 °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 singlehole rubber stopper and glass tubing 

5.5.3.4 Rack for holding 50-mL 

volumetric flasks in the manifold 

5.5.3.5 Cartridge—Mega Bond Elute, 

Non-polar, C18 Octadecyl, 10 g/60 mL 

(Analytichem International or 

equivalent), used for solid-phase 

cleanup of sample extracts (see Section 

11.2) 

5.5.3.5.1 Cartridge certification— 

Each cartridge lot must be certified to 

ensure recovery of the analytes of 

interest and removal of 2,4,6- 

trichlorophenol. To make the test 

mixture, add the trichlorophenol 

solution (Section 6.7.2.1) to the same 

standard used to prepare the Quality 

Control Check Sample (Section 6.8.3). 

Transfer the mixture to the column and 

dry the column. Pre-elute with three 10- 

mL portions of elution solvent, drying 

the column between elutions. Elute the 

cartridge with 10 mL each of methanol 

and water, as in Section 11.2.3.3. 

5.5.3.5.2 Concentrate the eluant to 

per Section 10.3.3, exchange to 

isooctane or hexane per Section 10.3.3, 

and inject 1.0 mL of the concentrated 

eluant into the GC using the procedure 

in Section 12. The recovery of all 

analytes (including the unresolved GC 

peaks) shall be within the ranges for 

calibration verification (Section 13.6 

and Table 4), and the peak for 

trichlorophenol shall not be detectable; 

otherwise the SPE cartridge is not 

performing properly and the cartridge 

lot shall be rejected. 

5.5.4 Sulfur removal tube—40- to 

50-mL bottle, test tube, or Erlenmeyer 

flask with fluoropolymer-lined screw 

cap 

5.6 Centrifuge apparatus 

5.6.1 Centrifuge—Capable of rotating 

500-mL centrifuge bottles or 15-mL 

centrifuge tubes at 5,000 rpm minimum 

5.6.2 Centrifuge bottle—500-mL, 

with screw cap, to fit centrifuge 

5.6.3 Centrifuge tube—15-mL, with 

screw cap, to fit centrifuge 

5.7 Miscellaneous lab ware— 

graduated cylinders, pipettes, beakers, 

volumetric flasks, vials, syringes, and 

other lab ware necessary to support the 

operations in this method 

5.8 Gas chromatograph—Dualcolumn 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 × 0.53-mm ID fused-silica capillary, 

0.83-mm film thickness. 

5.8.1.2 DB–1701 (or equivalent), 30- 

m long × 0.53-mm ID fused-silica 

capillary, 1.0-mm film thickness. 

5.8.1.3 Suggested operating 

conditions used to meet the retention 

times shown in Table 3 are: 

Carrier gas flow rate: approximately 7 

mL/min 

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Initial temperature: 150 °C for 0.5 

minute, 

Temperature program: 150–270 °C at 5 

°C/min, and 

Final temperature: 270 °C, until transPermethrin elutes 

Note: Other columns, internal diameters, 

film thicknesses, and operating conditions 

may be used, provided that the performance 

requirements in this method are met. 

However, the column pair chosen must have 

dissimilar phases/chemical properties in 

order to separate the compounds of interest 

in different retention time order. Columns 

that only differ in the length, ID, or film 

thickness, but use the same stationary phase 

do not qualify as ‘‘dissimilar.’’ 

5.8.2 Carrier gas—Helium or 

hydrogen. Data in the tables in this 

method were obtained using helium 

carrier gas. If hydrogen is used, 

analytical conditions may need to be 

adjusted for optimum performance, and 

calibration and all QC tests must be 

performed with hydrogen carrier gas. 

See Section 4.3 for precautions 

regarding the use of hydrogen as a 

carrier gas. 

5.8.3 Detector—Halogen-specific 

detector (electron capture detector 

(ECD), electrolytic conductivity detector 

(ELCD), or equivalent). The ECD has 

proven effective in the analysis of 

wastewaters for the analytes listed in 

Tables 1 and 2, and was used to develop 

the method performance data in Section 

17 and Tables 4 and 5. 

5.8.4 Data system—A computer 

system must be interfaced to the GC that 

allows continuous acquisition and 

storage of data from the detectors 

throughout the chromatographic 

program. The computer must have 

software that allows searching GC data 

for specific analytes, and for plotting 

responses versus time. Software must 

also be available that allows integrating 

peak areas or peak heights in selected 

retention time windows and calculating 

concentrations of the analytes. 

6. Reagents and Standards 

6.1 pH adjustment 

6.1.1 Sodium hydroxide solutions 

6.1.1.1 Concentrated (10 M)— 

Dissolve 40 g of NaOH (ACS) in reagent 

water and dilute to 100 mL. 

6.1.1.2 Dilute (1 M)—Dissolve 40 g 

NaOH in 1 L of reagent water. 

6.1.2 Sulfuric acid (1 + 1)—Slowly 

add 50 mL of H2SO4 (ACS, sp. gr. 1.84) 

to 50 mL of reagent water. 

6.1.3 Hydrochloric acid—Reagent 

grade, 6 N 

6.2 Sodium thiosulfate—(ACS) 

granular. 

6.3 Sodium sulfate—Sodium sulfate, 

reagent grade, granular anhydrous 

(Baker or equivalent), rinsed with 

methylene chloride (20 mL/g), baked in 

a shallow tray at 450 °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®—PR grade (60/100 

mesh), activated at 650—700 °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 °C in a foilcovered glass container and allow to 

cool. Alternatively, 500 mg cartridges 

(J.T. Baker, or equivalent) may be used. 

6.7.2 Solutions for solid-phase 

cleanup 

6.7.2.1 SPE cartridge calibration 

solution—2,4,6-trichlorophenol, 0.1 mg/ 

mL in acetone. 

6.7.2.2 SPE elution solvent— 

methylene chloride:acetonitrile:hexane 

(50:3:47). 

6.7.3 Alumina, neutral, Brockman 

Activity I, 80–200 mesh (Fisher 

Scientific certified, or equivalent). Heat 

in a glass bottle for 16 hours at 400 to 

450 °C. Seal and cool to room 

temperature. Add 7% (w/w) reagent 

water and mix for 10 to 12 hours. Keep 

bottle tightly sealed. 

6.7.4 Sulfur removal 

6.7.4.1 Copper foil or powder— 

Fisher, Alfa Aesar, or equivalent. Cut 

copper foil into approximately 1-cm 

squares. Copper must be activated on 

each day it will be used, as described 

below. 

6.7.4.1.1 Place the quantity of 

copper needed for sulfur removal 

(Section 11.5.1.3) in a ground-glassstoppered Erlenmeyer flask or bottle. 

Cover the foil or powder with methanol. 

6.7.4.1.2 Add HCl dropwise (0.5— 

1.0 mL) while swirling, until the copper 

brightens. 

6.7.4.1.3 Pour off the methanol/HCl 

and rinse 3 times with reagent water to 

remove all traces of acid, then 3 times 

with acetone, then 3 times with hexane. 

6.7.4.1.4 For copper foil, cover with 

hexane after the final rinse. Store in a 

stoppered flask under nitrogen until 

used. For the powder, dry on a rotary 

evaporator. Store in a stoppered flask 

under nitrogen until used. 

6.7.4.2 Tetrabutylammonium sulfite 

(TBA sulfite) 

6.7.4.2.1 Tetrabutylammonium 

hydrogen sulfate, [CH3(CH2)3]4NHSO4

6.7.4.2.2 Sodium sulfite, Na2SO3

6.7.4.2.3 Dissolve approximately 3 g 

tetrabutylammonium hydrogen sulfate 

in 100 mL of reagent water in an amber 

bottle with fluoropolymer-lined screw 

cap. Extract with three 20-mL portions 

of hexane and discard the hexane 

extracts. 

6.7.4.2.4 Add 25 g sodium sulfite to 

produce a saturated solution. Store at 

room temperature. Replace after 1 

month. 

6.8 Standard solutions—Purchase as 

solutions or mixtures with certification 

to their purity, concentration, and 

authenticity, or prepare from materials 

of known purity and composition. If 

compound purity is 96% or greater, the 

weight may be used without correction 

to compute the concentration of the 

standard. Store neat standards or single 

analyte standards in the dark at ¥20 to 

¥10 °C in screw-cap vials with 

fluoropolymer-lined caps. Store multianalyte standards at 4 °C or per 

manufacturer’s recommendations. Place 

a mark on the vial at the level of the 

solution so that solvent evaporation loss 

can be detected. Bring the vial to room 

temperature prior to use to re-dissolve 

any precipitate. 

6.8.1 Stock standard solutions— 

Standard solutions may be prepared 

from pure standard materials or 

purchased as certified solutions. 

Traceability must be to a national 

standard, when available. Except as 

noted below for solutions spiked into 

samples, prepare stock standards in 

isooctane or hexane. Observe the safety 

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precautions in Section 4. The following 

procedure may be used to prepare 

standards from neat materials. 

6.8.1.1 Dissolve an appropriate 

amount of assayed reference material in 

solvent. For example, weigh 10 mg of 

aldrin in a 10-mL ground-glassstoppered volumetric flask and fill to 

the mark with isooctane or hexane. 

Larger volumes may be used at the 

convenience of the laboratory. After the 

aldrin is completely dissolved, transfer 

the solution to a 15-mL vial with 

fluoropolymer-lined cap. 

6.8.1.2 Check for signs of 

degradation prior to preparation of 

calibration or performance-test 

standards. 

6.8.1.3 Replace stock solutions after 

12 months, or sooner if comparison with 

quality control check standards 

indicates a change in concentration. 

6.8.2 Calibration solutions—It is 

necessary to prepare calibration 

solutions for the analytes of interest 

(Section 1.4) only using an appropriate 

solvent (isooctane or hexane may be 

used). Whatever solvent is used, both 

the calibration standards and the final 

sample extracts must use the same 

solvent. Other analytes may be included 

as desired. 

6.8.2.1 Prepare calibration standards 

for the single-component analytes of 

interest and surrogates at a minimum of 

three concentration levels (five are 

suggested) by adding appropriate 

volumes of one or more stock standards 

to volumetric flasks. One of the 

calibration standards should be at a 

concentration of the analyte near the ML 

in Table 1 or 2. The ML value may be 

rounded to a whole number that is more 

convenient for preparing the standard, 

but must not exceed the ML values 

listed in Tables 1 or 2 for those analytes 

which list ML values. Alternatively, the 

laboratory may establish the ML for 

each analyte based on the concentration 

of the lowest calibration standard in a 

series of standards obtained from a 

commercial vendor, again, provided that 

the ML values does not exceed the MLs 

in Table 1 and 2, and provided that the 

resulting calibration meets the 

acceptance criteria in Section 7.5.2. 

based on the RSD, RSE, or R2. 

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; 

ax2 + bx + c) calibration. Calibrations 

higher than second order are not 

allowed. 

Given the number of analytes 

included in this method, it is highly 

likely that some will coelute on one or 

both of the GC columns used for the 

analysis. Therefore, divide the analytes 

two or more groups and prepare 

separate calibration standards for each 

group, at multiple concentrations (e.g., a 

five-point calibration will require ten 

solutions to cover two groups of 

analytes). 

Note: Many commercially available 

standards are divided into separate mixtures 

to address this issue. 

The other concentrations should 

correspond to the expected range of 

concentrations found in real samples or 

should define the working range of the 

GC system. A separate standard near the 

MDL may be analyzed as a check on 

sensitivity, but should not be included 

in the linearity assessment. A minimum 

of six concentration levels is required 

for a non-linear (e.g., quadratic) 

calibration (Section 7.5.2 or 7.6.2). The 

solvent for the standards must match 

the final solvent for the sample extracts 

(e.g., isooctane or hexane). 

Note: The option for non-linear calibration 

may be necessary to address specific 

instrumental techniques. However, it is not 

EPA’s intent to allow non-linear calibration 

to be used to compensate for detector 

saturation or to avoid proper instrument 

maintenance. 

6.8.2.2 Multi-component analytes 

(e.g., PCBs as Aroclors, and Toxaphene) 

6.8.2.2.1 A standard containing a 

mixture of Aroclor 1016 and Aroclor 

1260 will include many of the peaks 

represented in the other Aroclor 

mixtures. As a result, a multi-point 

initial calibration employing a mixture 

of Aroclors 1016 and 1260 at three to 

five concentrations should be sufficient 

to demonstrate the linearity of the 

detector response without the necessity 

of performing multi-point initial 

calibrations for each of the seven 

Aroclors. In addition, such a mixture 

can be used as a standard to 

demonstrate that a sample does not 

contain peaks that represent any one of 

the Aroclors. This standard can also be 

used to determine the concentrations of 

either Aroclor 1016 or Aroclor 1260, 

should they be present in a sample. 

Therefore, prepare a minimum of 

three calibration standards containing 

equal concentrations of both Aroclor 

1016 and Aroclor 1260 by dilution of 

the stock standard with isooctane or 

hexane. The concentrations should 

correspond to the expected range of 

concentrations found in real samples 

and should bracket the linear range of 

the detector. 

6.8.2.2.2 Single standards of each of 

the other five Aroclors are required to 

aid the analyst in pattern recognition. 

Assuming that the Aroclor 1016/1260 

standards described in Section 6.8.2.2.1 

have been used to demonstrate the 

linearity of the detector, these single 

standards of the remaining five Aroclors 

also may be used to determine the 

calibration factor for each Aroclor. 

Prepare a standard for each of the other 

Aroclors. The concentrations should 

generally correspond to the mid-point of 

the linear range of the detector, but 

lower concentrations may be employed 

at the discretion of the analyst based on 

project requirements. 

6.8.2.2.3 For Toxaphene, prepare a 

minimum of three calibration standards 

containing Toxaphene by dilution of the 

stock standard with isooctane or 

hexane. The concentrations should 

correspond to the expected range of 

concentrations found in real samples 

and should bracket the linear range of 

the detector. 

6.8.3 Quality Control (QC) Check 

Sample—Also known as the Laboratory 

Control Sample (LCS). Prepare a midlevel standard mixture in acetone (or 

water miscible solvent) from a stock 

solution from the same source as the 

calibration standards. This standard will 

be used to generate extracts to evaluate 

the capability of the laboratory. 

6.8.4 Second Source Standard— 

Obtain standards from a second source 

(different manufacturer or different 

certified lot), and prepare a mid-level 

standard mixture in isooctane or 

hexane. This standard will be analyzed 

with the calibration curve to verify the 

accuracy of the calibration. 

6.8.5 Internal standard solution—If 

the internal standard calibration 

technique is to be used, prepare 

pentachloronitrobenzene (PCNB) at a 

concentration of 10 mg/mL in ethyl 

acetate. Alternative and multiple 

internal standards; e.g., tetrachloro-mxylene, 4,4′-dibromobiphenyl, and/or 

decachlorobiphenyl may be used 

provided that the laboratory performs 

all QC tests and meets all QC acceptance 

criteria with the alternate or additional 

internal standard(s) as an integral part of 

this method. 

6.8.6 Surrogate solution—Prepare a 

solution containing one or more 

surrogates at a concentration of 2 mg/mL 

in acetone. Potential surrogates include: 

Dibutyl chlorendate (DBC), tetrachlorom-xylene (TCMX), 4,4′- 

dibromobiphenyl, or 

decachlorobiphenyl provided that the 

laboratory performs all QC tests and 

meets all QC acceptance criteria with 

the alternative surrogate(s) as an integral 

part of this method. If the internal 

standard calibration technique is used, 

do not use the internal standard as a 

surrogate. 

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6.8.7 DDT and endrin 

decomposition (breakdown) solution— 

Prepare a solution containing endrin at 

a concentration of 1 mg/mL and 4,4′- 

DDT at a concentration of 2 mg/mL, in 

isooctane or hexane. 

6.8.8 Quality control check sample 

(laboratory control sample; LCS) 

concentrate—See Sections 8.2.1 and 8.4. 

6.8.9 Stability of solutions—Analyze 

all standard solutions (Sections 6.8.1 

through 6.8.8) within 48 hours of 

preparation. Replace purchased certified 

stock standard solutions per the 

expiration date. Replace stock standard 

solutions prepared by the laboratory or 

mixed with purchased solutions after 

one year, or sooner if comparison with 

QC check samples indicates a problem. 

7. Calibration 

7.1 Establish gas chromatographic 

operating conditions equivalent to those 

in Section 5.8.1 and Footnote 2 to Table 

3. Alternative temperature program and 

flow rate conditions may be used. The 

system may be calibrated using the 

external standard technique (Section 

7.5) or the internal standard technique 

(Section 7.6). It is necessary to calibrate 

the system for the analytes of interest 

(Section 1.4) only. 

7.2 Separately inject the mid-level 

calibration standard for each calibration 

mixture. Store the retention time on 

each GC column. 

7.3 Demonstrate that each column/

detector system meets the MDLs in 

Table 3 or demonstrates sufficient 

sensitivity for the intended application 

and passes the DDT/endrin 

decomposition test (Section 13.5). 

7.4 Injection of calibration 

solutions—Inject a constant volume in 

the range of 0.5 to 2.0 mL of each 

calibration solution into the GC column/ 

detector pairs. Beginning with the 

lowest level mixture and proceeding to 

the highest level mixture may limit the 

risk of carryover from one standard to 

the next, but other sequences may be 

used. A blank sample should be 

analyzed after the highest standard to 

demonstrate that there is no carry-over 

within the system for this calibration 

range. For each analyte, compute, 

record, and store, as a function of the 

concentration injected, the retention 

time and peak area on each column/

detector system. If multi-component 

analytes are to be analyzed, store the 

retention time and peak area for the 

three to five exclusive (unique large) 

peaks for each PCB or technical 

chlordane. Use four to six peaks for 

toxaphene. 

7.5 External standard calibration 

7.5.1 From the calibration data 

(Section 7.4), calculate the calibration 

factor (CF) for each analyte at each 

concentration according to the following 

equation: 

where: 

Cs = Concentration of the analyte in the 

standard (ng/mL) 

As = Peak height or area 

For multi-component analytes, choose 

a series of characteristic peaks for each 

analyte (3 to 5 for each Aroclor, 4 to 6 

for toxaphene) and calculate individual 

calibration factors for each peak. 

Alternatively, for toxaphene, sum the 

areas of all of the peaks in the standard 

chromatogram and use the summed area 

to determine the calibration factor. (If 

this alternative is used, the same 

approach must be used to quantitate the 

analyte in the samples.) 

7.5.2 Calculate the mean (average) 

and relative standard deviation (RSD) of 

the calibration factors. If the RSD is less 

than 20%, linearity through the origin 

can be assumed and the average CF can 

be used for calculations. Alternatively, 

the results can be used to fit a linear or 

quadratic regression of response ratios, 

As/Ais, vs. concentration ratios Cs/Cis. If 

used, the regression must be weighted 

inversely proportional to concentration. 

The coefficient of determination (R2) of 

the weighted regression must be greater 

than 0.99. Alternatively, the relative 

standard error (Reference 10) may be 

used as an acceptance criterion. As with 

the RSD, the RSE must be less than 

20%. If an RSE less than 20% cannot be 

achieved for a quadratic regression, 

system performance is unacceptable and 

the system must be adjusted and recalibrated. 

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: 

where: 

As = Response for the analyte to be measured. 

Ais = Response for the internal standard. 

Cis = Concentration of the internal standard 

(ng/mL) 

Cs = Concentration of the analyte to be 

measured (ng/mL). 

7.6.2 Calculate the mean (average) 

and relative standard deviation (RSD) of 

the response factors. If the RSD is less 

than 15%, linearity through the origin 

can be assumed and the average RF can 

be used for calculations. Alternatively, 

the results can be used to prepare a 

calibration curve of response ratios, As/ 

Ais, vs. concentration ratios, Cs/Cis, for 

the analyte. A minimum of six 

concentration levels is required for a 

non-linear (e.g., quadratic) regression. If 

used, the regression must be weighted 

inversely proportional to concentration, 

and the correlation coefficient of the 

weighted regression must be greater 

than 0.99. The relative standard error 

(Reference 11) may also be used as an 

acceptance criterion. As with the RSD, 

the RSE must be less than 15%. If an 

RSE less than 15% cannot be achieved 

for a quadratic regression, system 

performance is unacceptable and the 

system must be adjusted and recalibrated. 

7.7 Second source standard—After 

the calibration curves are analyzed, 

analyze a second source standard at the 

mid-level concentration. This standard 

confirms the accuracy of the calibration 

curve. The concentrations must be 

within 20% difference of the true value. 

If the observed concentration exceeds 

this criteria, a third source may be 

analyzed to determine which standard 

was not accurate, and subsequent 

corrective actions taken. 

7.8 The working calibration curve, 

CF, or RF must be verified at the 

beginning and end of each 24-hour shift 

by the analysis of a mid-level calibration 

standard or the combined QC standard 

(Section 6.8.2.1.3). Requirements for 

calibration verification are given in 

Section 13.6 and Table 4. Alternatively, 

calibration verification may be 

performed after a set number of 

injections (e.g., every 20 injections), to 

include injection of extracts of field 

samples, QC samples, instrument 

blanks, etc. (i.e., it is based on the 

number of injections performed, not 

sample extracts). 

Note: The 24-hour shift begins after 

analysis of the combined QC standard 

(calibration verification) and ends 24 hours 

later. The ending calibration verification 

standard is run immediately after the last 

sample run during the 24-hour shift, so the 

beginning and ending calibration 

verifications are outside of the 24-hour shift. 

If calibration verification is based on the 

number of injections instead of time, then the 

ending verification standard for one group of 

20 injections may be used as the beginning 


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verification for the next group of 20 

injections. 

7.9 Florisil® calibration—The 

column cleanup procedure in Section 

11.3 utilizes Florisil column 

chromatography. Florisil® from different 

batches or sources may vary in 

adsorptive capacity. To standardize the 

amount of Florisil® 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®. The amount of Florisil®

to be used for each column is calculated 

by dividing 110 by this ratio and 

multiplying by 20 g. If cartridges 

containing Florisil® are used, then this 

step is not necessary. 

8. Quality Control 

8.1 Each laboratory that uses this 

method is required to operate a formal 

quality assurance program. The 

minimum requirements of this program 

consist of an initial demonstration of 

laboratory capability and ongoing 

analysis of spiked samples and blanks to 

evaluate and document data quality. 

The laboratory must maintain records to 

document the quality of data generated. 

Ongoing data quality checks are 

compared with established performance 

criteria to determine if the results of 

analyses meet performance 

requirements of this method. A quality 

control check standard (LCS, Section 

8.4) must be prepared and analyzed 

with each batch of samples to confirm 

that the measurements were performed 

in an in-control mode of operation. A 

laboratory may develop its own 

performance criteria (as QC acceptance 

criteria), provided such criteria are as or 

more restrictive than the criteria in this 

method. 

8.1.1 The laboratory must make an 

initial demonstration of the capability 

(IDC) to generate acceptable precision 

and recovery with this method. This 

demonstration is detailed in Section 8.2. 

On a continuing basis, the laboratory 

should repeat demonstration of 

capability (DOC) annually. 

8.1.2 In recognition of advances that 

are occurring in analytical technology, 

and to overcome matrix interferences, 

the laboratory is permitted certain 

options (Section 1.8 and 40 CFR 

136.6(b) [Reference 12]) to improve 

separations or lower the costs of 

measurements. These options may 

include alternative extraction (e.g., other 

solid-phase extraction materials and 

formats), concentration, and cleanup 

procedures, and changes in GC columns 

(Reference 12). Alternative 

determinative techniques, such as the 

substitution of spectroscopic or 

immunoassay techniques, and changes 

that degrade method performance, are 

not allowed. If an analytical technique 

other than the techniques specified in 

this method is used, that technique 

must have a specificity equal to or 

greater than the specificity of the 

techniques in this method for the 

analytes of interest. The laboratory is 

also encouraged to participate in 

performance evaluation studies (see 

Section 8.8). 

8.1.2.1 Each time a modification 

listed above is made to this method, the 

laboratory is required to repeat the 

procedure in Section 8.2. If the 

detection limit of the method will be 

affected by the change, the laboratory is 

required to demonstrate that the MDLs 

(40 CFR part 136, appendix B) are lower 

than one-third the regulatory 

compliance limit or as low as the MDLs 

in this method, whichever are greater. If 

calibration will be affected by the 

change, the instrument must be 

recalibrated per Section 7. Once the 

modification is demonstrated to 

produce results equivalent or superior 

to results produced by this method as 

written, that modification may be used 

routinely thereafter, so long as the other 

requirements in this method are met 

(e.g., matrix spike/matrix spike 

duplicate recovery and relative percent 

difference). 

8.1.2.1.1 If an allowed method 

modification, is to be applied to a 

specific discharge, the laboratory must 

prepare and analyze matrix spike/matrix 

spike duplicate (MS/MSD) samples 

(Section 8.3) and LCS samples (Section 

8.4). The laboratory must include 

surrogates (Section 8.7) in each of the 

samples. The MS/MSD and LCS 

samples must be fortified with the 

analytes of interest (Section 1.4). If the 

modification is for nationwide use, MS/ 

MSD samples must be prepared from a 

minimum of nine different discharges 

(See Section 8.1.2.1.2), and all QC 

acceptance criteria in this method must 

be met. This evaluation only needs to be 

performed once other than for the 

routine QC required by this method (for 

example it could be performed by the 

vendor of an alternate material) but any 

laboratory using that specific material 

must have the results of the study 

available. This includes a full data 

package with the raw data that will 

allow an independent reviewer to verify 

each determination and calculation 

performed by the laboratory (see Section 

8.1.2.2.5, items a–q). 

8.1.2.1.2 Sample matrices on which 

MS/MSD tests must be performed for 

nationwide use of an allowed 

modification: 

(a) Effluent from a POTW 

(b) ASTM D5905 Standard 

Specification for Substitute Wastewater 

(c) Sewage sludge, if sewage sludge 

will be in the permit 

(d) ASTM D1141 Standard 

Specification for Substitute Ocean 

Water, if ocean water will be in the 

permit 

(e) Untreated and treated wastewaters 

up to a total of nine matrix types (see 

http://water.epa.gov/scitech/wastetech/

guide/industry.cfm) for a list of 

industrial categories with existing 

effluent guidelines). 

At least one of the above wastewater 

matrix types must have at least one of 

the following characteristics: 

(i) Total suspended solids greater than 

40 mg/L 

(ii) Total dissolved solids greater than 

100 mg/L 

(iii) Oil and grease greater than 20 mg/ 

L 

(iv) NaCl greater than 120 mg/L 

(v) CaCO3 greater than 140 mg/L 

The interim acceptance criteria for 

MS, MSD recoveries that do not have 

recovery limits specified in Table 5, and 

recoveries for surrogates that do not 

have recovery limits specified in Table 

8, must be no wider than 60–140%, and 

the relative percent difference (RPD) of 

the concentrations in the MS and MSD 

that do not have RPD limits specified in 

Table 5 must be less than 30%. 

Alternatively, the laboratory may use 

the laboratory’s in-house limits if they 

are tighter. 

(f) A proficiency testing (PT) sample 

from a recognized provider, in addition 

to tests of the nine matrices (Section 

8.1.2.1.1). 

8.1.2.2 The laboratory must 

maintain records of modifications made 

to this method. These records include 

the following, at a minimum: 

8.1.2.2.1 The names, titles, street 

addresses, telephone numbers, and 

email addresses of the analyst(s) that 

performed the analyses and 

modification, and of the quality control 

officer that witnessed and will verify the 

analyses and modifications. 

8.1.2.2.2 A list of analytes, by name 

and CAS Registry number. 

8.1.2.2.3 A narrative stating 

reason(s) for the modifications. 

8.1.2.2.4 Results from all quality 

control (QC) tests comparing the 

modified method to this method, 

including: 

(a) Calibration (Section 7). 

(b) Calibration verification (Section 

13.6). 

(c) Initial demonstration of capability 

(Section 8.2). 

(d) Analysis of blanks (Section 8.5). 

(e) Matrix spike/matrix spike 

duplicate analysis (Section 8.3). 

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(f) Laboratory control sample analysis 

(Section 8.4). 

8.1.2.2.5 Data that will allow an 

independent reviewer to validate each 

determination by tracing the instrument 

output (peak height, area, or other 

signal) to the final result. These data are 

to include: 

(a) Sample numbers and other 

identifiers. 

(b) Extraction dates. 

(c) Analysis dates and times. 

(d) Analysis sequence/run 

chronology. 

(e) Sample weight or volume (Section 

10). 

(f) Extract volume prior to each 

cleanup step (Sections 10 and 11). 

(g) Extract volume after each cleanup 

step (Section 11). 

(h) Final extract volume prior to 

injection (Sections 10 and 12). 

(i) Injection volume (Sections 12.3 

and 13.2). 

(j) Sample or extract dilution (Section 

15.4). 

(k) Instrument and operating 

conditions. 

(l) Column (dimensions, material, 

etc). 

(m) Operating conditions 

(temperatures, flow rates, etc). 

(n) Detector (type, operating 

conditions, etc). 

(o) Chromatograms and other 

recordings of raw data. 

(p) Quantitation reports, data system 

outputs, and other data to link the raw 

data to the results reported. 

(q) A written Standard Operating 

Procedure (SOP) 

8.1.2.2.6 Each individual laboratory 

wishing to use a given modification 

must perform the start-up tests in 

Section 8.1.2 (e.g., DOC, MDL), with the 

modification as an integral part of this 

method prior to applying the 

modification to specific discharges. 

Results of the DOC must meet the QC 

acceptance criteria in Table 5 for the 

analytes of interest (Section 1.4), and 

the MDLs must be equal to or lower 

than the MDLs in Table 3 for the 

analytes of interest. 

8.1.3 Before analyzing samples, the 

laboratory must analyze a blank to 

demonstrate that interferences from the 

analytical system, lab ware, and 

reagents, are under control. Each time a 

batch of samples is extracted or reagents 

are changed, a blank must be extracted 

and analyzed as a safeguard against 

laboratory contamination. Requirements 

for the blank are given in Section 8.5. 

8.1.4 The laboratory must, on an 

ongoing basis, spike and analyze a 

minimum of 5% of all samples in a 

batch (Section 22.2) or from a given site 

or discharge, in duplicate, to monitor 

and evaluate method and laboratory 

performance on the sample matrix. This 

procedure is described in Section 8.3. 

8.1.5 The laboratory must, on an 

ongoing basis, demonstrate through 

analysis of a quality control check 

sample (laboratory control sample, LCS; 

on-going precision and recovery sample, 

OPR) that the measurement system is in 

control. This procedure is described in 

Section 8.4. 

8.1.6 The laboratory should 

maintain performance records to 

document the quality of data that is 

generated. This procedure is given in 

Section 8.7. 

8.1.7 The large number of analytes 

tested in performance tests in this 

method present a substantial probability 

that one or more will fail acceptance 

criteria when all analytes are tested 

simultaneously, and a re-test 

(reanalysis) is allowed if this situation 

should occur. If, however, continued retesting results in further repeated 

failures, the laboratory should 

document the failures and either avoid 

reporting results for the analytes that 

failed or report the problem and failures 

with the data. A QC failure does not 

relieve a discharger or permittee of 

reporting timely results. 

8.2 Demonstration of capability 

(DOC)—To establish the ability to 

generate acceptable recovery and 

precision, the laboratory must perform 

the DOC in Sections 8.2.1 through 8.2.6 

for the analytes of interest initially and 

in an on-going manner at least annually. 

The laboratory must also establish 

MDLs for the analytes of interest using 

the MDL procedure at 40 CFR part 136, 

appendix B. The laboratory’s MDLs 

must be equal to or lower than those 

listed in Table 3 or lower than one-third 

the regulatory compliance limit, 

whichever is greater. For MDLs not 

listed in Tables 1 or 2, the laboratory 

must determine the MDLs using the 

MDL procedure at 40 CFR part 136, 

appendix B under the same conditions 

used to determine the MDLs for the 

analytes listed in Tables 1 and 2. All 

procedures used in the analysis, 

including cleanup procedures, must be 

included in the DOC. 

8.2.1 For the DOC, a QC check 

sample concentrate containing each 

analyte of interest (Section 1.4) is 

prepared in a water-miscible solvent 

using the solution in Section 6.8.3. The 

QC check sample concentrate must be 

prepared independently from those 

used for calibration, but should be from 

the same source and prepared in a 

water-miscible solvent. The concentrate 

should produce concentrations of the 

analytes of interest in water at or below 

the mid-point of the calibration range. 

Multiple solutions may be required. 

Note: QC check sample concentrates are no 

longer available from EPA. 

8.2.2 Using a pipet or syringe, 

prepare four QC check samples by 

adding an appropriate volume of the 

concentrate and of the surrogate(s) to 

each of four 1–L aliquots of reagent 

water. Swirl or stir to mix. 

8.2.3 Extract and analyze the wellmixed 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 

individuals 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 laboratory 

must, on an ongoing basis, spike at least 

5% of the samples in duplicate from 

each sample site being monitored to 

assess accuracy (recovery and 

precision). The data user should 

identify the sample and the analytes of 

interest (Section 1.4) to be spiked. If 

direction cannot be obtained, the 

laboratory must spike at least one 

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sample in duplicate per extraction batch 

of up to 20 samples (Section 22.2) with 

the analytes in Table 1. Spiked sample 

results should be reported only to the 

data user whose sample was spiked, or 

as requested or required by a regulatory/ 

control authority. 

8.3.1. If, as in compliance 

monitoring, the concentration of a 

specific analyte will be checked against 

a regulatory concentration limit, the 

concentration of the spike should be at 

that limit; otherwise, the concentration 

of the spike should be one to five times 

higher than the background 

concentration determined in Section 

8.3.2, at or near the midpoint of the 

calibration range, or at the concentration 

in the LCS (Section 8.4) whichever 

concentration would be larger. When no 

information is available, the mid-point 

of the calibration may be used, as long 

as it is the same or less than the 

regulatory limit. 

8.3.2 Analyze one sample aliquot to 

determine the background concentration 

(B) of the each analyte of interest. If 

necessary to meet the requirement in 

Section 8.3.1, prepare a new check 

sample concentrate (Section 8.2.1) 

appropriate for the background 

concentration. Spike and analyze two 

additional sample aliquots of the same 

volume as the original sample, and 

determine the concentrations after 

spiking (A1 and A2) of each analyte. 

Calculate the percent recoveries (P1 and 

P2) as: 

where T is the known true value of the 

spike. 

Also calculate the relative percent 

difference (RPD) between the 

concentrations (A1 and A2): 

8.3.3 Compare the percent 

recoveries (P1 and P2) and the RPD for 

each analyte in the MS/MSD aliquots 

with the corresponding QC acceptance 

criteria for recovery (P) and RPD in 

Table 4. 

If any individual P falls outside the 

designated range for recovery in either 

aliquot, or the RPD limit is exceeded, 

the result for the analyte in the 

unspiked sample is suspect and may not 

be reported or used for permitting or 

regulatory compliance. See Section 8.1.7 

for disposition of failures. 

For analytes in Table 2 not listed in 

Table 5, QC acceptance criteria must be 

developed by the laboratory. EPA has 

provided guidance for development of 

QC acceptance criteria (References 12 

and 13). 

8.3.4 After analysis of a minimum of 

20 MS/MSD samples for each target 

analyte and surrogate, the laboratory 

must calculate and apply in-house QC 

limits for recovery and RPD of future 

MS/MSD samples (Section 8.3). The QC 

limits for recovery are calculated as the 

mean observed recovery ±3 standard 

deviations, and the upper QC limit for 

RPD is calculated as the mean RPD plus 

3 standard deviations of the RPDs. The 

in-house QC limits must be updated at 

least every two years and re-established 

after any major change in the analytical 

instrumentation or process. At least 

80% of the analytes tested in the MS/ 

MSD must have in-house QC acceptance 

criteria that are tighter than those in 

Table 4. If an in-house QC limit for the 

RPD is greater than the limit in Table 4, 

then the limit in Table 4 must be used. 

Similarly, if an in-house lower limit for 

recovery is below the lower limit in 

Table 4, then the lower limit in Table 4 

must be used, and if an in-house upper 

limit for recovery is above the upper 

limit in Table 4, then the upper limit in 

Table 4 must be used. The laboratory 

must evaluate surrogate recovery data in 

each sample against its in-house 

surrogate recovery limits. The laboratory 

may use 60–140% as interim acceptance 

criteria for surrogate recoveries until inhouse limits are developed. 

8.4 Laboratory control sample 

(LCS)—A QC check sample (laboratory 

control sample, LCS; on-going precision 

and recovery sample, OPR) containing 

each single-component analyte of 

interest (Section 1.4) must be extracted, 

concentrated, and analyzed with each 

extraction batch of up to 20 samples 

(Section 3.1) to demonstrate acceptable 

recovery of the analytes of interest from 

a clean sample matrix. If multi-peak 

analytes are required, extract and 

prepare at least one as an LCS for each 

batch. Alternatively, the laboratory may 

set up a program where multi-peak LCS 

is rotated with a single-peak LCS. 

8.4.1 Prepare the LCS by adding QC 

check sample concentrate (Section 

8.2.1) to reagent water. Include all 

analytes of interest (Section 1.4) in the 

LCS. The volume of reagent water must 

be the same as the nominal volume used 

for the sample, the DOC (Section 8.2), 

the blank (Section 8.5), and the MS/

MSD (Section 8.3). Also add a volume 

of the surrogate solution (Section 6.8.6). 

8.4.2 Analyze the LCS prior to 

analysis of samples in the extraction 

batch (Section 3.1). Determine the 

concentration (A) of each analyte. 

Calculate the percent recovery as: 

where T is the true value of the 

concentration in the LCS. 

8.4.3 For each analyte, compare the 

percent recovery (P) with its 

corresponding QC acceptance criterion 

in Table 4. For analytes of interest in 

Table 2 not listed in Table 4, use the QC 

acceptance criteria developed for the 

MS/MSD (Section 8.3.3.2). If the 

recoveries for all analytes of interest fall 

within the designated ranges, analysis of 

blanks and field samples may proceed. 

If any individual recovery falls outside 

the range, proceed according to Section 

8.4.4. 

Note: The large number of analytes in 

Tables 1 and 2 present a substantial 

probability that one or more will fail the 

acceptance criteria when all analytes are 

tested simultaneously. Because a re-test is 

allowed in event of failure (Sections 8.1.7 

and 8.4.4), it may be prudent to extract and 

analyze two LCSs together and evaluate 

results of the second analysis against the QC 

acceptance criteria only if an analyte fails the 

first test. 

8.4.4 Repeat the test only for those 

analytes that failed to meet the 

acceptance criteria (P). If these analytes 

now pass, system performance is 

acceptable and analysis of blanks and 

samples may proceed. Repeated failure, 

however, will confirm a general 

problem with the measurement system. 

If this occurs, repeat the test using a 

fresh LCS (Section 8.2.1) or an LCS 

prepared with a fresh QC check sample 

concentrate (Section 8.2.1), or perform 

and document system repair. 

Subsequent to repair, repeat the LCS test 

(Section 8.4). See Section 8.1.7 for 

disposition of repeated failures. 

8.4.5 After analysis of 20 LCS 

samples, the laboratory must calculate 

and apply in-house QC limits for 

recovery to future LCS samples (Section 

8.4). Limits for recovery in the LCS are 

calculated as the mean recovery ±3 

standard deviations. A minimum of 

80% of the analytes tested for in the 

LCS must have QC acceptance criteria 

tighter than those in Table 4. As noted 

in Section 8.6, each laboratory must 

develop QC acceptance criteria for the 

surrogates they employ. The laboratory 

should use 60–140% as interim 

acceptance criteria for recoveries of 

spiked analytes and surrogates until inhouse LCS and surrogate limits are 

developed. If an in-house lower limit for 

LCS recovery is lower than the lower 

limit in Table 4, the lower limit in Table 

4 must be used, and if an in-house 

upper limit for recovery is higher than 

the upper limit in Table 4, the upper 

limit in Table 4 must be used. 


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8.5 Blank—Extract and analyze a 

blank with each extraction batch 

(Section 22.2) to demonstrate that the 

reagents and equipment used for 

preparation and analysis are free from 

contamination. 

8.5.1 Prepare the blank from reagent 

water and spike it with the surrogates. 

The volume of reagent water must be 

the same as the volume used for 

samples, the DOC (Section 8.2), the LCS 

(Section 8.4), and the MS/MSD (Section 

8.3). Extract, concentrate, and analyze 

the blank using the same procedures 

and reagents used for the samples, LCS, 

and MS/MSD in the batch. Analyze the 

blank immediately after analysis of the 

LCS (Section 8.4) and prior to analysis 

of the MS/MSD and samples to 

demonstrate freedom from 

contamination. 

8.5.2 If any analyte of interest is 

found in the blank at a concentration 

greater than the MDL for the analyte, at 

a concentration greater than one-third 

the regulatory compliance limit, or at a 

concentration greater than one-tenth the 

concentration in a sample in the batch 

(Section 3.1), whichever is greatest, 

analysis of samples must be halted and 

samples in the batch must be reextracted 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 retesting of blanks results in repeated 

failures, the laboratory should 

document the failures and report the 

problem and failures with the data. 

8.6 Surrogate recovery—As a quality 

control check, the laboratory must spike 

all samples with the surrogate standard 

spiking solution (Section 6.8.6) per 

Section 10.2.2 or 10.4.2, analyze the 

samples, and calculate the percent 

recovery of each surrogate. QC 

acceptance criteria for surrogates must 

be developed by the laboratory. EPA has 

provided guidance for development of 

QC acceptance criteria (References 12 

and 13). If any recovery fails its 

criterion, attempt to find and correct the 

cause of the failure, and if sufficient 

volume is available, re-extract another 

aliquot of the affected sample. Surrogate 

recoveries from the blank and LCS may 

be used as pass/fail criteria by the 

laboratory or as required by a regulatory 

authority, or may be used to diagnose 

problems with the analytical system. 

8.7 As part of the QC program for 

the laboratory, it is suggested but not 

required that method accuracy for 

wastewater samples be assessed and 

records maintained. After analysis of 

five or more spiked wastewater samples 

as in Section 8.4, calculate the average 

percent recovery (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). 

8.8 It is recommended that the 

laboratory adopt additional quality 

assurance practices for use with this 

method. The specific practices that are 

most productive depend upon the needs 

of the laboratory and the nature of the 

samples. Field duplicates may be 

analyzed to assess the precision of 

environmental measurements. When 

doubt exists over the identification of a 

peak on the chromatogram, 

confirmatory techniques such as gas 

chromatography with another dissimilar 

column, specific element detector, or 

mass spectrometer must be used. 

Whenever possible, the laboratory 

should analyze standard reference 

materials and participate in relevant 

performance evaluation studies. 

9. Sample Collection, Preservation, and 

Handling 

9.1 Collect samples as grab samples 

in glass bottles, or in refrigerated bottles 

using automatic sampling equipment. 

Collect 1–L of ambient waters, effluents, 

and other aqueous samples. If high 

concentrations of the analytes of interest 

are expected (e.g., for untreated 

effluents or in-process waters), collect a 

smaller volume (e.g., 250 mL), but not 

less than 100 mL, in addition to the 1– 

L sample. Follow conventional 

sampling practices, except do not prerinse 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 °C from the time of collection until 

extraction, but do not freeze. If aldrin is 

to be determined and residual chlorine 

is present, add 80 mg/L of sodium 

thiosulfate but do not add excess. Any 

method suitable for field use may be 

employed to test for residual chlorine 

(Reference 14). If sodium thiosulfate 

interferes in the determination of the 

analytes, an alternative preservative 

(e.g., ascorbic acid or sodium sulfite) 

may be used. 

9.3 Extract all samples within seven 

days of collection and completely 

analyze within 40 days of extraction 

(Reference 1). If the sample will not be 

extracted within 72 hours of collection, 

adjust the sample pH to range of 5.0–9.0 

with sodium hydroxide solution or 

sulfuric acid. Record the volume of acid 

or base used. 

10. Sample Extraction 

10.1 This section contains 

procedures for separatory funnel liquidliquid extraction (SFLLE, Section 10.2), 

continuous liquid-liquid extraction 

(CLLE, Section 10.4), and disk-based 

solid-phase extraction (SPE, Section 

10.5). SFLLE is faster, but may not be as 

effective as CLLE for extracting polar 

analytes. SFLLE is labor intensive and 

may result in formation of emulsions 

that are difficult to break. CLLE is less 

labor intensive, avoids emulsion 

formation, but requires more time (18– 

24 hours), more hood space, and may 

require more solvent. SPE can be faster, 

unless the particulate load in an 

aqueous sample is so high that it slows 

the filtration process. If an alternative 

extraction scheme to those detailed in 

this method is used, all QC tests must 

be performed and all QC acceptance 

criteria must be met with that extraction 

scheme as an integral part of this 

method. 

10.2 Separatory funnel liquid-liquid 

extraction (SFLLE). 

10.2.1 The SFLLE procedure below 

assumes a sample volume of 1 L. When 

a different sample volume is extracted, 

adjust the volume of methylene chloride 

accordingly. 

10.2.2 Mark the water meniscus on 

the side of the sample bottle for later 

determination of sample volume. Pour 

the entire sample into the separatory 

funnel. Pipet the surrogate standard 

spiking solution (Section 6.8.6) into the 

separatory funnel. If the sample will be 

used for the LCS or MS or MSD, pipet 

the appropriate QC check sample 

concentrate (Section 8.2.1) into the 

separatory funnel. Mix well. If the 

sample arrives in a larger sample bottle, 

1 L may be measured in a graduated 

cylinder, then added to the separatory 

funnel. 

Note: Instances in which the sample is 

collected in an oversized bottle should be 

reported by the laboratory to the data user. 

Of particular concern is that fact that this 

practice precludes rinsing the empty bottle 

with solvent as described below, which 

could leave hydrophobic pesticides on the 

wall of the bottle, and underestimate the 

actual sample concentrations. 

10.2.3 Add 60 mL of methylene 

chloride to the sample bottle, seal, and 

shake for 30 seconds to rinse the inner 

surface. Transfer the solvent to the 

separatory funnel and extract the 

sample by shaking the funnel for two 

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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 onethird the volume of the solvent layer, 

employ mechanical techniques to 

complete the phase separation. The 

optimum technique depends upon the 

sample, but may include stirring, 

filtration of the emulsion through glass 

wool, centrifugation, freezing, or other 

physical methods. Collect the 

methylene chloride extract in a flask. If 

the emulsion cannot be broken 

(recovery of less than 80% of the 

methylene chloride, corrected for the 

water solubility of methylene chloride), 

transfer the sample, solvent, and 

emulsion into the extraction chamber of 

a continuous extractor and proceed as 

described in Section 10.4. 

10.2.4 Add a second 60-mL volume 

of methylene chloride to the sample 

bottle and repeat the extraction 

procedure a second time, combining the 

extracts in the flask. Perform a third 

extraction in the same manner. Proceed 

to macro-concentration (Section 10.3.1). 

10.2.5 Determine the original sample 

volume by refilling the sample bottle to 

the mark and transferring the liquid to 

an appropriately sized graduated 

cylinder. Record the sample volume to 

the nearest 5 mL. Sample volumes may 

also be determined by weighing the 

container before and after extraction or 

filling to the mark with water. 

10.3 Concentration. 

10.3.1 Macro concentration. 

10.3.1.1 Assemble a Kuderna-Danish 

(K–D) concentrator by attaching a 10-mL 

concentrator tube to a 500-mL 

evaporative flask. Other concentration 

devices or techniques may be used in 

place of the K–D concentrator so long as 

the requirements of Section 8.2 are met. 

10.3.1.2 Pour the extract through a 

solvent-rinsed drying column 

containing about 10 cm of anhydrous 

sodium sulfate, and collect the extract 

in the K–D concentrator. Rinse the flask 

and column with 20–30 mL of 

methylene chloride to complete the 

quantitative transfer. 

10.3.1.3 If no cleanup is to be 

performed on the sample, add 500 mL 

(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 °C) 

so that the concentrator tube is partially 

immersed in the hot water, and the 

entire lower rounded surface of the flask 

is bathed with hot vapor. Adjust the 

vertical position of the apparatus and 

the water temperature as required to 

complete the concentration in 15–20 

minutes. At the proper rate of 

evaporation the balls of the column will 

actively chatter but the chambers will 

not flood with condensed solvent. When 

the apparent volume of liquid reaches 1 

mL or other determined amount, remove 

the K–D apparatus from the water bath 

and allow it to drain and cool for at least 

10 minutes. 

10.3.1.5 If the extract is to be 

cleaned up by a procedure for sulfur 

removal, remove the Snyder column 

and rinse the flask and its lower joint 

into the concentrator tube with 1 to 2 

mL of methylene chloride. A 5-mL 

syringe is recommended for this 

operation. Adjust the final volume to 10 

mL in methylene chloride and proceed 

to sulfur removal (Section 11.5). If the 

extract is to cleaned up using one of the 

other cleanup procedures or is to be 

injected into the GC, proceed to 

Kuderna-Danish micro-concentration 

(Section 10.3.2) or nitrogen evaporation 

and solvent exchange (Section 10.3.3). 

10.3.2 Kuderna-Danish micro 

concentration. 

10.3.2.1 Add another one or two 

clean boiling chips to the concentrator 

tube and attach a two-ball micro-Snyder 

column. Pre-wet the Snyder column by 

adding about 0.5 mL of methylene 

chloride to the top. Place the K–D 

apparatus on a hot water bath (60–65 °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® 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 °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 mL, 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 mL. 

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®, 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 fluoropolymerlined cap. Seal the vial and label with 

the sample number. Store in the dark at 

room temperature until ready for GC 

analysis. If GC analysis will not be 

performed on the same day, store the 

vial in the dark at 4 °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 

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of methylene chloride and add the 

rinses to the extractor. 

10.4.4 Add a suitable volume of 

methylene chloride to the distilling 

flask (generally 200–500 mL) and 

sufficient reagent water to ensure proper 

operation of the extractor, and extract 

the sample for 18–24 hours. A shorter or 

longer extraction time may be used if all 

QC acceptance criteria are met. Test 

and, if necessary, adjust the pH of the 

water during the second or third hour of 

the extraction. After extraction, allow 

the apparatus to cool, then detach the 

distilling flask. Dry, concentrate, solvent 

exchange, and transfer the extract to a 

vial with fluoropolymer-lined cap, per 

Section 10.3. 

10.4.5 Determine the original sample 

volume by refilling the sample bottle to 

the mark and transferring the liquid to 

an appropriately sized graduated 

cylinder. Record the sample volume to 

the nearest 5 mL. Sample volumes may 

also be determined by weighing the 

container before and after extraction or 

filling to the mark with water. 

10.5 Solid-phase extraction of 

aqueous samples. 

The steps in this section address the 

extraction of aqueous field samples 

using disk-based solid-phase extraction 

(SPE) media, based on an ATP approved 

by EPA in 1995 (Reference 20). This 

application of SPE is distinct from that 

used in this method for the cleanup of 

sample extracts in Section 11.2. 

Analysts must be careful not to confuse 

the equipment, supplies, or the 

procedural steps from these two 

different uses of SPE. 

Note: Changes to the extraction conditions 

described below may be made by the 

laboratory under the allowance for method 

flexibility described in Section 8.1, provided 

that the performance requirements in Section 

8.2 are met. However, changes in SPE 

materials, formats, and solvents must meet 

the requirements in Section 8.1.2 and its 

subsections. 

10.5.1 Mark the water meniscus on 

the side of the sample bottle for later 

determination of sample volume. If the 

sample contains particulates, let stand 

to settle out the particulates before 

extraction. 

10.5.2 Extract the sample as follows: 

10.5.2.1 Place a 90-mm standard 

filter apparatus on a vacuum filtration 

flask or manifold and attach to a 

vacuum source. The vacuum gauge 

should read at least 25 in. of mercury 

when all valves are closed. Position a 

90-mm C18 extraction disk onto the 

filter screen. Wet the entire disk with 

methanol. To aid in filtering samples 

with particulates, a 1-mm glass fiber 

filter or Empore® Filter Aid 400 can be 

placed on the top of the disk and wetted 

with methanol. Install the reservoir and 

clamp. Resume vacuum to dry the disk. 

Interrupt the vacuum. Wash the disk 

and reservoir with 20 mL of methylene 

chloride. Resume the vacuum briefly to 

pull methylene chloride through the 

disk. Interrupt the vacuum and allow 

the disk to soak for about a minute. 

Resume vacuum and completely dry the 

disk. 

10.5.2.2 Condition the disk with 20 

mL of methanol. Apply vacuum until 

nearly all the solvent has passed 

through the disk, interrupting it while 

solvent remains on the disk. Allow the 

disk to soak for about a minute. Resume 

vacuum to pull most of the methanol 

through, but interrupting it to leave a 

layer of methanol on the surface of the 

disk. Do not allow disk to dry. 

For uniform flow and good recovery, 

it is critical the disk not be allowed to 

dry from now until the end of the 

extraction. Discard waste solvent. Rinse 

the disk with 20 mL of deionized water. 

Resume vacuum to pull most of the 

water through, but interrupt it to leave 

a layer of water on the surface of the 

disk. Do not allow the disk to dry. If 

disk does dry, recondition with 

methanol as above. 

10.5.2.3 Add the water sample to the 

reservoir and immediately apply the 

vacuum. If particulates have settled in 

the sample, gently decant the clear layer 

into the apparatus until most of the 

sample has been processed. Then pour 

the remainder including the particulates 

into the reservoir. Empty the sample 

bottle completely. When the filtration is 

complete, dry the disk for three 

minutes. Turn off the vacuum. 

10.5.3 Discard sample filtrate. Insert 

tube to collect the eluant. The tube 

should fit around the drip tip of the 

base. Reassemble the apparatus. Add 5.0 

mL of acetone to the center of the disk, 

allowing it to spread evenly over the 

disk. Turn the vacuum on and quickly 

off when the filter surface nears dryness 

but still remains wet. Allow to soak for 

15 seconds. Add 20 mL of methylene 

chloride to the sample bottle, seal and 

shake to rinse the inside of the bottle. 

Transfer the methylene chloride from 

the bottle to the filter. Resume the 

vacuum slowly so as to avoid splashing. 

Interrupt the vacuum when the filter 

surface nears dryness but still remains 

wet. Allow disk to soak in solvent for 20 

seconds. Rinse the reservoir glass and 

disk with 10 mL of methylene chloride. 

Resume vacuum slowly. Interrupt 

vacuum when disk is covered with 

solvent. Allow to soak for 20 seconds. 

Resume vacuum to dry the disk. 

Remove the sample tube. 

10.5.4 Dry, concentrate, solvent 

exchange, and transfer the extract to a 

vial with fluoropolymer-lined cap, per 

Section 10.3. 

10.5.5 Determine the original sample 

volume by refilling the sample bottle to 

the mark and transferring the liquid to 

an appropriately sized graduated 

cylinder. Record the sample volume to 

the nearest 5 mL. Sample volumes may 

also be determined by weighing the 

container before and after extraction or 

filling to the mark with water. 

11. Extract Cleanup 

11.1 Cleanup may not be necessary 

for a relatively clean sample matrix. If 

particular circumstances require the use 

of a cleanup procedure, the laboratory 

may use any or all of the procedures 

below or any other appropriate 

procedure (e.g., gel permeation 

chromatography). However, the 

laboratory must first repeat the tests in 

Sections 8.2, 8.3, and 8.4 to demonstrate 

that the requirements of those sections 

can be met using the cleanup 

procedure(s) as an integral part of this 

method. This is particularly important 

when the target analytes for the analysis 

include any of the single component 

pesticides in Table 2, because some 

cleanups have not been optimized for 

all of those analytes. 

11.1.1 The solid-phase cartridge 

(Section 11.2) removes polar organic 

compounds such as phenols. 

11.1.2 The Florisil® column (Section 

11.3) allows for selected fractionation of 

the organochlorine analytes and will 

also eliminate polar interferences. 

11.1.3 Alumina column cleanup 

(Section 11.4) also removes polar 

materials. 

11.1.4 Elemental sulfur, which 

interferes with the electron capture gas 

chromatography of some of the 

pesticides, may be removed using 

activated copper, or TBA sulfite. Sulfur 

removal (Section 11.5) is required when 

sulfur is known or suspected to be 

present. Some chlorinated pesticides 

which also contain sulfur may be 

removed by this cleanup. 

11.2 Solid-phase extraction (SPE) as 

a cleanup. 

In order to use the C18 SPE cartridge 

in Section 5.5.3.5 as a cleanup 

procedure, the sample extract must be 

exchanged from methylene chloride to 

methylene chloride: acetonitrile:hexane. 

Follow the solvent exchange steps in 

Section 10.3.3.2 prior to attempting 

solid-phase cleanup. 

Note: This application of SPE is distinct 

from that used in this method for the 

extraction of aqueous samples in Section 

10.5. Analysts must be careful not to confuse 

the equipment, supplies, or procedural steps 

from these two different uses of SPE. 

11.2.1 Setup. 

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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®. 

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®

cleanup. 

Note: Alternative formats for this cleanup 

may be used by the laboratory, including 

cartridges containing Florisil®. 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 precleaned glass wool in the column 

(Section 5.2.4) to retain the Florisil®. 

Place the mass of Florisil® (nominally 

20 g) predetermined by calibration 

(Section 7.9 and Table 6) in a 

chromatographic column. Tap the 

column to settle the Florisil® 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®. 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 °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 precleaned 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® column cleanup. If 

Florisil® cleanup is not used, or to 

remove sulfur from any of the Florisil®

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 

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the copper does not remain bright, add 

more and swirl occasionally for another 

30–60 minutes. 

11.5.1.4 After drying and sulfur 

removal, quantitatively transfer the 

extract to a nitrogen-evaporation vial or 

tube and proceed to Section 10.3.3 for 

nitrogen evaporation and solvent 

exchange, taking care to leave the 

sodium sulfate and copper foil in the 

flask. 

11.5.2 Removal with TBA sulfite. 

11.5.2.1 Using small volumes of 

hexane, quantitatively transfer the 

extract to a 40- to 50-mL centrifuge tube 

with fluoropolymer-lined screw cap. 

11.5.2.2 Add 1–2 mL of TBA sulfite 

reagent (Section 6.7.4.2.4), 2–3 mL of 2- 

propanol, and approximately 0.7 g of 

sodium sulfite (Section 6.7.4.2.2) 

crystals to the tube. Cap and shake for 

1–2 minutes. If the sample is colorless 

or if the initial color is unchanged, and 

if clear crystals (precipitated sodium 

sulfite) are observed, sufficient sodium 

sulfite is present. If the precipitated 

sodium sulfite disappears, add more 

crystalline sodium sulfite in 

approximately 0.5-g portions until a 

solid residue remains after repeated 

shaking. 

11.5.2.3 Add 5–10 mL of reagent 

water and shake for 1–2 minutes. 

Centrifuge to settle the solids. 

11.5.2.4 Quantitatively transfer the 

hexane (top) layer through a small 

funnel containing a few grams of 

granular anhydrous sodium sulfate to a 

nitrogen-evaporation vial or tube and 

proceed to Section 10.3.3 for microconcentration 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 mL of 10 mg/mL internal standard 

solution into the extract, assuming no 

dilutions. Mix thoroughly. 

12.3 Simultaneously inject an 

appropriate volume of the sample 

extract or standard solution onto both 

columns, using split, splitless, solvent 

purge, large-volume, or on-column 

injection. Alternatively, if using a 

single-column GC configuration, inject 

an appropriate volume of the sample 

extract or standard solution onto each 

GC column independently. If the sample 

is injected manually, the solvent-flush 

technique should be used. The injection 

volume depends upon the technique 

used and the sensitivity needed to meet 

MDLs or reporting limits for regulatory 

compliance. Injected volumes must be 

the same for all standards and sample 

extracts. Record the volume injected to 

the nearest 0.05 mL. 

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 °C, protected from light, in screw-cap 

vials equipped with un-pierced 

fluoropolymer-lined septa. 

13. System and Laboratory Performance 

13.1 At the beginning of each shift 

during which standards or extracts are 

analyzed, GC system performance and 

calibration must be verified for all 

analytes and surrogates on both column/ 

detector systems. Adjustment and/or 

recalibration (per Section 7) are 

performed until all performance criteria 

are met. Only after all performance 

criteria are met may samples, blanks 

and other QC samples, and standards be 

analyzed. 

13.2 Inject an aliquot of the 

combined QC standard (Section 6.8.4) 

on both columns. Inject an aliquot of 

each of the multi-component standards. 

13.3 Retention times—The absolute 

retention times of the peak maxima 

shall be within ±2 seconds of the 

retention times in the calibration 

verification (Section 7.8). 

13.4 GC resolution—Resolution is 

acceptable if the valley height between 

two peaks (as measured from the 

baseline) is less than 40% of the shorter 

of the two peaks. 

13.4.1 DB–608 column—DDT and 

endrin aldehyde. 

13.4.2 DB–1701 column—alpha and 

gamma chlordane. 

Note: If using other GC columns or 

stationary phases, these resolution criteria 

apply to these four target analytes and any 

other closely eluting analytes on those other 

GC columns. 

13.5 Decomposition of DDT and 

endrin—If DDT, endrin, or their 

breakdown products are to be 

determined, this test must be performed 

prior to calibration verification (Section 

13.6). DDT decomposes to DDE and 

DDD. Endrin decomposes to endrin 

aldehyde and endrin ketone. 

13.5.1 Inject 1 mL of the DDT and 

endrin decomposition solution (Section 

6.9.5). 

13.5.2 Measure the areas of the 

peaks for DDT, DDE, DDD, Endrin, 

Endrin aldehyde, and Endrin ketone in 

the chromatogram and calculate the 

percent breakdown as shown in the 

equations below: 

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 


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specification (the widest range). For 

analytes in Table 2 not listed in Table 

4, QC acceptance criteria must be 

developed by the laboratory. EPA has 

provided guidance for development of 

QC acceptance criteria (References 13 

and 14). If the recoveries for all analytes 

meet the acceptance criteria, system 

performance is acceptable and analysis 

of blanks and samples may continue. If, 

however, any recovery falls outside the 

calibration verification range, system 

performance is unacceptable for that 

analyte. If this occurs, repair the system 

and repeat the test (Section 13.6), or 

prepare a fresh calibration standard and 

repeat the test, or recalibrate (Section 7). 

See Section 8.1.7 for information on 

repeated test failures. 

13.7 Laboratory control sample. 

13.7.1 Analyze the extract of the 

combined QC standard (a.k.a. LCS) 

(Section 6.8.3) extracted with each 

sample batch (Section 8.4). 

13.7.2 Compute the percent recovery 

of each analyte and of the coeluting 

analytes. 

13.7.3 For each analyte or coeluting 

analytes, compare the percent recovery 

with the limits for ‘‘P’’ in Table 4. For 

coeluting analytes, use the coeluting 

analyte with the least restrictive 

specification (widest range). If all 

analytes pass, the extraction, 

concentration, and cleanup processes 

are in control and analysis of blanks and 

samples may proceed. If, however, any 

of the analytes fail, these processes are 

not in control. In this event, correct the 

problem, re-extract the sample batch, 

and repeat the ongoing precision and 

recovery test. 

13.7.4 It is suggested, but not 

required, that the laboratory update 

statements of data quality. Add results 

that pass the specifications in Section 

13.7.3 to initial (Section 8.7) and 

previous ongoing data. Update QC 

charts to form a graphic representation 

of continued laboratory performance. 

Develop a statement of laboratory data 

quality for each analyte by calculating 

the average percent recovery (R) and the 

standard deviation of percent recovery, 

sr. Express the accuracy as a recovery 

interval from R¥2sr to R + 2sr. For 

example, if R = 95% and sr = 5%, the 

accuracy is 85 to 105%. 

13.8 Internal standard response—If 

internal standard calibration is used, 

verify that detector sensitivity has not 

changed by comparing the response 

(area or height) of each internal standard 

in the sample, blank, LCS, MS, and 

MSD to the response in the combined 

QC standard (Section 6.8.3). The peak 

area or height of the internal standard 

should be within 50% to 200% (1⁄2 to 

2×) of its respective peak area or height 

in the verification standard. If the area 

or height is not within this range, 

compute the concentration of the 

analytes using the external standard 

method (Section 7.5). 

14. Qualitative Identification 

14.1 Identification is accomplished 

by comparison of data from analysis of 

a sample, blank, or other QC sample 

with data from calibration verification 

(Section 7.7.1 or 13.5), and with data 

stored in the retention-time and 

calibration libraries (Section 7.7). The 

retention time window is determined as 

described in Section 14.2. Identification 

is confirmed when retention time agrees 

on both GC columns, as described 

below. 

14.2 Establishing retention time 

windows. 

14.2.1 Using the data from the multipoint initial calibration (Section 7.4), 

determine the retention time in decimal 

minutes (not minutes:seconds) of each 

peak representing a single-component 

target analyte on each column/detector 

system. For the multi-component 

analytes, use the retention times of the 

five largest peaks in the chromatograms 

on each column/detector system. 

14.2.2 Calculate the standard 

deviation of the retention times for each 

single-component analyte on each 

column/detector system and for the 

three to five exclusive (unique large) 

peaks for each multi-component 

analyte. 

14.2.3 Define the width of the 

retention time window as three times 

that standard deviation. Establish the 

center of the retention time window for 

each analyte by using the absolute 

retention time for each analyte from the 

calibration verification standard at the 

beginning of the analytical shift. For 

samples run during the same shift as an 

initial calibration, use the retention time 

of the mid-point standard of the initial 

calibration. If the calculated RT window 

is less than 0.02 minutes, then use 0.02 

minutes as the window. 

Note: Procedures for establishing retention 

time windows from other sources may be 

employed provided that they are clearly 

documented and provide acceptable 

performance. Such performance may be 

evaluated using the results for the spiked QC 

samples described in this method, such as 

laboratory control samples and matrix spike 

samples. 

14.2.4 New retention time windows 

must be established when a new GC 

column is installed or if a GC column 

has been shortened during maintenance 

to a degree that the retention times of 

analytes in the calibration verification 

standard have shifted close to the lower 

limits of the established retention time 

windows. 

14.2.5 RT windows should be 

checked periodically by examining the 

peaks in spiked samples such as the 

LCS or MS/MSD to confirm that peaks 

for known analytes are properly 

identified. 

14.2.6 If the retention time of an 

analyte in the initial calibration data has 

been evaluated as described in Section 

7.4.1 and it varied by more than 5 

seconds across the calibration range as 

a function of the concentration of the 

standard (see Section 7.4.2), then using 

the standard deviation of the retention 

times to set the width of the retention 

time window may not adequately serve 

to identify the analyte in question under 

routine conditions. In such cases, data 

from additional analyses of standards 

may be required to adequately model 

the chromatographic behavior of the 

analyte. 

14.3 Identifying the analyte in a 

sample. 

14.3.1 In order to identify a singlecomponent analyte from analysis of a 

sample, blank, or other QC sample, the 

peak representing the analyst must fall 

within its respective retention time 

windows on both column/detector 

systems (as defined in Section 14.2). 

That identification is further supported 

by the comparison of the numerical 

results on both columns, as described in 

Section 15.7. 

14.3.2 In order to identify a multicomponent analyte, pattern matching 

(fingerprinting) may be used, or the 

three to five exclusive (unique, baseline 

resolved, and largest) peaks for that 

analyte must fall within their respective 

retention time windows on both 

column/detector systems (as defined in 

Section 14.2). That identification is 

further supported by the comparison of 

the numerical results on both columns, 

as described in Section 15.7. 

14.4 GC/MS confirmation. 

When the concentration of an analyte 

is sufficient, or if the presence or 

identity is suspect, its presence should 

be confirmed by GC/MS. In order to 

match the sensitivity of the GC/ECD, 

confirmation will have to be by SIM– 

GC/MS, or estimated the concentration 

would have to be 100 times higher than 

the GC/ECD calibration range. 

14.5 Additional information that 

may aid the laboratory in the 

identification of an analyte. 

The occurrence of peaks eluting near 

the retention time of an analyte of 

interest increases the probability of a 

false positive for the analyte. If the 

concentration is insufficient for 

confirmation by GC/MS, the laboratory 

may use the cleanup procedures in this 

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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: 

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: 

where: 

Cex = Concentration of the analyte in the 

extract (ng/mL) 

As = Peak height or area for the analyte in 

the standard or sample 

Cis = Concentration of the internal standard 

(ng/mL) 

Ais = Area of the internal standard 

RF = Response factor, as defined in Section 

7.6.1 

15.3 Calculate the concentration of 

the analyte in the sample using the 

concentration in the extract, the extract 

volume, the sample volume, and the 

dilution factor, per the following 

equation: 

where: 

Cs = Concentration of the analyte in the 

sample (mg/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 mg/ 

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 multicomponent analytes 

15.5.1 PCBs as Aroclors 

Quantify an Aroclor by comparing the 

sample chromatogram to that of the 

most similar Aroclor standard as 

indicated in Section 14.3.2. Compare 

the responses of 3 to 5 major peaks in 

the calibration standard for that Aroclor 

with the peaks observed in the sample 

extract. The amount of Aroclor is 

calculated using the individual 

calibration factor for each of the 3 to 5 

characteristic peaks chosen in Sec. 

7.5.1. Determine the concentration of 

each of the characteristic peaks, using 

the average calibration factor calculated 

for that peak in Sec. 7.5.2, and then 

those 3 to 5 concentrations are averaged 

to determine the concentration of that 

Aroclor. 

15.5.2 Other multi-component 

analytes 

Quantify any other multi-component 

analytes (technical chlordane or 

toxaphene) using the same peaks used 

to develop the average calibration 

factors in Section 7.5.2. Determine the 

concentration of each of the 

characteristic peaks, and then the 

concentrations represented by those 

characteristic peaks are averaged to 

determine the concentration of the 

analyte. Alternatively, for toxaphene, 

the analyst may determine the 

calibration factor in Section 7.5.2 by 

summing the areas of all of the peaks for 

the analyte and using the summed of the 

peak areas in the sample chromatogram 

to determine the concentration. 

However, the approach used for 

toxaphene must be the same for the 

calibration and the sample analyses. 

15.6 Reporting of results. 

As noted in Section 1.6.1, EPA has 

promulgated this method at 40 CFR part 

136 for use in wastewater compliance 

monitoring under the National Pollutant 

Discharge Elimination System (NPDES). 

The data reporting practices described 

here are focused on such monitoring 

needs and may not be relevant to other 

uses of the method. 

15.6.1 Report results for wastewater 

samples in mg/L without correction for 

recovery. (Other units may be used if 

required by in a permit.) Report all QC 

data with the sample results. 

15.6.2 Reporting level. 

Unless otherwise specified in by a 

regulatory authority or in a discharge 

permit, results for analytes that meet the 

identification criteria are reported down 

to the concentration of the ML 

established by the laboratory through 

calibration of the instrument (see 

Section 7.5 or 7.6 and the glossary for 

the derivation of the ML). EPA 

considers the terms ‘‘reporting limit,’’ 

‘‘quantitation limit,’’ and ‘‘minimum 

level’’ to be synonymous. 

15.6.2.1 Report the lower result from 

the two columns (see Section 15.7 

below) for each analyte in each sample, 

blank, or standard at or above the ML 

to 3 significant figures. Report a result 

for each analyte found in each sample 

below the ML as ‘‘ML,’’ or as required 

by the regulatory authority or permit. 

Results are reported without blank 

subtraction unless requested or required 

by a regulatory authority or in a permit. 

In this case, both the sample result and 

the blank results must be reported 

together. 

15.6.2.2 In addition to reporting 

results for samples and blank(s) 

separately, the concentration of each 

analyte in a blank or field blank 

associated with that sample may be 

subtracted from the result for that 

sample, but only if requested or 

required by a regulatory authority or in 

a permit. In this case, both the sample 

result and the blank results must be 

reported together. 

15.6.2.3 Report the result for an 

analyte in a sample or extract that has 

been diluted at the least dilute level at 

which the peak area is within the 

calibration range (i.e., above the ML for 

the analyte) and the MS/MSD recovery 

and RPD are within their respective QC 

acceptance criteria (Table 4). This may 


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require reporting results for some 

analytes from different analyses. 

The results for each analyte in the 

MS/MSD samples should be reported 

from the same GC column as used to 

report the results for that analyte in the 

unspiked sample. If the MS/MSD 

recoveries and RPDs calculated in this 

manner do not meet the acceptance 

criteria in Table 4, then the analyst may 

use the results from the other GC 

column to determine if the MS/MSD 

results meet the acceptance criteria. If 

such a situation occurs, the results for 

the sample should be recalculated using 

the same GC column data as used for the 

MS/MSD samples, and reported with 

appropriate annotations that alert the 

data user of the issue. 

15.6.2.4 Results from tests 

performed with an analytical system 

that is not in control (i.e., that does not 

meet acceptance criteria for all of QC 

tests in this method) must not be 

reported or otherwise used for 

permitting or regulatory compliance 

purposes, but do not relieve a discharger 

or permittee of reporting timely results. 

If the holding time would be exceeded 

for a re-analysis of the sample, the 

regulatory/control authority should be 

consulted for disposition. 

15.6.3 Analyze the sample by GC/

MS or on a third column when analytes 

have co-eluted or interfere with 

determination on both columns. 

Note: Dichlone and kepone do not elute 

from the DB–1701 column and must be 

confirmed on a DB–5 column, or by GC/MS. 

15.7 Quantitative information that 

may aid in the confirmation of the 

presence of an analyte 

15.7.1 As noted in Section 14.3, the 

relative agreement between the 

numerical results from the two GC 

columns may be used to support the 

identification of the target analyte by 

providing evidence that that co-eluting 

interferences are not present at the 

retention time of the target analyte. 

Calculate the percent difference (%D) 

between the results for the analyte from 

both columns, as follows: 

In general, if the %D of the two 

results is less than 50% (e.g., a factor of 

2), then the pesticide is present. This 

%D is generous and allows for the 

pesticide that has the largest 

measurement error. 

Note: Laboratories may employ metrics less 

than 50% for this comparison, including 

those specified in other analytical methods 

for these pesticides (e.g., CLP or SW–846). 

15.7.2 If the amounts do not agree, 

and the RT data indicate the presence of 

the analyte (per Section 14), it is likely 

that a positive interference is present on 

the column that yielded the higher 

result. That interferent may be 

represented by a separate peak on the 

other column that does not coincide 

with the retention time of any of the 

target analytes. If the interfering peak is 

evident on the other column, report the 

result from that column and advise the 

data user that the interference resulted 

in a %D value greater than 50%. 

If an interferent is not identifiable on 

the second column, then the results 

must be reported as ‘‘not detected’’ at 

the lower concentration. In this event, 

the pesticide is not confirmed and the 

reporting limit is elevated. 

Note: The resulting elevation of the 

reporting limit may not meet the 

requirements for compliance monitoring and 

the use of additional cleanup procedures may 

be required. 

16. Analysis of Complex Samples 

16.1 Some samples may contain 

high levels (greater than 1 mg/L) of the 

analytes of interest, interfering analytes, 

and/or polymeric materials. Some 

samples may not concentrate to 1.0 mL 

(Section 10.3.3.3.2); others may 

overload the GC column and/or 

detector. 

16.2 When an interference is known 

or suspected to be present, the 

laboratory should attempt to clean up 

the sample extract using the SPE 

cartridge (Section 11.2), by Florisil®

(Section 11.3), Alumina (Section 11.4), 

sulfur removal (Section 11.5), or another 

clean up procedure appropriate to the 

analytes of interest. If these techniques 

do not remove the interference, the 

extract is diluted by a known factor and 

reanalyzed (Section 12). Dilution until 

the extract is lightly colored is 

preferable. Typical dilution factors are 

2, 5, and 10. 

16.3 Recovery of surrogate(s)—In 

most samples, surrogate recoveries will 

be similar to those from reagent water. 

If surrogate recovery is outside the range 

developed in Section 8.6, the sample is 

re-extracted and reanalyzed if there is 

sufficient sample and if it is within the 

7-day extraction holding time. If the 

surrogate recovery is still outside this 

range, extract and analyze one-tenth the 

volume of sample to overcome any 

matrix interference problems. If a 

sample is highly colored or suspected to 

be high in concentration, a 1–L sample 

aliquot and a 100-mL sample aliquot 

could be extracted simultaneously and 

still meet the holding time criteria, 

while providing information about a 

complex matrix. 

16.4 Recovery of the matrix spike 

and matrix spike duplicate (MS/MSD)— 

In most samples, MS/MSD recoveries 

will be similar to those from reagent 

water. If either the MS or MSD recovery 

is outside the range specified in Section 

8.3.3, one-tenth the volume of sample is 

spiked and analyzed. If the matrix spike 

recovery is still outside the range, the 

result for the unspiked sample may not 

be reported or used for permitting or 

regulatory compliance purposes. Poor 

matrix spike recovery does not relieve a 

discharger or permittee of reporting 

timely results. 

17. Method Performance 

17.1 This method was tested for 

linearity of spike recovery from reagent 

water and has been demonstrated to be 

applicable over the concentration range 

from 4x MDL to 1000x MDL with the 

following exceptions: Chlordane 

recovery at 4x MDL was low (60%); 

Toxaphene recovery was demonstrated 

linear over the range of 10x MDL to 

1000x MDL (Reference 3). 

17.2 The 1984 version of this 

method was tested by 20 laboratories 

using reagent water, drinking water, 

surface water, and three industrial 

wastewaters spiked at six 

concentrations (Reference 2). 

Concentrations used in the study ranged 

from 0.5 to 30 mg/L for singlecomponent pesticides and from 8.5 to 

400 mg/L for multi-component analytes. 

These data are for a subset of analytes 

described in the current version of the 

method. 

17.3 During the development of 

Method 1656, a similar EPA procedure 

for the organochlorine pesticides, 

single-operator precision, overall 

precision, and method accuracy were 

found to be directly related to the 

concentration of the analyte and 

essentially independent of the sample 

matrix. Linear equations to describe 

these relationships are presented in 

Table 5. 


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18. Pollution Prevention 

18.1 Pollution prevention 

encompasses any technique that reduces 

or eliminates the quantity or toxicity of 

waste at the point of generation. Many 

opportunities for pollution prevention 

exist in laboratory operations. EPA has 

established a preferred hierarchy of 

environmental management techniques 

that places pollution prevention as the 

management option of first choice. 

Whenever feasible, the laboratory 

should use pollution prevention 

techniques to address waste generation. 

When wastes cannot be reduced at the 

source, the Agency recommends 

recycling as the next best option. 

18.2 The analytes in this method are 

used in extremely small amounts and 

pose little threat to the environment 

when managed properly. Standards 

should be prepared in volumes 

consistent with laboratory use to 

minimize the disposal of excess 

volumes of expired standards. This 

method utilizes significant quantities of 

methylene chloride. Laboratories are 

encouraged to recover and recycle this 

and other solvents during extract 

concentration. 

18.3 For information about pollution 

prevention that may be applied to 

laboratories and research institutions, 

consult Less is Better: Laboratory 

Chemical Management for Waste 

Reduction (Reference 19). 

19. Waste Management 

19.1 The laboratory is responsible 

for complying with all Federal, State, 

and local regulations governing waste 

management, particularly the hazardous 

waste identification rules and land 

disposal restrictions, and to protect the 

air, water, and land by minimizing and 

controlling all releases from fume hoods 

and bench operations. Compliance is 

also required with any sewage discharge 

permits and regulations. An overview of 

requirements can be found in 

Environmental Management Guide for 

Small Laboratories (EPA 233–B–98– 

001). 

19.2 Samples at pH <2, or pH >12 

are hazardous and must be neutralized 

before being poured down a drain, or 

must be handled as hazardous waste. 

19.3 Many analytes in this method 

decompose above 500 ßC. Low-level 

waste such as absorbent paper, tissues, 

animal remains, and plastic gloves may 

be burned in an appropriate incinerator. 

Gross quantities of neat or highly 

concentrated solutions of toxic or 

hazardous chemicals should be 

packaged securely and disposed of 

through commercial or governmental 

channels that are capable of handling 

toxic wastes. 

20. References 

1. ‘‘Determination of Pesticides and 

PCBs in Industrial and Municipal 

Wastewaters,’’ EPA 600/4–82–023, 

National Technical Information 

Service, PB82–214222, Springfield, 

Virginia 22161, April 1982. 

2. ‘‘EPA Method Study 18 Method 608- 

Organochlorine Pesticides and 

PCBs,’’ EPA 600/4–84–061, 

National Technical Information 

Service, PB84–211358, Springfield, 

Virginia 22161, June 1984. 

3. ‘‘Method Detection Limit and 

Analytical Curve Studies, EPA 

Methods 606, 607, and 608,’’ 

Special letter report for EPA 

Contract 68–03–2606, U.S. 

Environmental Protection Agency, 

Environmental Monitoring and 

Support Laboratory, Cincinnati, 

Ohio 45268, June 1980. 

4. ASTM Annual Book of Standards, 

Part 31, D3694–78. ‘‘Standard 

Practice for Preparation of Sample 

Containers and for Preservation of 

Organic Constituents,’’ American 

Society for Testing and Materials, 

Philadelphia. 

5. Giam, C.S., Chan, H.S., and Nef, G.S. 

‘‘Sensitive Method for 

Determination of Phthalate Ester 

Plasticizers in Open-Ocean Biota 

Samples,’’ Analytical Chemistry, 

47, 2225 (1975). 

6. Giam, C.S. and Chan, H.S. ‘‘Control 

of Blanks in the Analysis of 

Phthalates in Air and Ocean Biota 

Samples,’’ U.S. National Bureau of 

Standards, Special Publication 442, 

pp. 701–708, 1976. 

7. Solutions to Analytical Chemistry 

Problems with Clean Water Act 

Methods, EPA 821–R–07–002, 

March 2007. 

8. ‘‘Carcinogens-Working With 

Carcinogens,’’ Department of 

Health, Education, and Welfare, 

Public Health Service, Center for 

Disease Control, National Institute 

for Occupational Safety and Health, 

Publication No. 77–206, August 

1977. 

9. ‘‘Occupational Exposure to 

Hazardous Chemicals in 

Laboratories,’’ (29 CFR part 1910, 

subpart 1450), Occupational Safety 

and Health Administration, OSHA. 

10. 40 CFR 136.6(b)(4)(j). 

11. Mills, P.A. ‘‘Variation of Florisil 

Activity: Simple Method for 

Measuring Absorbent Capacity and 

Its Use in Standardizing Florisil 

Columns,’’ Journal of the 

Association of Official Analytical 

Chemists, 51, 29, (1968). 

12. 40 CFR 136.6(b)(2)(i). 

13. Protocol for EPA Approval of New 

Methods for Organic and Inorganic 

Analytes in Wastewater and 

Drinking Water (EPA–821–B–98– 

003) March 1999. 

14. Methods 4500 Cl F and 4500 Cl G, 

Standard Methods for the 

Examination of Water and 

Wastewater, published jointly by 

the American Public Health 

Association, American Water Works 

Association, and Water 

Environment Federation, 1015 

Fifteenth St. Washington, DC 

20005, 20th Edition, 2000. 

15. ‘‘Manual of Analytical Methods for 

the Analysis of Pesticides in Human 

and Environmental Samples,’’ EPA– 

600/8–80–038, U.S. Environmental 

Protection Agency, Health Effects 

Research Laboratory, Research 

Triangle Park, North Carolina. 

16. USEPA, 2000, Method 1656 OrganoHalide 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-isbetter.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. 

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21. Tables 

TABLE 1—PESTICIDES 1

Analyte CAS No. MDL 2

(ng/L) 

ML 3

(ng/L) 

Aldrin ............................................................................................................................................ 309–00–2 8 24 

alpha-BHC ................................................................................................................................... 319–84–6 6 18 

beta-BHC ..................................................................................................................................... 319–85–7 7 21 

delta-BHC .................................................................................................................................... 319–86–8 5 15 

gamma-BHC (Lindane) ................................................................................................................ 58–89–9 1 33 

alpha-Chlordane .......................................................................................................................... 5103–71–9 9 27 

gamma-Chlordane ....................................................................................................................... 5103–74–2 8 24 

4,4′-DDD ...................................................................................................................................... 72–54–8 5 15 

4,4′-DDE ...................................................................................................................................... 72–55–9 10 30 

4,4′-DDT ....................................................................................................................................... 50–29–3 12 36 

Dieldrin ......................................................................................................................................... 60–57–1 6 18 

Endosulfan I ................................................................................................................................. 959–98–8 11 33 

Endosulfan II ................................................................................................................................ 33213–65–9 8 24 

Endosulfan sulfate ....................................................................................................................... 1031–07–8 7 21 

Endrin ........................................................................................................................................... 72–20–8 4 12 

Endrin aldehyde ........................................................................................................................... 7421–93–4 11 33 

Heptachlor .................................................................................................................................... 76–44–8 5 15 

Heptachlor epoxide ...................................................................................................................... 1024–57–3 12 36 

1All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A). 

2 40 CFR 136, Appendix B. MDLs were obtained by a single laboratory with an electrolytic conductivity detector, and are estimates of what can 

be achieved using an electron capture detector. 3 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 2—ADDITIONAL ANALYTES

Analyte CAS No. MDL 3

(ng/L) 

ML 4

(ng/L) 

Acephate ...................................................................................................................................... 30560–19–1 2,000 6,000 

Alachlor ........................................................................................................................................ 15972–60–8 20 60 

Atrazine ........................................................................................................................................ 1912–24–9 500 1,500 

Benfluralin (Benefin) .................................................................................................................... 1861–40–1 20 60 

Bromacil ....................................................................................................................................... 314–40–9 70 210 

Bromoxynil octanoate .................................................................................................................. 1689–99–2 30 90 

Butachlor ...................................................................................................................................... 23184–66–9 30 90 

Captafol ........................................................................................................................................ 2425–06–1 100 300 

Captan ......................................................................................................................................... 133–06–2 100 300 

Carbophenothion (Trithion) .......................................................................................................... 786–19–6 50 150 

Chlorobenzilate ............................................................................................................................ 510–15–6 25 75 

Chloroneb (Terraneb) .................................................................................................................. 2675–77–6 ........................ ........................

Chloropropylate (Acaralate) ......................................................................................................... 5836–10–2 ........................ ........................

Chlorothalonil ............................................................................................................................... 1897–45–6 15 45 

Cyanazine .................................................................................................................................... 21725–46–2 ........................ ........................

DCPA (Dacthal) ........................................................................................................................... 1861–32–1 3 9 

2,4′-DDD ...................................................................................................................................... 53–19–0 ........................ ........................

2,4′-DDE ...................................................................................................................................... 3424–82–6 ........................ ........................

2,4′-DDT ....................................................................................................................................... 789–02–6 ........................ ........................

Diallate (Avadex) ......................................................................................................................... 2303–16–4 45 135 

1,2-Dibromo-3-chloropropane (DBCP) ........................................................................................ 96–12–8 ........................ ........................

Dichlone ....................................................................................................................................... 117–80–6 ........................ ........................

Dichloran ...................................................................................................................................... 99–30–9 ........................ ........................

Dicofol .......................................................................................................................................... 115–32–2 ........................ ........................

Endrin ketone ............................................................................................................................... 53494–70–5 8 24 

Ethalfluralin (Sonalan) ................................................................................................................. 55283–68–6 5 15 

Etridiazole .................................................................................................................................... 2593–15–9 ........................ ........................

Fenarimol (Rubigan) .................................................................................................................... 60168–88–9 20 30 

Hexachlorobenzene 1 ................................................................................................................... 118–74–1 ........................ ........................

Hexachlorocyclopentadiene 1 ....................................................................................................... 77–47–4 ........................ ........................

Isodrin .......................................................................................................................................... 465–73–6 13 39 

Isopropalin (Paarlan) ................................................................................................................... 33820–53–0 20 60 

Kepone ......................................................................................................................................... 143–50–0 100 300 

Methoxychlor ................................................................................................................................ 72–43–5 30 90 

Metolachlor .................................................................................................................................. 51218–45–2 ........................ ........................

Metribuzin .................................................................................................................................... 21087–64–9 5 15 

Mirex ............................................................................................................................................ 2385–85–5 4 12 

Nitrofen (TOK) ............................................................................................................................. 1836–75–5 13 39 

cis-Nonachlor ............................................................................................................................... 5103–73–1 ........................ ........................

trans-Nonachlor ........................................................................................................................... 39765–80–5 ........................ ........................

Norfluorazon ................................................................................................................................ 27314–13–2 50 150 

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TABLE 2—ADDITIONAL ANALYTES—Continued 

Analyte CAS No. MDL 3

(ng/L) 

ML 4

(ng/L) 

Octachlorostyrene ........................................................................................................................ 29082–74–4 ........................ ........................

Oxychlordane ............................................................................................................................... 27304–13–8 ........................ ........................

PCNB (Pentachloronitrobenzene) ............................................................................................... 82–68–8 6 18 

Pendamethalin (Prowl) ................................................................................................................ 40487–42–1 ........................ ........................

cis-Permethrin .............................................................................................................................. 61949–76–6 200 600 

trans-Permethrin .......................................................................................................................... 61949–77–7 200 600 

Perthane (Ethylan) ....................................................................................................................... 72–56–0 ........................ ........................

Propachlor .................................................................................................................................... 1918–16–7 ........................ ........................

Propanil ........................................................................................................................................ 709–98–8 ........................ ........................

Propazine ..................................................................................................................................... 139–40–2 ........................ ........................

Quintozene ................................................................................................................................... 82–68–8 ........................ ........................

Simazine ...................................................................................................................................... 122–34–9 400 1,200 

Strobane ...................................................................................................................................... 8001–50–1 ........................ ........................

Technazene ................................................................................................................................. 117–18–0 ........................ ........................

Technical Chlordane 2 .................................................................................................................. ........................ ........................ ........................

Terbacil ........................................................................................................................................ 5902–51–2 200 600 

Terbuthylazine ............................................................................................................................. 5915–41–3 300 900 

Toxaphene 1 ................................................................................................................................. 8001–35–2 910 2,730 

Trifluralin ...................................................................................................................................... 1582–09–8 50 150 

PCB–1016 1 ................................................................................................................................. 12674–11–2 150 450 

PCB–1221 1 ................................................................................................................................. 11104–28–2 150 450 

PCB–1232 1 ................................................................................................................................. 11141–16–5 150 450 

PCB–1242 1 ................................................................................................................................. 53469–21–9 150 450 

PCB–1248 1 ................................................................................................................................. 12672–29–6 150 450 

PCB–1254 1 ................................................................................................................................. 11097–69–1 150 450 

PCB–1260 1 ................................................................................................................................. 11096–82–5 140 420 

1Priority Pollutants (40 CFR part 423, appendix A). 

2Technical Chlordane may be used in cases where historical reporting has only been for this form of Chlordane. 

3 40 CFR part 136, appendix B. MDLs were obtained by a single laboratory with an electrolytic conductivity detector, and are estimates of what 

can be achieved using an electron capture detector. 4 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 3—EXAMPLE RETENTION

TIMES 1

Analyte 

Retention time 

(min) 2

DB-608 DB-1701 

Acephate ................... 5.03 (3) 

Trifluralin ................... 5.16 6.79 

Ethalfluralin ............... 5.28 6.49 

Benfluralin ................. 5.53 6.87 

Diallate-A .................. 7.15 6.23 

Diallate-B .................. 7.42 6.77 

alpha-BHC ................ 8.14 7.44 

PCNB ........................ 9.03 7.58 

Simazine ................... 9.06 9.29 

Atrazine ..................... 9.12 9.12 

Terbuthylazine .......... 9.17 9.46 

gamma-BHC (Lindane) ..................... 9.52 9.91 

beta-BHC .................. 9.86 11.90 

Heptachlor ................ 10.66 10.55 

Chlorothalonil ............ 10.66 10.96 

Dichlone .................... 10.80 (4) 

Terbacil ..................... 11.11 12.63 

delta-BHC ................. 11.20 12.98 

Alachlor ..................... 11.57 11.06 

Propanil ..................... 11.60 14.10 

Aldrin ......................... 11.84 11.46 

DCPA ........................ 12.18 12.09 

Metribuzin ................. 12.80 11.68 

Triadimefon ............... 12.99 13.57 

Isopropalin ................ 13.06 13.37 

Isodrin ....................... 13.47 11.12 

Heptachlor epoxide ... 13.97 12.56 

Pendamethalin .......... 14.21 13.46 

Bromacil .................... 14.39 (3) 

TABLE 3—EXAMPLE RETENTION

TIMES 1—Continued 

Analyte 

Retention time 

(min) 2

DB-608 DB-1701 

alpha-Chlordane ....... 14.63 14.20 

Butachlor ................... 15.03 15.69 

gamma-Chlordane .... 15.24 14.36 

Endosulfan I .............. 15.25 13.87 

4,4′-DDE ................... 16.34 14.84 

Dieldrin ...................... 16.41 15.25 

Captan ...................... 16.83 15.43 

Chlorobenzilate ......... 17.58 17.28 

Endrin ....................... 17.80 15.86 

Nitrofen (TOK) .......... 17.86 17.47 

Kepone ..................... 17.92 (3 5) 

4,4′-DDD ................... 18.43 17.77 

Endosulfan II ............. 18.45 18.57 

Bromoxynil octanoate 18.85 18.57 

4,4′-DDT ................... 19.48 18.32 

Carbophenothion ...... 19.65 18.21 

Endrin aldehyde ........ 19.72 19.18 

Endosulfan sulfate .... 20.21 20.37 

Captafol .................... 22.51 21.22 

Norfluorazon ............. 20.68 22.01 

Mirex ......................... 22.75 19.79 

Methoxychlor ............ 22.80 20.68 

Endrin ketone ........... 23.00 21.79 

Fenarimol .................. 24.53 23.79 

cis-Permethrin ........... 25.00 23.59 

trans-Permethrin ....... 25.62 23.92 

PCB-1242.

PCB-1232.

PCB-1016.

PCB-1221.

TABLE 3—EXAMPLE RETENTION

TIMES 1—Continued 

Analyte 

Retention time 

(min) 2

DB-608 DB-1701 

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 × 0.53-mm ID fusedsilica capillary; DB-608, 0.83 μm; and DB1701, 1.0 μm. 

Conditions suggested to meet retention 

times shown: 150 °C for 0.5 minute, 150–270 

°C at 5 °C/min, and 270 °C until transPermethrin 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. 

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TABLE 4—QC ACCEPTANCE CRITERIA

Analyte 

Calibration 

verification 

(%) 

Test 

concentration 

(μg/L) 

Limit for s 

(% SD) 

Range for X 

(%) 

Range for P 

(%) 

Maximum 

MS/MSD RPD 

(%) 

Aldrin .......................................................... 75–125 2.0 25 54–130 42–140 35 

alpha-BHC .................................................. 69–125 2.0 28 49–130 37–140 36 

beta-BHC ................................................... 75–125 2.0 38 39–130 17–147 44 

delta-BHC ................................................... 75–125 2.0 43 51–130 19–140 52 

gamma-BHC .............................................. 75–125 2.0 29 43–130 32–140 39 

alpha-Chlordane ......................................... 73–125 50.0 24 55–130 45–140 35 

gamma-Chlordane ..................................... 75–125 50.0 24 55–130 45–140 35 

4,4′-DDD .................................................... 75–125 10.0 32 48–130 31–141 39 

4,4′-DDE .................................................... 75–125 2.0 30 54–130 30–145 35 

4,4′-DDT ..................................................... 75–125 10.0 39 46–137 25–160 42 

Dieldrin ....................................................... 48–125 2.0 42 58–130 36–146 49 

Endosulfan I ............................................... 75–125 2.0 25 57–141 45–153 28 

Endosulfan II .............................................. 75–125 10.0 63 22–171 D–202 53 

Endosulfan sulfate ..................................... 70–125 10.0 32 38–132 26–144 38 

Endrin ......................................................... 5–125 10.0 42 51–130 30–147 48 

Heptachlor .................................................. 75–125 2.0 28 43–130 34–140 43 

Heptachlor epoxide .................................... 75–125 2.0 22 57–132 37–142 26 

Toxaphene ................................................. 68–134 50.0 30 56–130 41–140 41 

PCB-1016 ................................................... 75–125 50.0 24 61–103 50–140 36 

PCB-1221 ................................................... 75–125 50.0 50 44–150 15–178 48 

PCB-1232 ................................................... 75–125 50.0 32 28–197 10–215 25 

PCB-1242 ................................................... 75–125 50.0 26 50–139 39–150 29 

PCB-1248 ................................................... 75–125 50.0 32 58–140 38–158 35 

PCB-1254 ................................................... 75–125 50.0 34 44–130 29–140 45 

PCB-1260 ................................................... 75–125 50.0 28 37–130 8–140 38 

S = Standard deviation of four recovery measurements (Section 8.2.4). 

Note: These criteria were developed from data in Table 5 (Reference 2). Where necessary, limits for recovery have been broadened to assure 

applicability to concentrations below those in Table 5. 

TABLE 5—PRECISION AND RECOVERY AS FUNCTIONS OF CONCENTRATION

Analyte Recovery, X′ 

(μg/L) 

Single analyst precision, sr′ 

(μg/L) 

Overall precision, 

S′ 

(μg/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 μg/L. 

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Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 9025 

TABLE 6—DISTRIBUTION OF

CHLORINATED PESTICIDES AND

PCBS INTO FLORISIL® COLUMN

FRACTIONS

Analyte 

Percent recovery 

by fraction 1

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 

TABLE 6—DISTRIBUTION OF

CHLORINATED PESTICIDES AND

PCBS INTO FLORISIL® COLUMN

FRACTIONS—Continued 

Analyte 

Percent recovery 

by fraction 1

1 2 3 

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 

TABLE 6—DISTRIBUTION OF

CHLORINATED PESTICIDES AND

PCBS INTO FLORISIL® COLUMN

FRACTIONS—Continued 

Analyte 

Percent recovery 

by fraction 1

1 2 3 

PCB-1232 ..................... 95 4 

PCB-1242 ..................... 97 

PCB-1248 ..................... 103 

PCB-1254 ..................... 90 

PCB-1260.

1Eluant composition: 

Fraction 1—6% ethyl ether in hexane 

Fraction 2—15% ethyl ether in hexane 

Fraction 3—50% ethyl ether in hexane. 

BILLING CODE 6560–50–P 


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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 

°C degrees Celsius 

mg microgram 

mL microliter 

< less than 

≤ less than or equal to 

> greater than 

% percent 

23.1.2 Abbreviations (in alphabetical 

order) 

cm centimeter 

g gram 


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250 

90·mm GMF 150 

Flask 

Figure 2 Disk-based solid-phase extraction apparatus 
Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 9027 

hr hour 

ID inside diameter 

in. inch 

L liter 

M molar solution—one mole or gram 

molecular weight of solute in one liter 

of solution 

mg milligram 

min minute 

mL milliliter 

mm millimeter 

N Normality—one equivalent of solute 

in one liter of solution 

ng nanogram 

psia pounds-per-square inch absolute 

psig pounds-per-square inch gauge 

v/v volume per unit volume 

w/v weight per unit volume 

23.2 Definitions and acronyms (in 

alphabetical order) 

Analyte—A compound or mixture of 

compounds (e.g., PCBs) tested for by 

this method. The analytes are listed in 

Tables 1 and 2. 

Analytical batch—The set of samples 

analyzed on a given instrument during 

a 24-hour period that begins and ends 

with calibration verification (Sections 

7.8 and 13). See also ‘‘Extraction batch.’’ 

Blank (method blank; laboratory 

blank)—An aliquot of reagent water that 

is treated exactly as a sample including 

exposure to all glassware, equipment, 

solvents, reagents, internal standards, 

and surrogates that are used with 

samples. The blank is used to determine 

if analytes or interferences are present 

in the laboratory environment, the 

reagents, or the apparatus. 

Calibration factor (CF)—See Section 

7.5.1. 

Calibration standard—A solution 

prepared from stock solutions and/or a 

secondary standards and containing the 

analytes of interest, surrogates, and 

internal standards. This standard is 

used to model the response of the GC 

instrument against analyte 

concentration. 

Calibration verification—The process 

of confirming that the response of the 

analytical system remains within 

specified limits of the calibration. 

Calibration verification standard— 

The combined QC standard (Section 7.7) 

used to verify calibration (Section 13.5) 

and for LCS tests (Section 8.4). 

Extraction Batch—A set of up to 20 

field samples (not including QC 

samples) started through the extraction 

process in a given 24-hour shift. Each 

extraction batch of 20 or fewer samples 

must be accompanied by a blank 

(Section 8.5), a laboratory control 

sample (LCS, Section 8.4), a matrix 

spike and duplicate (MS/MSD; Section 

8.3), resulting in a minimum of five 

samples (1 field sample, 1 blank, 1 LCS, 

1 MS, and 1 MSD) and a maximum of 

24 samples (20 field samples, 1 blank, 

1 LCS, 1 MS, and 1 MSD) for the batch. 

If greater than 20 samples are to be 

extracted in a 24-hour shift, the samples 

must be separated into extraction 

batches of 20 or fewer samples. 

Field Duplicates—Two samples 

collected at the same time and place 

under identical conditions, and treated 

identically throughout field and 

laboratory procedures. Results of 

analyses the field duplicates provide an 

estimate of the precision associated with 

sample collection, preservation, and 

storage, as well as with laboratory 

procedures. 

Field blank—An aliquot of reagent 

water or other reference matrix that is 

placed in a sample container in the 

field, and treated as a sample in all 

respects, including exposure to 

sampling site conditions, storage, 

preservation, and all analytical 

procedures. The purpose of the field 

blank is to determine if the field or 

sample transporting procedures and 

environments have contaminated the 

sample. See also ‘‘Blank.’’ 

GC—Gas chromatograph or gas 

chromatography 

Gel-permeation chromatography 

(GPC)—A form of liquid 

chromatography in which the analytes 

are separated based on exclusion from 

the solid phase by size. 

Internal standard—A compound 

added to an extract or standard solution 

in a known amount and used as a 

reference for quantitation of the analytes 

of interest and surrogates. Also see 

Internal standard quantitation. 

Internal standard quantitation—A 

means of determining the concentration 

of an analyte of interest (Tables 1 and 

2) by reference to a compound not 

expected to be found in a sample. 

IDC—Initial Demonstration of 

Capability (Section 8.2); four aliquots of 

a reference matrix spiked with the 

analytes of interest and analyzed to 

establish the ability of the laboratory to 

generate acceptable precision and 

recovery. An IDC is performed prior to 

the first time this method is used and 

any time the method or instrumentation 

is modified. 

Laboratory Control Sample (LCS; 

laboratory fortified blank; Section 8.4)— 

An aliquot of reagent water spiked with 

known quantities of the analytes of 

interest and surrogates. The LCS is 

analyzed exactly like a sample. Its 

purpose is to assure that the results 

produced by the laboratory remain 

within the limits specified in this 

method for precision and recovery. 

Laboratory Fortified Sample Matrix— 

See Matrix spike. 

Laboratory reagent blank—See blank. 

Matrix spike (MS) and matrix spike 

duplicate (MSD) (laboratory fortified 

sample matrix and duplicate)—Two 

aliquots of an environmental sample to 

which known quantities of the analytes 

of interest and surrogates are added in 

the laboratory. The MS/MSD are 

prepared and analyzed exactly like a 

field sample. Their purpose is to 

quantify any additional bias and 

imprecision caused by the sample 

matrix. The background concentrations 

of the analytes in the sample matrix 

must be determined in a separate 

aliquot and the measured values in the 

MS/MSD corrected for background 

concentrations. 

May—This action, activity, or 

procedural step is neither required nor 

prohibited. 

May not—This action, activity, or 

procedural step is prohibited. 

Method detection limit (MDL)—A 

detection limit determined by the 

procedure at 40 CFR part 136, appendix 

B. The MDLs determined by EPA are 

listed in Tables 1 and 2. As noted in 

Sec. 1.6, use the MDLs in Tables 1 and 

2 in conjunction with current MDL data 

from the laboratory actually analyzing 

samples to assess the sensitivity of this 

procedure relative to project objectives 

and regulatory requirements (where 

applicable). 

Minimum level (ML)—The term 

‘‘minimum level’’ refers to either the 

sample concentration equivalent to the 

lowest calibration point in a method or 

a multiple of the method detection limit 

(MDL), whichever is higher. Minimum 

levels may be obtained in several ways: 

They may be published in a method; 

they may be based on the lowest 

acceptable calibration point used by a 

laboratory; or they may be calculated by 

multiplying the MDL in a method, or 

the MDL determined by a laboratory, by 

a factor of 3. For the purposes of NPDES 

compliance monitoring, EPA considers 

the following terms to be synonymous: 

‘‘quantitation limit,’’ ‘‘reporting limit,’’ 

and ‘‘minimum level.’’ 

MS—Mass spectrometer or mass 

spectrometry. 

Must—This action, activity, or 

procedural step is required. 

Preparation blank—See blank. 

Quality control sample (QCS)—A 

sample containing analytes of interest at 

known concentrations. The QCS is 

obtained from a source external to the 

laboratory or is prepared from standards 

obtained from a different source than 

the calibration standards. The purpose 

is to check laboratory performance using 

test materials that have been prepared 

independent of the normal preparation 

process. 

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9028 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

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 

§ 1910.1200. United Nations Globally 

Harmonized System of Classification 

and Labelling of Chemicals (GHS), third 

revised edition, United Nations, 2009. 

Should—This action, activity, or 

procedural step is suggested but not 

required. 

SPE—Solid-phase extraction; a 

sample extraction or extract cleanup 

technique in which an analyte is 

selectively removed from a sample or 

extract by passage over or through a 

material capable of reversibly adsorbing 

the analyte. 

Stock solution—A solution containing 

an analyte that is prepared using a 

reference material traceable to EPA, the 

National Institute of Science and 

Technology (NIST), or a source that will 

attest to the purity and authenticity of 

the reference material. 

Surrogate—A compound unlikely to 

be found in a sample, which is spiked 

into the sample in a known amount 

before extraction, and which is 

quantified with the same procedures 

used to quantify other sample 

components. The purpose of the 

surrogate is to monitor method 

performance with each sample. 

* * * * * 

Method 611—Haloethers 

1. Scope and Application 

1.1 This method covers the 

determination of certain haloethers. The 

following parameters can be determined 

by this method: 

Parameter STORET No. CAS No. 

Bis(2-chloroethyl) ether ............................................................................................................................................ 34273 111–44–4 

Bis(2-chloroethoxy) methane ................................................................................................................................... 34278 111–91–1 

2, 2′-oxybis (1-chloropropane) ................................................................................................................................. 34283 108–60–1 

4-Bromophenyl phenyl ether ................................................................................................................................... 34636 101–55–3 

4-Chlorophenyl phenyl either ................................................................................................................................... 34641 7005–72–3 

* * * * * 

Method 624.1—Purgeables by GC/MS 

1. Scope and Application 

1.1 This method is for determination 

of purgeable organic pollutants in 

industrial discharges and other 

environmental samples by gas 

chromatography combined with mass 

spectrometry (GC/MS), as provided 

under 40 CFR 136.1. This revision is 

based on previous protocols (References 

1–3), on the revision promulgated 

October 26, 1984 (49 FR 43234), and on 

an interlaboratory method validation 

study (Reference 4). Although this 

method was validated through an 

interlaboratory study conducted more 

than 29 years ago, the fundamental 

chemistry principles used in this 

method remain sound and continue to 

apply. 

1.2 The analytes that may be 

qualitatively and quantitatively 

determined using this method and their 

CAS Registry numbers are listed in 

Table 1. The method may be extended 

to determine the analytes listed in Table 

2; however, poor purging efficiency or 

gas chromatography of some of these 

analytes may make quantitative 

determination difficult. For example, an 

elevated temperature may be required to 

purge some analytes from water. If an 

elevated temperature is used, calibration 

and all quality control (QC) tests must 

be performed at the elevated 

temperature. EPA encourages the use of 

this method to determine additional 

compounds amenable to purge-and-trap 

GC/MS. 

1.3 The large number of analytes in 

Tables 1 and 2 of this method makes 

testing difficult if all analytes are 

determined simultaneously. Therefore, 

it is necessary to determine and perform 

QC tests for ‘‘analytes of interest’’ only. 

Analytes of interest are those required to 

be determined by a regulatory/control 

authority or in a permit, or by a client. 

If a list of analytes is not specified, the 

analytes in Table 1 must be determined, 

at a minimum, and QC testing must be 

performed for these analytes. The 

analytes in Table 1 and some of the 

analytes in Table 2 have been identified 

as Toxic Pollutants (40 CFR 401.15), 

expanded to a list of Priority Pollutants 

(40 CFR part 423, appendix A). 

1.4 Method detection limits (MDLs; 

Reference 5) for the analytes in Table 1 

are listed in that table. These MDLs 

were determined in reagent water 

(Reference 6). Advances in analytical 

technology, particularly the use of 

capillary (open-tubular) columns, 

allowed laboratories to routinely 

achieve MDLs for the analytes in this 

method that are 2–10 times lower than 

those in the version promulgated in 

1984 (40 FR 43234). The MDL for a 

specific wastewater may differ from 

those listed, depending on the nature of 

interferences in the sample matrix. 

1.4.1 EPA has promulgated this 

method at 40 CFR part 136 for use in 

wastewater compliance monitoring 

under the National Pollutant Discharge 

Elimination System (NPDES). The data 

reporting practices described in Section 

13.2 are focused on such monitoring 

needs and may not be relevant to other 

uses of the method. 

1.4.2 This method includes 

‘‘reporting limits’’ based on EPA’s 

‘‘minimum level’’ (ML) concept (see the 

glossary in Section 20). Table 1 contains 

MDL values and ML values for many of 

the analytes. The MDL for an analyte in 

a specific wastewater may differ from 

that listed in Table 1, depending upon 

the nature of interferences in the sample 

matrix. 

1.5 This method is performancebased. 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. 

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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 purgeand-trap system and a gas 

chromatograph/mass spectrometer and 

in the interpretation of mass spectra. 

Each analyst must demonstrate the 

ability to generate acceptable results 

with this method using the procedure in 

Section 8.2. 

1.7 Terms and units of measure used 

in this method are given in the glossary 

at the end of the method. 

2. Summary of Method 

2.1 A gas is bubbled through a 

measured volume of water in a 

specially-designed purging chamber 

(Figure 1). The purgeables are efficiently 

transferred from the aqueous phase to 

the vapor phase. The vapor is swept 

through a sorbent trap where the 

purgeables are trapped (Figure 2). After 

purging is completed, the trap is heated 

and backflushed with the gas to desorb 

the purgeables onto a gas 

chromatographic column (Figures 3 and 

4). The column is temperature 

programmed to separate the purgeables 

which are then detected with a mass 

spectrometer. 

2.2 Different sample sizes in the 

range of 5–25 mL are allowed in order 

to meet differing sensitivity 

requirements. Calibration and QC 

samples must have the same volume as 

field samples. 

3. Interferences 

3.1 Impurities in the purge gas, 

organic compounds outgassing from the 

plumbing ahead of the trap, and solvent 

vapors in the laboratory account for the 

majority of contamination problems. 

The analytical system must be 

demonstrated to be free from 

contamination under the conditions of 

the analysis by analyzing blanks as 

described in Section 8.5. Fluoropolymer 

tubing, fittings, and thread sealant 

should be used to avoid contamination. 

3.2 Samples can be contaminated by 

diffusion of volatile organics 

(particularly fluorocarbons and 

methylene chloride) through the septum 

seal into the sample during shipment 

and storage. Protect samples from 

sources of volatiles during collection, 

shipment, and storage. A reagent water 

field blank carried through sampling 

and analysis can serve as a check on 

such contamination. 

3.3 Contamination by carry-over can 

occur whenever high level and low level 

samples are analyzed sequentially. To 

reduce the potential for carry-over, the 

purging device and sample syringe must 

be rinsed with reagent water between 

sample analyses. Whenever an 

unusually concentrated sample is 

encountered, it should be followed by 

an analysis of a blank to check for cross 

contamination. For samples containing 

large amounts of water-soluble 

materials, suspended solids, high 

boiling compounds or high purgeable 

levels, it may be necessary to wash the 

purging device with a detergent 

solution, rinse it with distilled water, 

and then dry it in a 105 °C oven 

between analyses. The trap and other 

parts of the system are also subject to 

contamination; therefore, frequent 

bakeout and purging of the entire 

system may be required. Screening 

samples at high dilution may prevent 

introduction of contaminants into the 

system. 

4. Safety 

4.1 The toxicity or carcinogenicity of 

each reagent used in this method has 

not been precisely defined; however, 

each chemical compound should be 

treated as a potential health hazard. 

From this viewpoint, exposure to these 

chemicals must be reduced to the lowest 

possible level. The laboratory is 

responsible for maintaining a current 

awareness file of OSHA regulations 

regarding the safe handling of the 

chemicals specified in this method. A 

reference file of safety data sheets 

(SDSs, OSHA, 29 CFR 1910.1200(g)) 

should also be made available to all 

personnel involved in sample handling 

and chemical analysis. Additional 

references to laboratory safety are 

available and have been identified 

(References 7–9) for the information of 

the analyst. 

4.2. The following analytes covered 

by this method have been tentatively 

classified as known or suspected human 

or mammalian carcinogens: Benzene; 

carbon tetrachloride; chloroform; 1,4- 

dichlorobenzene; 1,2-dichloroethane; 

1,2-dichloropropane; methylene 

chloride; tetrachloroethylene; 

trichloroethylene; and vinyl chloride. 

Primary standards of these toxic 

compounds should be prepared in a 

chemical fume hood, and a NIOSH/

MESA approved toxic gas respirator 

should be worn when handling high 

concentrations of these compounds. 

4.3 This method allows the use of 

hydrogen as a carrier gas in place of 

helium (Section 5.3.1.2). The laboratory 

should take the necessary precautions in 

dealing with hydrogen, and should limit 

hydrogen flow at the source to prevent 

buildup of an explosive mixture of 

hydrogen in air. 

5. Apparatus and Materials 

Note: Brand names, suppliers, and part 

numbers are cited for illustration purposes 

only. No endorsement is implied. Equivalent 

performance may be achieved using 

equipment and materials other than those 

specified here. Demonstration of equivalent 

performance that meets the requirements of 

this method is the responsibility of the 

laboratory. Suppliers for equipment and 

materials in this method may be found 

through an on-line search. 

5.1 Sampling equipment for discrete 

sampling. 

5.1.1 Vial—25 or 40 mL capacity, or 

larger, with screw cap with a hole in the 

center (Pierce #13075 or equivalent). 

Unless pre-cleaned, detergent wash, 

rinse with tap and reagent water, and 

dry at 105 °C before use. 

5.1.2 Septum—Fluoropolymer-faced 

silicone (Pierce #12722 or equivalent). 

Unless pre-cleaned, detergent wash, 

rinse with tap and reagent water, and 

dry at 105 ± 5 °C for one hour before 

use. 

5.2 Purge-and-trap system—The 

purge-and-trap system consists of three 

separate pieces of equipment: A purging 

device, trap, and desorber. Several 

complete systems are commercially 

available. Any system that meets the 

performance requirements in this 

method may be used. 

5.2.1 The purging device should 

accept 5- to 25-mL samples with a water 

column at least 3 cm deep. The purge 

gas must pass though the water column 

as finely divided bubbles. The purge gas 

must be introduced no more than 5 mm 

from the base of the water column. The 

purging device illustrated in Figure 1 

meets these design criteria. Purge 

devices of a different volume may be 

used so long as the performance 

requirements in this method are met. 

5.2.2 The trap should be at least 25 

cm long and have an inside diameter of 

at least 0.105 in. The trap should be 

packed to contain the following 

minimum lengths of adsorbents: 1.0 cm 

of methyl silicone coated packing 

(Section 6.3.2), 15 cm of 2,6- 

diphenylene oxide polymer (Section 

6.3.1), and 8 cm of silica gel (Section 

6.3.3). The minimum specifications for 

the trap are illustrated in Figure 2. A 

trap with different dimensions and 

packing materials is acceptable so long 

as the performance requirements in this 

method are met. 

5.2.3 The desorber should be 

capable of rapidly heating the trap to the 

temperature necessary to desorb the 

analytes of interest, and of maintaining 

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this temperature during desorption. The 

trap should not be heated higher than 

the maximum temperature 

recommended by the manufacturer. The 

desorber illustrated in Figure 2 meets 

these design criteria. 

5.2.4 The purge-and-trap system 

may be assembled as a separate unit or 

coupled to a gas chromatograph as 

illustrated in Figures 3 and 4. 

5.3 GC/MS system. 

5.3.1 Gas chromatograph (GC)—An 

analytical system complete with a 

temperature programmable gas 

chromatograph and all required 

accessories, including syringes and 

analytical columns. Autosamplers 

designed for purge-and-trap analysis of 

volatiles also may be used. 

5.3.1.1 Injection port—Volatiles 

interface, split, splitless, temperature 

programmable split/splitless (PTV), 

large volume, on-column, backflushed, 

or other. 

5.3.1.2 Carrier gas—Data in the 

tables in this method were obtained 

using helium carrier gas. If another 

carrier gas is used, analytical conditions 

may need to be adjusted for optimum 

performance, and calibration and all QC 

tests must be performed with the 

alternate carrier gas. See Section 4.3 for 

precautions regarding the use of 

hydrogen as a carrier gas. 

5.3.2 GC column—See the footnote 

to Table 3. Other columns or column 

systems may be used provided all 

requirements in this method are met. 

5.3.3 Mass spectrometer—Capable of 

repetitively scanning from 35–260 

Daltons (amu) every 2 seconds or less, 

utilizing a 70 eV (nominal) electron 

energy in the electron impact ionization 

mode, and producing a mass spectrum 

which meets all criteria in Table 4 when 

50 ng or less of 4-bromofluorobenzene 

(BFB) is injected through the GC inlet. 

If acrolein, acrylonitrile, chloromethane, 

and vinyl chloride are to be determined, 

it may be necessary to scan from below 

25 Daltons to measure the peaks in the 

26—35 Dalton range for reliable 

identification. 

5.3.4 GC/MS interface—Any GC to 

MS interface that meets all performance 

requirements in this method may be 

used. 

5.3.5 Data system—A computer 

system must be interfaced to the mass 

spectrometer that allows continuous 

acquisition and storage of mass spectra 

throughout the chromatographic 

program. The computer must have 

software that allows searching any GC/ 

MS data file for specific m/z’s (masses) 

and plotting m/z abundances versus 

time or scan number. This type of plot 

is defined as an extracted ion current 

profile (EICP). Software must also be 

available that allows integrating the 

abundance at any EICP between 

specified time or scan number limits. 

5.4 Syringes—Graduated, 5–25 mL, 

glass hypodermic with Luerlok tip, 

compatible with the purging device. 

5.5 Micro syringes—Graduated, 25– 

1000 mL, 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 °C while bubbling 

contaminant free gas through it for 

approximately 1 hour. While still hot, 

transfer the water to screw-cap bottles 

and seal with a fluoropolymer-lined 

cap. 

6.2 Sodium thiosulfate—(ACS) 

Granular. 

6.3 Trap materials. 

6.3.1 2,6-Diphenylene oxide 

polymer—Tenax, 60/80 mesh, 

chromatographic grade, or equivalent. 

6.3.2 Methyl silicone packing—3% 

OV–1 on Chromosorb-W, 60/80 mesh, or 

equivalent. 

6.3.3 Silica gel—35/60 mesh, 

Davison, Grade-15 or equivalent. 

Other trap materials are acceptable if 

performance requirements in this 

method are met. 

6.4 Methanol—Demonstrated to be 

free from the target analytes and 

potentially interfering compounds. 

6.5 Stock standard solutions—Stock 

standard solutions may be prepared 

from pure materials, or purchased as 

certified solutions. Traceability must be 

to the National Institute of Standards 

and Technology (NIST) or other national 

standard. Stock solution concentrations 

alternate to those below may be used. 

Prepare stock standard solutions in 

methanol using assayed liquids or gases 

as appropriate. Because some of the 

compounds in this method are known to 

be toxic, primary dilutions should be 

prepared in a hood, and a NIOSH/MESA 

approved toxic gas respirator should be 

worn when high concentrations of neat 

materials are handled. The following 

procedure may be used to prepare 

standards from neat materials: 

6.5.1 Place about 9.8 mL of 

methanol in a 10-mL ground-glassstoppered volumetric flask. Allow the 

flask to stand, unstoppered, for about 10 

minutes or until all alcohol wetted 

surfaces have dried. Weigh the flask to 

the nearest 0.1 mg. 

6.5.2 Add the assayed reference 

material. 

6.5.2.1 Liquids—Using a 100 mL 

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 mg/ 

mL from the net gain in weight. 

6.5.2.2 Gases—To prepare standards 

for any of compounds that boil below 30 

°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 mg/mL 

from the net gain in weight. 

6.5.3 When compound purity is 

assayed to be 96% or greater, the weight 

may be used without correction to 

calculate the concentration of the stock 

standard. Commercially prepared stock 

standards may be used at any 

concentration if they are certified by the 

manufacturer or by an independent 

source. 

6.5.4 Prepare fresh standards weekly 

for the gases and 2-chloroethylvinyl 

ether. All standards should be replaced 

after one month, or sooner if the 

concentration of an analyte changes by 

more than 10 percent. 

Note: 2-Chloroethylvinyl ether has been 

shown to be stable for as long as one month 

if prepared as a separate standard, and the 

other analytes have been shown to be stable 

for as long as 2 months if stored at less than 

¥10 °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 

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surrogate in methanol as described in 

Section 6.5, and prepare a solution for 

spiking the surrogates into all blanks, 

LCSs, and MS/MSDs. The spiking 

solution should be prepared such that 

spiking a small volume will result in 

surrogate concentrations near the midpoint of the calibration range. For 

example, adding 10 mL of a spiking 

solution containing the surrogates at a 

concentration of 15 mg/mL in methanol 

to a 5-mL aliquot of water would result 

in a concentration of 30 mg/L for each 

surrogate. Other surrogate 

concentrations may be used. 

6.8 BFB standard—Prepare a 

solution of BFB in methanol as 

described in Sections 6.5 and 6.6. The 

solution should be prepared such that 

an injection or purging from water will 

result in introduction of ≤50 ng into the 

GC. BFB may be included in a mixture 

with the internal standards and/or 

surrogates. 

6.9 Quality control check sample 

concentrate—See Section 8.2.1. 

6.10 Storage—When not being used, 

store standard solutions (Sections 6.5– 

6.9) at ¥10 to ¥20 °C, protected from 

light, in fluoropolymer-sealed glass 

containers with minimal headspace. 

7. Calibration 

7.1 Assemble a purge-and-trap 

system that meets the specifications in 

Section 5.2. Prior to first use, condition 

the trap overnight at 180 °C by 

backflushing with gas at a flow rate of 

at least 20 mL/min. Condition the trap 

daily prior to use. 

7.2 Connect the purge-and-trap 

system to the gas chromatograph. The 

gas chromatograph should be operated 

using temperature and flow rate 

conditions equivalent to those given in 

the footnotes to Table 3. Alternative 

temperature and flow rate conditions 

may be used provided that performance 

requirements in this method are met. 

7.3 Internal standard calibration. 

7.3.1 Internal standards. 

7.3.1.1 Select three or more internal 

standards similar in chromatographic 

behavior to the compounds of interest. 

Suggested internal standards are listed 

in Table 5. Use the base peak m/z as the 

primary m/z for quantification of the 

standards. If interferences are found at 

the base peak, use one of the next two 

most intense m/z’s for quantitation. 

Demonstrate that measurement of the 

internal standards are not affected by 

method or matrix interferences. 

7.3.1.2 To assure accurate analyte 

identification, particularly when 

selected ion monitoring (SIM) is used, it 

may be advantageous to include more 

internal standards than those suggested 

in Section 7.3.1.1. An analyte will be 

located most accurately if its retention 

time relative to an internal standard is 

in the range of 0.8 to 1.2. 

7.3.1.3 Prepare a stock standard 

solution for each internal standard 

surrogate in methanol as described in 

Section 6.5, and prepare a solution for 

spiking the internal standards into all 

blanks, LCSs, and MS/MSDs. The 

spiking solution should be prepared 

such that spiking a small volume will 

result in internal standard 

concentrations near the mid-point of the 

calibration range. For example, adding 

10 mL of a spiking solution containing 

the internal standards at a concentration 

of 15 mg/mL in methanol to a 5-mL 

aliquot of water would result in a 

concentration of 30 mg/L for each 

internal standard. Other concentrations 

may be used. The internal standard 

solution and the surrogate standard 

spiking solution (Section 6.7) may be 

combined, if desired. Store the solution 

at <6 °C in fluoropolymer-sealed glass 

containers with a minimum of 

headspace. Replace the solution after 1 

month, or more frequently if 

comparison with QC standards indicates 

a problem. 

7.3.2 Calibration. 

7.3.2.1 Calibration standards. 

7.3.2.1.1 Prepare calibration 

standards at a minimum of five 

concentration levels for each analyte of 

interest by adding appropriate volumes 

of one or more stock standards to a fixed 

volume (e.g., 40 mL) of reagent water in 

volumetric glassware. Fewer levels may 

be necessary for some analytes based on 

the sensitivity of the MS. The 

concentration of the lowest calibration 

standard for an analyte should be at or 

near the ML value in Table 1 for an 

analyte listed in that table. The ML 

value may be rounded to a whole 

number that is more convenient for 

preparing the standard, but must not 

exceed the ML values listed in Table 1 

for those analytes which list ML values. 

Alternatively, the laboratory may 

establish the ML for each analyte based 

on the concentration of the lowest 

calibration standard in a series of 

standards obtained from a commercial 

vendor, again, provided that the ML 

values does not exceed the MLs in Table 

1, and provided that the resulting 

calibration meets the acceptance criteria 

in Section 7.3.4, based on the RSD, RSE, 

or R2. 

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; 

ax2 + bx + c) calibration. Calibrations 

higher than second order are not 

allowed. 

7.3.2.1.2 To each calibration 

standard or standard mixture, add a 

known constant volume of the internal 

standard spiking solution (Section 

7.3.1.3) and surrogate standard spiking 

solution (Section 6.7) or the combined 

internal standard solution and surrogate 

spiking solution (Section 7.3.1.3). 

Aqueous standards may be stored up to 

24 hours, if held in sealed vials with 

zero headspace as described in Section 

9.1. If not so stored, they must be 

discarded after one hour. 

7.3.2.2 Prior to analysis of the 

calibration standards, analyze the BFB 

standard (Section 6.8) and adjust the 

scan rate of the MS to produce a 

minimum of 5 mass spectra across the 

BFB GC peak, but do not exceed 2 

seconds per scan. Adjust instrument 

conditions until the BFB criteria in 

Table 4 are met. 

Note: The BFB spectrum may be evaluated 

by summing the intensities of the m/z’s 

across the GC peak, subtracting the 

background at each m/z in a region of the 

chromatogram within 20 scans of but not 

including any part of the BFB peak. The BFB 

spectrum may also be evaluated by fitting a 

Gaussian to each m/z and using the intensity 

at the maximum for each Gaussian, or by 

integrating the area at each m/z and using the 

integrated areas. Other means may be used 

for evaluation of the BFB spectrum so long 

as the spectrum is not distorted to meet the 

criteria in Table 4. 

7.3.2.3 Analyze the mid-point 

standard and enter or review the 

retention time, relative retention time, 

mass spectrum, and quantitation m/z in 

the data system for each analyte of 

interest, surrogate, and internal 

standard. If additional analytes (Table 2) 

are to be quantified, include these 

analytes in the standard. The mass 

spectrum for each analyte must be 

comprised of a minimum of 2 m/z’s; 3 

to 5 m/z’s assure more reliable analyte 

identification. Suggested quantitation 

m/z’s are shown in Table 6 as the 

primary m/z. For analytes in Table 6 

that do not have a secondary m/z, 

acquire a mass spectrum and enter one 

or more secondary m/z’s for more 

reliable identification. If an interference 

occurs at the primary m/z, use one of 

the secondary m/z’s or an alternate m/ 

z. A single m/z only is required for 

quantitation. 

7.3.2.4 For SIM operation, determine 

the analytes in each descriptor, the 

quantitation m/z for each analyte (the 

quantitation m/z can be the same as for 

full-scan operation; Section 7.3.2.3), the 

dwell time on each m/z for each analyte, 

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and the beginning and ending retention 

time for each descriptor. Analyze the 

verification standard in scan mode to 

verify m/z’s and establish retention 

times for the analytes. There must be a 

minimum of two m/z’s for each analyte 

to assure analyte identification. To 

maintain sensitivity, the number of m/ 

z’s in a descriptor should be limited. For 

example, for a descriptor with 10 m/z’s 

and a chromatographic peak width of 5 

sec, a dwell time of 100 ms at each m/ 

z would result in a scan time of 1 

second and provide 5 scans across the 

GC peak. The quantitation m/z will 

usually be the most intense peak in the 

mass spectrum. The quantitation m/z 

and dwell time may be optimized for 

each analyte. However, if a GC peak 

spans two (or more) descriptors, the 

dwell time and cycle time (scans/sec) 

should be set to the same value in both 

segments in order to maintain 

equivalent response. The acquisition 

table used for SIM must take into 

account the mass defect (usually less 

than 0.2 Dalton) that can occur at each 

m/z monitored. 

7.3.2.5 For combined scan and SIM 

operation, set up the scan segments and 

descriptors to meet requirements in 

Sections 7.3.2.2–7.3.2.4. 

7.3.3 Analyze each calibration 

standard according to Section 10 and 

tabulate the area at the quantitation m/ 

z against concentration for each analyte 

of interest, surrogate, and internal 

standard. Calculate the response factor 

(RF) for each compound at each 

concentration using Equation 1. 

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 

(mg/L). 

Cs = Concentration of the analyte to be 

measured (mg/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 

(R2) 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 recalibrated. 

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 incontrol mode of operation. A laboratory 

may develop its own performance 

criteria (as QC acceptance criteria), 

provided such criteria are as or more 

restrictive than the criteria in this 

method. 

8.1.1 The laboratory must make an 

initial demonstration of capability 

(DOC) to generate acceptable precision 

and recovery with this method. This 

demonstration is detailed in Section 8.2. 

8.1.2 In recognition of advances that 

are occurring in analytical technology, 

and to overcome matrix interferences, 

the laboratory is permitted certain 

options (Section 1.5 and 40 CFR 

136.6(b)) to improve separations or 

lower the costs of measurements. These 

options may include an alternate purgeand-trap device, and changes in both 

column and type of mass spectrometer 

(see 40 CFR 136.6(b)(4)(xvi)). Alternate 

determinative techniques, such as 

substitution of spectroscopic or 

immunoassay techniques, and changes 

that degrade method performance, are 

not allowed. If an analytical technique 

other than GC/MS is used, that 

technique must have a specificity equal 

to or greater than the specificity of GC/ 

MS for the analytes of interest. The 

laboratory is also encouraged to 

participate in inter-comparison and 

performance evaluation studies (see 

Section 8.9). 

8.1.2.1 Each time a modification is 

made to this method, the laboratory is 

required to repeat the procedure in 

Section 8.2. If the detection limit of the 

method will be affected by the change, 

the laboratory must demonstrate that the 

MDLs (40 CFR part 136, appendix B) are 

lower than one-third the regulatory 

compliance limit, or at least as low as 

the MDLs listed in this method, 

whichever are greater. If calibration will 

be affected by the change, the 

instrument must be recalibrated per 

Section 7. Once the modification is 

demonstrated to produce results 

equivalent or superior to results 

produced by this method, that 

modification may be used routinely 

thereafter, so long as the other 

requirements in this method are met 

(e.g., matrix spike/matrix spike 

duplicate recovery and relative percent 

difference). 

8.1.2.1.1 If a modification is to be 

applied to a specific discharge, the 

laboratory must prepare and analyze 

matrix spike/matrix spike duplicate 

(MS/MSD) samples (Section 8.3) and 

LCS samples (Section 8.4). The 

laboratory must include internal 

standards and surrogates (Section 8.7) in 

each of the samples. The MS/MSD and 

LCS samples must be fortified with the 

analytes of interest (Section 1.3.). If the 

modification is for nationwide use, MS/ 


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MSD samples must be prepared from a 

minimum of nine different discharges 

(See Section 8.1.2.1.2), and all QC 

acceptance criteria in this method must 

be met. This evaluation only needs to be 

performed once, other than for the 

routine QC required by this method (for 

example it could be performed by the 

vendor of the alternate materials) but 

any laboratory using that specific 

material must have the results of the 

study available. This includes a full data 

package with the raw data that will 

allow an independent reviewer to verify 

each determination and calculation 

performed by the laboratory (see Section 

8.1.2.2.5, items a–l). 

8.1.2.1.2 Sample matrices on which 

MS/MSD tests must be performed for 

nationwide use of an allowed 

modification: 

(a) Effluent from a POTW 

(b) ASTM D5905 Standard 

Specification for Substitute Wastewater 

(c) Sewage sludge, if sewage sludge 

will be in the permit 

(d) ASTM D1141 Standard 

Specification for Substitute Ocean 

Water, if ocean water will be in the 

permit 

(e) Untreated and treated wastewaters 

up to a total of nine matrix types (see 

http:water.epa.gov/scitech/wastetech/

guide/industry.cfm) for a list of 

industrial categories with existing 

effluent guidelines). 

At least one of the above wastewater 

matrix types must have at least one of 

the following characteristics: 

(i) Total suspended solids greater than 

40 mg/L 

(ii) Total dissolved solids greater than 

100 mg/L 

(iii) Oil and grease greater than 20 mg/ 

L 

(iv) NaCl greater than 120 mg/L 

(v) CaCO3 greater than 140 mg/L 

The interim acceptance criteria for 

MS, MSD recoveries that do not have 

recovery limits specified in Table 7, and 

recoveries for surrogates that do not 

have recovery limits specified in Table 

7, must be no wider than 60–140%, and 

the relative percent difference (RPD) of 

the concentrations in the MS and MSD 

that do not have RPD limits specified in 

Table 7 must be less than 30%. 

Alternatively, the laboratory may use 

the laboratory’s in-house limits if they 

are tighter. 

(f) A proficiency testing (PT) sample 

from a recognized provider, in addition 

to tests of the nine matrices (Section 

8.1.2.1.1). 

8.1.2.2 The laboratory is required to 

maintain records of modifications made 

to this method. These records include 

the following, at a minimum: 

8.1.2.2.1 The names, titles, street 

addresses, telephone numbers, and 

email addresses of the analyst(s) that 

performed the analyses and 

modification, and of the quality control 

officer that witnessed and will verify the 

analyses and modifications. 

8.1.2.2.2 A list of analytes, by name 

and CAS Registry Number. 

8.1.2.2.3 A narrative stating 

reason(s) for the modifications. 

8.1.2.2.4 Results from all quality 

control (QC) tests comparing the 

modified method to this method, 

including: 

(a) Calibration (Section 7). 

(b) Calibration verification/LCS 

(Section 8.4). 

(c) Initial demonstration of capability 

(Section 8.2). 

(d) Analysis of blanks (Section 8.5). 

(e) Matrix spike/matrix spike 

duplicate analysis (Section 8.3). 

(f) Laboratory control sample analysis 

(Section 8.4). 

8.1.2.2.5 Data that will allow an 

independent reviewer to validate each 

determination by tracing the instrument 

output (peak height, area, or other 

signal) to the final result. These data are 

to include: 

(a) Sample numbers and other 

identifiers. 

(b) Analysis dates and times. 

(c) Analysis sequence/run chronology. 

(d) Sample volume (Section 10). 

(e) Sample dilution (Section 13.2). 

(f) Instrument and operating 

conditions. 

(g) Column (dimensions, material, 

etc). 

(h) Operating conditions (temperature 

program, flow rate, etc). 

(i) Detector (type, operating 

conditions, etc). 

(j) Chromatograms, mass spectra, and 

other recordings of raw data. 

(k) Quantitation reports, data system 

outputs, and other data to link the raw 

data to the results reported. 

(l) A written Standard Operating 

Procedure (SOP). 

8.1.2.2.6 The individual laboratory 

wishing to use a given modification 

must perform the start-up tests in 

Section 8.1.2 (e.g., DOC, MDL), with the 

modification as an integral part of this 

method prior to applying the 

modification to specific discharges. 

Results of the DOC must meet the QC 

acceptance criteria in Table 7 for the 

analytes of interest (Section 1.3), and 

the MDLs must be equal to or lower 

than the MDLs in Table3 for the 

analytes of interest 

8.1.3 Before analyzing samples, the 

laboratory must analyze a blank to 

demonstrate that interferences from the 

analytical system, labware, and reagents 

are under control. Each time a batch of 

samples is analyzed or reagents are 

changed, a blank must be analyzed as a 

safeguard against laboratory 

contamination. Requirements for the 

blank are given in Section 8.5. 

8.1.4 The laboratory must, on an 

ongoing basis, spike and analyze a 

minimum of one sample, in duplicate, 

with the batch of samples run during a 

given 12-hour shift (see the note at 

Section 8.4). The laboratory must also 

spike and analyze, in duplicate, a 

minimum of 5% of all samples from a 

given site or discharge to monitor and 

evaluate method and laboratory 

performance on the sample matrix. The 

batch and site/discharge samples may 

be the same. The procedure for spiking 

and analysis is given in Section 8.3. 

8.1.5 The laboratory must, on an 

ongoing basis, demonstrate through 

analysis of a quality control check 

sample (laboratory control sample, LCS; 

on-going precision and recovery sample, 

OPR) that the measurement system is in 

control. This procedure is given in 

Section 8.4. 

8.1.6 The laboratory should 

maintain performance records to 

document the quality of data that is 

generated. This procedure is given in 

Section 8.8. 

8.1.7 The large number of analytes 

tested in performance tests in this 

method present a substantial probability 

that one or more will fail acceptance 

criteria when many analytes are tested 

simultaneously, and a re-test is allowed 

if this situation should occur. If, 

however, continued re-testing results in 

further repeated failures, the laboratory 

should document the failures (e.g., as 

qualifiers on results) and either avoid 

reporting results for analytes that failed 

or report the problem and failures with 

the data. Failure to report does not 

relieve a discharger or permittee of 

reporting timely results. Results for 

regulatory compliance must be 

accompanied by QC results that meet all 

acceptance criteria. 

8.2 Initial demonstration of 

capability (DOC)—To establish the 

ability to generate acceptable recovery 

and precision, the laboratory must 

perform the DOC in Sections 8.2.1 

through 8.2.6 for the analytes of interest. 

The laboratory must also establish 

MDLs for the analytes of interest using 

the MDL procedure at 40 CFR part 136, 

appendix B. The laboratory’s MDLs 

must be equal to or lower than those 

listed in Table 1 for those analytes 

which list MDL values, or lower than 

one-third the regulatory compliance 

limit, whichever is greater. For MDLs 

not listed in Table 1, the laboratory 

must determine the MDLs using the 

MDL procedure at 40 CFR part 136, 

appendix B under the same conditions 

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used to determine the MDLs for the 

analytes listed in Table 1. All 

procedures used in the analysis must be 

included in the DOC. 

8.2.1 For the DOC, a QC check 

sample concentrate containing each 

analyte of interest (Section 1.3) is 

prepared in methanol. The QC check 

sample concentrate must be prepared 

independently from those used for 

calibration, but may be from the same 

source as the second-source standard 

used for calibration verification/LCS 

(Sections 7.4 and 8.4). The concentrate 

should produce concentrations of the 

analytes of interest in water at the midpoint 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 mg/L were 

used to develop the QC acceptance 

criteria in Table 7. An alternative 

volume and sample concentration may 

be used, provided that all QC tests are 

performed and all QC acceptance 

criteria in this method are met. Also add 

an aliquot of the surrogate spiking 

solution (Section 6.7) and internal 

standard spiking solution (Section 

7.3.1.3) to the reagent-water aliquots. 

8.2.3 Analyze the four LCSs 

according to the method beginning in 

Section 10. 

8.2.4 Calculate the average percent 

recovery (x) and the standard deviation 

of the percent recovery (s) for each 

analyte using the four results. 

8.2.5 For each analyte, compare s 

and x with the corresponding 

acceptance criteria for precision and 

recovery in Table 7. For analytes in 

Tables 1 and 2 not listed in Table 7, 

DOC QC acceptance criteria must be 

developed by the laboratory. EPA has 

provided guidance for development of 

QC acceptance criteria (References 11 

and 12). If s and x for all analytes of 

interest meet the acceptance criteria, 

system performance is acceptable and 

analysis of blanks and samples may 

begin. If any individual s exceeds the 

precision limit or any individual x falls 

outside the range for recovery, system 

performance is unacceptable for that 

analyte. 

Note: The large number of analytes in 

Tables 1 and 2 present a substantial 

probability that one or more will fail at least 

one of the acceptance criteria when many or 

all analytes are determined simultaneously. 

Therefore, the analyst is permitted to conduct 

a ‘‘re-test’’ as described in Sec. 8.2.6. 

8.2.6 When one or more of the 

analytes tested fail at least one of the 

acceptance criteria, repeat the test for 

only the analytes that failed. If results 

for these analytes pass, system 

performance is acceptable and analysis 

of samples and blanks may proceed. If 

one or more of the analytes again fail, 

system performance is unacceptable for 

the analytes that failed the acceptance 

criteria. Correct the problem and repeat 

the test (Section 8.2). See Section 8.1.7 

for disposition of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between this pair 

of tests. 

8.3 Matrix spike and matrix spike 

duplicate (MS/MSD)—The laboratory 

must, on an ongoing basis, spike at least 

5% of the samples from each sample 

site being monitored in duplicate to 

assess accuracy (recovery and 

precision). The data user should 

identify the sample and the analytes of 

interest (Section 1.3) to be spiked. If 

direction cannot be obtained, the 

laboratory must spike at least one 

sample per batch of samples analyzed 

on a given 12-hour shift with the 

analytes in Table 1. Spiked sample 

results should be reported only to the 

data user whose sample was spiked, or 

as requested or required by a regulatory/ 

control authority, or in a permit. 

8.3.1 If, as in compliance 

monitoring, the concentration of a 

specific analyte will be checked against 

a regulatory concentration limit, the 

concentration of the spike should be at 

that limit; otherwise, the concentration 

of the spike should be one to five times 

higher than the background 

concentration determined in Section 

8.3.2, at or near the midpoint of the 

calibration range, or at the concentration 

in the LCS (Section 8.4) whichever 

concentration would be larger. 

8.3.2 Analyze one sample aliquot to 

determine the background concentration 

(B) of the each analyte of interest. If 

necessary, prepare a new check sample 

concentrate (Section 8.2.1) appropriate 

for the background concentration. Spike 

and analyze two additional sample 

aliquots, and determine the 

concentration after spiking (A1 and A2) 

of each analyte. Calculate the percent 

recoveries (P1 and P2) as 100 (A1–B)/T 

and 100 (A2–B)/T, where T is the known 

true value of the spike. Also calculate 

the relative percent difference (RPD) 

between the concentrations (A1 and A2) 

as 200 ⎢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 6, if desired. 

8.3.3.1 If any individual P falls 

outside the designated range for 

recovery in either aliquot, or the RPD 

limit is exceeded, the result for the 

analyte in the unspiked sample is 

suspect and may not be reported or used 

for permitting or regulatory compliance 

purposes. See Section 8.1.7 for 

disposition of failures. 

8.3.3.2 The acceptance criteria in 

Table 7 were calculated to include an 

allowance for error in measurement of 

both the background and spike 

concentrations, assuming a spike to 

background ratio of 5:1. This error will 

be accounted for to the extent that the 

spike to background ratio approaches 

5:1 (Reference 13). If spiking is 

performed at a concentration lower than 

20 mg/L, the laboratory must use either 

the QC acceptance criteria in Table 7, or 

optional QC acceptance criteria 

calculated for the specific spike 

concentration. To use the optional 

acceptance criteria: (1) Calculate 

recovery (X′) using the equation in Table 

8, substituting the spike concentration 

(T) for C; (2) Calculate overall precision 

(S′) using the equation in Table 8, 

substituting X′ for x; (3) Calculate the 

range for recovery at the spike 

concentration as (100 X′/T) ± 2.44(100 

S′/T)% (Reference 4). For analytes of 

interest in Tables 1 and 2 not listed in 

Table 7, QC acceptance criteria must be 

developed by the laboratory. EPA has 

provided guidance for development of 

QC acceptance criteria (References 11 

and 12). 

8.3.4 After analysis of a minimum of 

20 MS/MSD samples for each target 

analyte and surrogate, the laboratory 

must calculate and apply in-house QC 

limits for recovery and RPD of future 

MS/MSD samples (Section 8.3). The QC 

limits for recovery are calculated as the 

mean observed recovery ± 3 standard 

deviations, and the upper QC limit for 

RPD is calculated as the mean RPD plus 

3 standard deviations of the RPDs. The 

in-house QC limits must be updated at 

least every two years and re-established 

after any major change in the analytical 

instrumentation or process. At least 

80% of the analytes tested in the MS/ 

MSD must have in-house QC acceptance 

criteria that are tighter than those in 

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Table 7. If an in-house QC limit for the 

RPD is greater than the limit in Table 7, 

then the limit in Table 7 must be used. 

Similarly, if an in-house lower limit for 

recovery is below the lower limit in 

Table 7, then the lower limit in Table 7 

must be used, and if an in-house upper 

limit for recovery is above the upper 

limit in Table 7, then the upper limit in 

Table 7 must be used. The laboratory 

must evaluate surrogate recovery data in 

each sample against its in-house 

surrogate recovery limits. The laboratory 

may use 60–140% as interim acceptance 

criteria for surrogate recoveries until inhouse limits are developed. 

8.4 Calibration verification/

laboratory control sample (LCS)—The 

working calibration curve or RF must be 

verified at the beginning of each 12-hour 

shift by the measurement of an LCS. 

Note: The 12-hour shift begins after 

analysis of the blank that follows the LCS 

and ends 12 hours later. The blank is outside 

of the 12-hour shift. The MS and MSD are 

treated as samples and are analyzed within 

the 12-hour shift. 

8.4.1 Prepare the LCS by adding QC 

check sample concentrate (Section 

8.2.1) to reagent water. Include all 

analytes of interest (Section 1.3) in the 

LCS. The LCS may be the same sample 

prepared for the DOC (Section 8.2.1). 

The volume of reagent water must be 

the same as the volume used for the 

sample, blank (Section 8.5), and MS/

MSD (Section 8.3). Also add an aliquot 

of the surrogate solution (Section 6.7) 

and internal standard solution (Section 

7.3.1.3). The concentration of the 

analytes in reagent water should be the 

same as the concentration in the DOC 

(Section 8.2.2). 

8.4.2 Analyze the LCS prior to 

analysis of field samples in the batch of 

samples analyzed during the 12-hour 

shift (see the Note at Section 8.4). 

Determine the concentration (A) of each 

analyte. Calculate the percent recovery 

(Q) as 100 (A/T) %, where T is the true 

value of the concentration in the LCS. 

8.4.3 Compare the percent recovery 

(Q) for each analyte with its 

corresponding QC acceptance criterion 

in Table 7. For analytes of interest in 

Tables 1 and 2 not listed in Table 7, use 

the QC acceptance criteria developed for 

the MS/MSD (Section 8.3.3.2). If the 

recoveries for all analytes of interest fall 

within their respective QC acceptance 

criteria, analysis of blanks and field 

samples may proceed. If any individual 

Q falls outside the range, proceed 

according to Section 8.4.4. 

Note: The large number of analytes in 

Tables 1–2 present a substantial probability 

that one or more will fail the acceptance 

criteria when all analytes are tested 

simultaneously. Because a re-test is allowed 

in event of failure (Sections 8.1.7 and 8.4.3), 

it may be prudent to analyze two LCSs 

together and evaluate results of the second 

analysis against the QC acceptance criteria 

only if an analyte fails the first test. 

8.4.4 Repeat the test only for those 

analytes that failed to meet the 

acceptance criteria (Q). If these analytes 

now pass, system performance is 

acceptable and analysis of blanks and 

samples may proceed. Repeated failure, 

however, will confirm a general 

problem with the measurement system. 

If this occurs, repeat the test using a 

fresh LCS (Section 8.2.2) or an LCS 

prepared with a fresh QC check sample 

concentrate (Section 8.2.1), or perform 

and document system repair. 

Subsequent to repair, repeat the 

calibration verification/LCS test 

(Section 8.4). If the acceptance criteria 

for Q cannot be met, re-calibrate the 

instrument (Section 7). If failure of the 

LCS indicates a systemic problem with 

samples analyzed during the 12-hour 

shift, re-analyze the samples analyzed 

during that 12-hour shift. See Section 

8.1.7 for disposition of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between this pair 

of tests. 

8.4.5 After analysis of 20 LCS 

samples, the laboratory must calculate 

and apply in-house QC limits for 

recovery to future LCS samples (Section 

8.4). Limits for recovery in the LCS are 

calculated as the mean recovery ±3 

standard deviations. A minimum of 

80% of the analytes tested for in the 

LCS must have QC acceptance criteria 

tighter than those in Table 7. Many of 

the analytes and surrogates may not 

contain recommended acceptance 

criteria. The laboratory should use 60– 

140% as interim acceptance criteria for 

recoveries of spiked analytes and 

surrogates that do not have recovery 

limits specified in Table 7, until inhouse LCS and surrogate limits are 

developed. If an in-house lower limit for 

recovery is lower than the lower limit in 

Table 7, the lower limit in Table 7 must 

be used, and if an in-house upper limit 

for recovery is higher than the upper 

limit in Table 7, the upper limit in Table 

7 must be used. 

8.5 Blank—A blank must be 

analyzed at the beginning of each 12- 

hour shift to demonstrate freedom from 

contamination. A blank must also be 

analyzed after a sample containing a 

high concentration of an analyte or 

potentially interfering compound to 

demonstrate freedom from carry-over. 

8.5.1 Spike the internal standards 

and surrogates into the blank. Analyze 

the blank immediately after analysis of 

the LCS (Section 8.4) and prior to 

analysis of the MS/MSD and samples to 

demonstrate freedom from 

contamination. 

8.5.2 If any analyte of interest is 

found in the blank: (1) at a 

concentration greater than the MDL for 

the analyte, (2) at a concentration 

greater than one-third the regulatory 

compliance limit, or (3) at a 

concentration greater than one-tenth the 

concentration in a sample analyzed 

during the 12-hour shift (Section 8.4), 

whichever is greater; analysis of 

samples must be halted and samples 

affected by the blank must be reanalyzed. Samples must be associated 

with an uncontaminated blank before 

they may be reported or used for 

permitting or regulatory compliance 

purposes. 

8.6 Surrogate recoveries—Spike the 

surrogates into all samples, blanks, 

LCSs, and MS/MSDs. Compare 

surrogate recoveries against the QC 

acceptance criteria in Table 7. For 

surrogates in Table 5 without QC 

acceptance criteria in Table 7, and for 

other surrogates that may be used by the 

laboratory, limits must be developed by 

the laboratory. EPA has provided 

guidance for development of QC 

acceptance criteria (References 11 and 

12). If any recovery fails its criteria, 

attempt to find and correct the cause of 

the failure. Surrogate recoveries from 

the blank and LCS may be used as pass/ 

fail criteria by the laboratory or as 

required by a regulatory authority, or 

may be used to diagnose problems with 

the analytical system. 

8.7 Internal standard responses. 

8.7.1 Calibration verification/LCS— 

The responses (GC peak heights or 

areas) of the internal standards in the 

calibration verification/LCS must be 

within 50% to 200% (1⁄2 to 2x) of their 

respective responses in the mid-point 

calibration standard. If they are not, 

repeat the LCS test using a fresh QC 

check sample (Section 8.4.1) or perform 

and document system repair. 

Subsequent to repair, repeat the 

calibration verification/LCS test 

(Section 8.4). If the responses are still 

not within 50% to 200%, re-calibrate 

the instrument (Section 7) and repeat 

the calibration verification/LCS test. 

8.7.2 Samples, blanks, and MS/

MSDs—The responses (GC peak heights 

or areas) of the internal standards in 

each sample, blank, and MS/MSD must 

be within 50% to 200% (1⁄2 to 2x) of its 

respective response in the most recent 

LCS. If, as a group, all internal standard 

are not within this range, perform and 

document system repair, repeat the 

calibration verification/LCS test 

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(Section 8.4), and re-analyze the affected 

samples. If a single internal standard is 

not within the 50% to 200% range, use 

an alternate internal standard for 

quantitation of the analyte referenced to 

the affected internal standard. 

8.8 As part of the QC program for 

the laboratory, control charts or 

statements of accuracy for wastewater 

samples must be assessed and records 

maintained periodically (see 40 CFR 

136.7(c)(1)(viii)). After analysis of five 

or more spiked wastewater samples as 

in Section 8.3, calculate the average 

percent recovery (x) and the standard 

deviation of the percent recovery (sp). 

Express the accuracy assessment as a 

percent interval from x ¥2sp to x +2sp. 

For example, if x = 90% and sp = 10%, 

the accuracy interval is expressed as 70– 

110%. Update the accuracy assessment 

for each analyte on a regular basis (e.g., 

after each 5–10 new accuracy 

measurements). 

8.9 It is recommended that the 

laboratory adopt additional quality 

assurance practices for use with this 

method. The specific practices that are 

most productive depend upon the needs 

of the laboratory and the nature of the 

samples. Field duplicates may be 

analyzed to assess the precision of 

environmental measurements. 

Whenever possible, the laboratory 

should analyze standard reference 

materials and participate in relevant 

performance evaluation studies. 

9. Sample Collection, Preservation, and 

Handling 

9.1 Collect the sample as a grab 

sample in a glass container having a 

total volume of at least 25 mL. Fill the 

sample bottle just to overflowing in 

such a manner that no air bubbles pass 

through the sample as the bottle is being 

filled. Seal the bottle so that no air 

bubbles are entrapped in it. If needed, 

collect additional sample(s) for the MS/ 

MSD (Section 8.3). 

9.2 Ice or refrigerate samples at <6 

°C from the time of collection until 

analysis, but do not freeze. If residual 

chlorine is present, add sodium 

thiosulfate preservative (10 mg/40 mL is 

sufficient for up to 5 ppm Cl2) to the 

empty sample bottle just prior to 

shipping to the sampling site. Any 

method suitable for field use may be 

employed to test for residual chlorine 

(Reference 14). Field test kits are also 

available for this purpose. If sodium 

thiosulfate interferes in the 

determination of the analytes, an 

alternate preservative (e.g., ascorbic acid 

or sodium sulfite) may be used. If 

preservative has been added, shake the 

sample vigorously for one minute. 

Maintain the hermetic seal on the 

sample bottle until time of analysis. 

9.3 If acrolein is to be determined, 

analyze the sample within 3 days. To 

extend the holding time to 14 days, 

acidify a separate sample to pH 4–5 

with HCl using the procedure in Section 

9.7. 

9.4 Experimental evidence indicates 

that some aromatic compounds, notably 

benzene, toluene, and ethyl benzene are 

susceptible to rapid biological 

degradation under certain 

environmental conditions (Reference 3). 

Refrigeration alone may not be adequate 

to preserve these compounds in 

wastewaters for more than seven days. 

To extend the holding time for aromatic 

compounds to 14 days, acidify the 

sample to approximately pH 2 using the 

procedure in Section 9.7. 

9.5 If halocarbons are to be 

determined, either use the acidified 

aromatics sample in Section 9.4 or 

acidify a separate sample to a pH of 

about 2 using the procedure in Section 

9.7. Aqueous samples should not be 

preserved with acid if the ethers in 

Table 2, or the alcohols that they would 

form upon hydrolysis, are of analytes of 

interest. 

9.6 The ethers listed in Table 2 are 

prone to hydrolysis at pH 2 when a 

heated purge is used. Aqueous samples 

should not be acid preserved if these 

ethers are of interest, or if the alcohols 

they would form upon hydrolysis are of 

interest and the ethers are anticipated to 

present. 

9.7 Sample acidification—Collect 

about 500 mL of sample in a clean 

container and adjust the pH of the 

sample to 4–5 for acrolein (Section 9.3), 

or to about 2 for the aromatic 

compounds (Section 9.4) by adding 1+1 

HCl while swirling or stirring. Check the 

pH with narrow range pH paper. Fill a 

sample container as described in 

Section 9.1. Alternatively, fill a 

precleaned vial (Section 5.1.1) that 

contains approximately 0.25 mL of 1+1 

HCl with sample as in Section 9.1. If 

preserved using this alternative 

procedure, the pH of the sample can be 

verified to be <2 after some of the 

sample is removed for analysis. 

Acidification will destroy 2- 

chloroethylvinyl ether; therefore, 

determine 2-chloroethylvinyl ether from 

the unacidified sample. 

9.8 All samples must be analyzed 

within 14 days of collection (Reference 

3), unless specified otherwise in 

Sections 9.3–9.7. 

10. Sample Purging and Gas 

Chromatography 

10.1 The footnote to Table 3 gives 

the suggested GC column and operating 

conditions. Included in Table 3 are 

retention times and MDLs that can be 

achieved under these conditions. 

Sections 10.2 through 10.7 suggest 

procedures that may be used with a 

manual purge-and-trap system. Autosamplers and other columns or 

chromatographic conditions may be 

used if requirements in this method are 

met. 

10.2 Attach the trap inlet to the 

purging device, and set the purge-andtrap system to purge (Figure 3). Open 

the syringe valve located on the purging 

device sample introduction needle. 

10.3 Allow the sample to come to 

ambient temperature prior to pouring an 

aliquot into the syringe. Remove the 

plunger from a syringe and attach a 

closed syringe valve. Open the sample 

bottle (or standard) and carefully pour 

the sample into the syringe barrel to just 

short of overflowing. Replace the 

syringe plunger and compress the 

sample. Open the syringe valve and vent 

any residual air while adjusting the 

sample volume. Since this process of 

taking an aliquot destroys the validity of 

the sample for future analysis, the 

analyst should fill a second syringe at 

this time to protect against possible loss 

of data. Add the surrogate spiking 

solution (Section 6.7) and internal 

standard spiking solution (Section 

7.3.1.3) through the valve bore, then 

close the valve. The surrogate and 

internal standards may be mixed and 

added as a single spiking solution. 

Autosamplers designed for purge-andtrap 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 lessvolatile analytes onto the trap, yet short 

enough to prevent blowing the morevolatile 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 purgeand-trap system to the desorb mode 

(Figure 4), and begin to temperature 

program the gas chromatograph. 

Introduce the trapped materials to the 

GC column by rapidly heating the trap 

to the desorb temperature while 

backflushing the trap with carrier gas at 

the flow rate and for the time necessary 

to desorb the analytes of interest. The 

optimum temperature, flow rate, and 

time should be determined by test. The 

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same temperature, desorb time, and 

flow rate must be used for all 

calibration, QC, and field samples. If 

heating of the trap does not result in 

sharp peaks for the early eluting 

analytes, the GC column may be used as 

a secondary trap by cooling to an 

ambient or subambient temperature. To 

avoid carry-over and interferences, 

maintain the trap at the desorb 

temperature and flow rate until the 

analytes, interfering compounds, and 

excess water are desorbed. The 

optimum conditions should be 

determined by test. 

10.7 Start MS data acquisition at the 

start of the desorb cycle and stop data 

collection when the analytes of interest, 

potentially interfering compounds, and 

water have eluted (see the footnote to 

Table 3 for conditions). 

10.8 Cool the trap to the purge 

temperature and return the trap to the 

purge mode (Figure 3). When the trap is 

cool, the next sample can be analyzed. 

11. Performance Tests 

11.1 At the beginning of each 12- 

hour shift during which analyses are to 

be performed, GC/MS performance must 

be verified before blanks or samples 

may be analyzed (Section 8.4). Use the 

instrument operating conditions in the 

footnotes to Table 3 for these 

performance tests. Alternate conditions 

may be used so as long as all QC 

requirements are met. 

11.2 BFB—Inject 50 ng of BFB 

solution directly on the column. 

Alternatively, add BFB to reagent water 

or an aqueous standard such that 50 ng 

or less of BFB will be introduced into 

the GC. Analyze according to Section 

10. Confirm that all criteria in Section 

7.3.2.2 and Table 4 are met. If all criteria 

are not met, perform system repair, 

retune the mass spectrometer, and 

repeat the test until all criteria are met. 

11.3 GC resolution—There must be a 

valley between 1,2-dibromoethane and 

chlorobenzene, and the height of the 

valley must not exceed 25 percent of the 

shorter of the two peaks. For an 

alternate GC column, apply this valley 

height criterion to two representative 

GC peaks separated by no more than 7 

seconds. 

11.4 Verify calibration with the LCS 

(Section 8.4) after the criteria for BFB 

are met (Reference 15) and prior to 

analysis of a blank or sample. After 

verification, analyze a blank (Section 

8.5) to demonstrate freedom from 

contamination and carry-over at the 

MDL. 

12. Qualitative Identification 

12.1 Target analytes are identified 

by comparison of results from analysis 

of a sample or blank with data stored in 

the GC/MS data system (Section 

7.3.2.3). Identification of an analyte is 

confirmed per Sections 12.1.1 through 

12.1.4. 

12.1.1 The signals for all 

characteristic m/z’s stored in the data 

system (Section 7.3.2.3) for each analyte 

of interest must be present and must 

maximize within the same two 

consecutive scans. 

12.1.2 Based on the relative 

retention time (RRT), the RRT for the 

analyte must be within ± 0.06 of the 

RRT of the analyte in the LCS run at the 

beginning of the shift (Section 8.4). 

Relative retention time is used to 

establish the identification window 

because it compensates for small 

changes in the GC temperature program 

whereas the absolute retention time 

does not (see Section 7.3.1.2). 

Note: RRT is a unitless quantity (see Sec. 

20.2), although some procedures refer to 

‘‘RRT units’’ in providing the specification 

for the agreement between the RRT values in 

the sample and the LCS or other standard. 

12.1.3 Either (1) the background 

corrected EICP areas, or (2) the corrected 

relative intensities of the mass spectral 

peaks at the GC peak maximum, must 

agree within 50% to 200% (1⁄2 to 2 

times) for all m/z’s in the reference mass 

spectrum stored in the data system 

(Section 7.3.2.3), or from a reference 

library. For example, if a peak has an 

intensity of 20% relative to the base 

peak, the analyte is identified if the 

intensity of the peak in the sample is in 

the range of 10% to 40% of the base 

peak. 

12.1.4 The m/z’s present in the 

acquired mass spectrum for the sample 

that are not present in the reference 

mass spectrum must be accounted for by 

contaminant or background m/z’s. A 

reference library may be helpful to 

identify and account for background or 

contaminant m/z’s. If the acquired mass 

spectrum is contaminated, or if 

identification is ambiguous, an 

experienced spectrometrist (Section 1.6) 

must determine the presence or absence 

of the compound. 

12.2 Structural isomers that have 

very similar mass spectra can be 

identified only if the resolution between 

authentic isomers in a standard mix is 

acceptable. Acceptable resolution is 

achieved if the baseline to valley height 

between the isomers is less than 50% of 

the height of the shorter of the two 

peaks. Otherwise, structural isomers are 

identified as isomeric pairs. 

13. Calculations 

13.1 When an analyte has been 

identified, quantitation of that analyte is 

based on the integrated abundance from 

the EICP of the primary characteristic 

m/z in Table 5 or 6. Calculate the 

concentration using the response factor 

(RF) determined in Section 7.3.3 and 

Equation 2. If a calibration curve was 

used, calculate the concentration using 

the regression equation for the curve. If 

the concentration of an analyte exceeds 

the calibration range, dilute the sample 

by the minimum amount to bring the 

concentration into the calibration range, 

and re-analyze. Determine a dilution 

factor (DF) from the amount of the 

dilution. For example, if the extract is 

diluted by a factor of 2, DF = 2. 

Where: 

Cs = Concentration of the analyte in the 

sample, and the other terms are as defined 

in Section 7.3.3. 

13.2 Reporting of results. 

As noted in Section 1.4.1, EPA has 

promulgated this method at 40 CFR part 

136 for use in wastewater compliance 

monitoring under the National Pollutant 

Discharge Elimination System (NPDES). 

The data reporting practices described 

here are focused on such monitoring 

needs and may not be relevant to other 

uses of the method. 

13.2.1 Report results for wastewater 

samples in mg/L without correction for 

recovery. (Other units may be used if 

required by in a permit.) Report all QC 

data with the sample results. 

13.2.2 Reporting level. 

Unless otherwise specified in by a 

regulatory authority or in a discharge 

permit, results for analytes that meet the 

identification criteria are reported down 

to the concentration of the ML 

established by the laboratory through 

calibration of the instrument (see 

Section 7.3.2 and the glossary for the 

derivation of the ML). EPA considers 

the terms ‘‘reporting limit,’’ 

‘‘quantitation limit,’’ and ‘‘minimum 

level’’ to be synonymous. 

13.2.2.1 Report a result for each 

analyte in each sample, blank, or 

standard at or above the ML to 3 

significant figures. Report a result for 

each analyte found in each sample 

below the ML as ‘‘<ML,’’ or as required 

by the regulatory authority or permit. 

Results are reported without blank 

subtraction unless requested or required 

by a regulatory authority or in a permit. 

In this case, both the sample result and 

the blank results must be reported 

together. 

13.2.2.2 In addition to reporting 

results for samples and blanks 

separately, the concentration of each 

analyte in a blank associated with the 


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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. 

13.2.2.3 Report a result for an 

analyte found in a sample 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 

7). This may require reporting results for 

some analytes from different analyses. 

13.2.3 Results from tests performed 

with an analytical system that is not in 

control (i.e., that does not meet 

acceptance criteria for all of QC tests in 

this method) must not be reported or 

otherwise used for permitting or 

regulatory compliance purposes, but do 

not relieve a discharger or permittee of 

reporting timely results. If the holding 

time would be exceeded for a reanalysis of the sample, the regulatory/

control authority should be consulted 

for disposition. 

14. Method Performance 

14.1 This method was tested by 15 

laboratories using reagent water, 

drinking water, surface water, and 

industrial wastewaters spiked at six 

concentrations over the range 5–600 mg/ 

L (References 4 and 16). 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 8. 

14.2 As noted in Sec. 1.1, this 

method was validated through an 

interlaboratory study conducted more 

than 29 years ago. However, the 

fundamental chemistry principles used 

in this method remain sound and 

continue to apply. 

15. Pollution Prevention 

15.1 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. 

15.2 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. 

15.3 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. 

16. Waste Management 

16.1 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). 

16.2 Samples at pH <2, or pH >12, 

are hazardous and must be neutralized 

before being poured down a drain, or 

must be handled and disposed of as 

hazardous waste. 

16.3 Many analytes in this method 

decompose above 500 °C. Low-level 

waste such as absorbent paper, tissues, 

and plastic gloves may be burned in an 

appropriate incinerator. Gross quantities 

of neat or highly concentrated solutions 

of toxic or hazardous chemicals should 

be packaged securely and disposed of 

through commercial or governmental 

channels that are capable of handling 

these types of wastes. 

16.4 For further information on 

waste management, consult The Waste 

Management Manual for Laboratory 

Personnel and Less is Better-Laboratory 

Chemical Management for Waste 

Reduction, available from the American 

Chemical Society’s Department of 

Government Relations and Science 

Policy, 1155 16th Street NW., 

Washington, DC 20036, 202/872–4477. 

17. References 

1. Bellar, T.A. and Lichtenberg, J.J. 

‘‘Determining Volatile Organics at 

Microgram-per-Litre Levels by Gas 

Chromatography,’’ Journal American 

Water Works Association, 66, 739 (1974). 

2. ‘‘Sampling and Analysis Procedures for 

Screening of Industrial Effluents for 

Priority Pollutants,’’ U.S. Environmental 

Protection Agency, Environmental 

Monitoring and Support Laboratory, 

Cincinnati, Ohio 45268, March 1977, 

Revised April 1977. 

3. Bellar, T.A. and Lichtenberg, J.J. ‘‘SemiAutomated Headspace Analysis of 

Drinking Waters and Industrial Waters 

for Purgeable Volatile Organic 

Compounds,’’ Measurement of Organic 

Pollutants in Water and Wastewater, C.E. 

Van Hall, editor, American Society for 

Testing and Materials, Philadelphia, PA. 

Special Technical Publication 686, 1978. 

4. ‘‘EPA Method Study 29 EPA Method 624- 

Purgeables,’’ EPA 600/4–84–054, 

National Technical Information Service, 

PB84–209915, Springfield, Virginia 

22161, June 1984. 

5. 40 CFR part 136, appendix B. 

6. ‘‘Method Detection Limit for Methods 624 

and 625,’’ Olynyk, P., Budde, W.L., and 

Eichelberger, J.W. Unpublished report, 

May 14, 1980. 

7. ‘‘Carcinogens-Working With Carcinogens,’’ 

Department of Health, Education, and 

Welfare, Public Health Service, Center 

for Disease Control, National Institute for 

Occupational Safety and Health, 

Publication No. 77–206, August 1977. 

8. ‘‘OSHA Safety and Health Standards, 

General Industry,’’ (29 CFR part 1910), 

Occupational Safety and Health 

Administration, OSHA 2206 (Revised, 

January 1976). 

9. ‘‘Safety in Academic Chemistry 

Laboratories,’’ American Chemical 

Society Publication, Committee on 

Chemical Safety, 7th Edition, 2003. 

10. 40 CFR 136.6(b)(5)(x). 

11. 40 CFR 136.6(b)(2)(i). 

12. Protocol for EPA Approval of New 

Methods for Organic and Inorganic 

Analytes in Wastewater and Drinking 

Water (EPA–821–B–98–003) March 1999 

13. Provost, L.P. and Elder, R.S. 

‘‘Interpretation of Percent Recovery 

Data,’’ American Laboratory, 15, 58–63 

(1983). 

14. 40 CFR 136.3(a), Table IB, Chlorine— 

Total residual 

15. Budde, W.L. and Eichelberger, J.W. 

‘‘Performance Tests for the Evaluation of 

Computerized Gas Chromatography/

Mass Spectrometry Equipment and 

Laboratories,’’ EPA–600/4–80–025, U.S. 

Environmental Protection Agency, 

Environmental Monitoring and Support 

Laboratory, Cincinnati, Ohio 45268, 

April 1980. 

16. ‘‘Method Performance Data for Method 

624,’’ Memorandum from R. Slater and 

T. Pressley, U.S. Environmental 

Protection Agency, Environmental 

Monitoring and Support Laboratory, 

Cincinnati, Ohio 45268, January 17, 

1984. 

18. Tables 

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TABLE 1—PURGEABLES 1

Analyte CAS Registry No. MDL (μg/L) 2 ML (μg/L) 3

Acrolein ...................................................................................................................... 107–02–8 

Acrylonitrile ................................................................................................................ 107–13–1 

Benzene ..................................................................................................................... 71–43–2 4.4 13.2 

Bromodichloromethane .............................................................................................. 75–27–4 2.2 6.6 

Bromoform ................................................................................................................. 75–25–2 4.7 14.1 

Bromomethane .......................................................................................................... 74–83–9 

Carbon tetrachloride .................................................................................................. 56–23–5 2.8 8.4 

Chlorobenzene ........................................................................................................... 108–90–7 6.0 18.0 

Chloroethane ............................................................................................................. 75–00–3 

2-Chloroethylvinyl ether ............................................................................................. 110–75–8 

Chloroform ................................................................................................................. 67–66–3 1.6 4.8 

Chloromethane .......................................................................................................... 74–87–3 

Dibromochloromethane .............................................................................................. 124–48–1 3.1 9.3 

1,2-Dichlorobenzene .................................................................................................. 95–50–1 

1,3-Dichlorobenzene .................................................................................................. 541–73–1 

1,4-Dichlorobenzene .................................................................................................. 106–46–7 

1,1-Dichloroethane ..................................................................................................... 75–34–3 4.7 14.1 

1,2-Dichloroethane ..................................................................................................... 107–06–2 2.8 8.4 

1,1-Dichloroethene ..................................................................................................... 75–35–4 2.8 8.4 

trans-1,2-Dichloroethene ........................................................................................... 156–60–5 1.6 4.8 

1,2-Dichloropropane .................................................................................................. 78–87–5 6.0 18.0 

cis-1,3-Dichloropropene ............................................................................................. 10061–01–5 5.0 15.0 

trans-1,3-Dichloropropene ......................................................................................... 10061–02–6 

Ethyl benzene ............................................................................................................ 100–41–4 7.2 21.6 

Methylene chloride ..................................................................................................... 75–09–2 2.8 8.4 

1,1,2,2-Tetrachloroethane .......................................................................................... 79–34–5 6.9 20.7 

Tetrachloroethene ...................................................................................................... 127–18–4 4.1 12.3 

Toluene ...................................................................................................................... 108–88–3 6.0 18.0 

1,1,1-Trichloroethane ................................................................................................. 71–55–6 3.8 11.4 

1,1,2-Trichloroethane ................................................................................................. 79–00–5 5.0 15.0 

Trichloroethene .......................................................................................................... 79–01–6 1.9 5.7 

Vinyl chloride ............................................................................................................. 75–01–4 

1All the analytes in this table are Priority Pollutants (40 CFR part 423, appendix A) 

2 MDL values from the 1984 promulgated version of Method 624 

3 ML = Minimum Level—see Glossary for definition and derivation 

TABLE 2—ADDITIONAL PURGEABLES

Analyte CAS Registry 

Acetone 1 .............................. 67–64–1 

Acetonitrile 2 .......................... 75–05–8 

Allyl alcohol 1 ........................ 107–18–6 

Allyl chloride ......................... 107–05–1 

t-Amyl ethyl ether (TAEE) .... 919–94–8 

t-Amyl methyl ether (TAME) 994–058 

Benzyl chloride ..................... 100–44–7 

Bromoacetone 2 .................... 598–31–2 

Bromobenzene ..................... 108–86–1 

Bromochloromethane ........... 74–97–5 

1,3-Butadiene ....................... 106–99–0 

n-Butanol 1 ............................ 71–36–3 

2-Butanone (MEK) 1 2 ............ 78–93–3 

t-Butyl alcohol (TBA) ............ 75–65–0 

n-Butylbenzene ..................... 104–51–8 

sec-Butylbenzene ................. 135–98–8 

t-Butylbenzene ...................... 98–06–6 

t-Butyl ethyl ether (ETBE) .... 637–92–3 

Carbon disulfide .................... 75–15–0 

Chloral hydrate 2 ................... 302–17–0 

Chloroacetonitrile 1 ................ 107–14–2 

1-Chlorobutane ..................... 109–69–3 

Chlorodifluoromethane ......... 75–45–6 

2-Chloroethanol 2 ............ 107–07–3 

bis (2-Chloroethyl) sulfide 2 ............................ 505–60–2 

1-Chlorohexanone ................ 20261–68–1 

Chloroprene (2-chloro-1,3- 

butadiene) ......................... 126–99–8 

3-Chloropropene ................... 107–05–1 

3-Chloropropionitrile ............. 542–76–7 

TABLE 2—ADDITIONAL PURGEABLES— 

Continued 

Analyte CAS Registry 

2-Chlorotoluene .................... 95–49–8 

4-Chlorotoluene .................... 106–43–4 

Crotonaldehyde 1 2 ................ 123–73–9 

Cyclohexanone ..................... 108–94–1 

1,2-Dibromo-3-chloropropane 96–12–8 

1,2-Dibromoethane ............... 106–93–4 

Dibromomethane .................. 74–95–3 

cis-1,4-Dichloro-2-butene ..... 1476–11–5 

trans-1,4-Dichloro-2-butene .. 110–57–6 

cis-1,2-Dichloroethene .......... 156–59–2 

Dichlorodifluoromethane ....... 75–71–8 

1,3-Dichloropropane ............. 142–28–9 

2,2-Dichloropropane ............. 590–20–7 

1,3-Dichloro-2-propanol 2 ...... 96–23–1 

1,1-Dichloropropene ............. 563–58–6 

cis-1,3-Dichloropropene ........ 10061–01–5 

1:2,3:4-Diepoxybutane .......... 1464–53–5 

Diethyl ether ......................... 60–29–7 

Diisopropyl ether (DIPE) ....... 108–20–3 

1,4-Dioxane 2 ........................ 123–91–1 

Epichlorohydrin 2 ................... 106–89–8 

Ethanol 2 ............................... 64–17–5 

Ethyl acetate 2 ....................... 141–78–6 

Ethyl methacrylate ................ 97–63–2 

Ethylene oxide 2 .................... 75–21–8 

Hexachlorobutadiene ............ 87–63–3 

Hexachloroethane ................. 67–72–1 

2-Hexanone 2 ........................ 591–78–6 

Iodomethane ......................... 74–88–4 

Isobutyl alcohol 1 ................... 78–83–1 

TABLE 2—ADDITIONAL PURGEABLES— 

Continued 

Analyte CAS Registry 

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 

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TABLE 2—ADDITIONAL PURGEABLES— 

Continued 

Analyte CAS Registry 

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 

°C. 

2 May be detectable at a purge temperature 

of 80 °C. 3 Determined in combination separated by 

GC column. Most GC columns will resolve oxylene from m+p-xylene. Report using the 

CAS number for the individual xylene or the 

combination, as determined. 

TABLE 3—EXAMPLE RETENTION TIMES

Analyte Retention 

time (min) 

Chloromethane ......................... 3.68 

Vinyl chloride ............................ 3.92 

Bromomethane ......................... 4.50 

Chloroethane ............................ 4.65 

Trichlorofluoromethane ............. 5.25 

Diethyl ether ............................. 5.88 

Acrolein ..................................... 6.12 

1,1-Dichloroethene ................... 6.30 

Acetone ..................................... 6.40 

TABLE 3—EXAMPLE RETENTION

TIMES—Continued 

Analyte Retention 

time (min) 

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 

TABLE 3—EXAMPLE RETENTION

TIMES—Continued 

Analyte Retention 

time (min) 

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 μm widebore DB–624. 

Conditions: 40°C for 4 min, 9°C/min to 

200°C, 20°C/min (or higher) to 250°C, hold for 

20 min at 250°C to remove water. 

Carrier gas flow rate: 6–7 mL/min at 40°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. 

1Abundance criteria are for a quadrupole 

mass spectrometer; contact the manufacturer 

for criteria for other types of mass 

spectrometers. 

TABLE 5—SUGGESTED SURROGATE AND INTERNAL STANDARDS

Analyte Retention time 

(min) 1 Primary m/z Secondary m/z’s 

Benzene-d6 .......................................................................................................................... 10.95 84 ....................

4-Bromofluorobenzene ........................................................................................................ 18.80 95 174, 176 

Bromochloromethane ........................................................................................................... 9.88 128 49, 130, 51 

2-Bromo-1-chloropropane .................................................................................................... 14.80 77 79, 156 

2-Butanone-d5 ...................................................................................................................... 9.33 77 ....................

Chloroethane-d5 ................................................................................................................... 4.63 71 ....................

Chloroform-13C .................................................................................................................... 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 

1For chromatographic conditions, see the footnote to Table 3. 

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TABLE 6—CHARACTERISTIC M/Z’S FOR PURGEABLE ORGANICS

Analyte Primary m/z Secondary m/z’s 

Chloromethane ......................................................................................................... 50 52. 

Bromomethane ......................................................................................................... 94 96. 

Vinyl chloride ............................................................................................................ 62 64. 

Chloroethane ............................................................................................................ 64 66. 

Methylene chloride ................................................................................................... 84 49, 51, and 86. 

Trichlorofluoromethane ............................................................................................. 101 103. 

1,1-Dichloroethene ................................................................................................... 96 61 and 98. 

1,1-Dichloroethane ................................................................................................... 63 65, 83, 85, 98, and 100. 

trans-1,2-Dichloroethene .......................................................................................... 96 61 and 98. 

Chloroform ................................................................................................................ 83 85. 

1,2-Dichloroethane ................................................................................................... 98 62, 64, and 100. 

1,1,1-Trichloroethane ................................................................................................ 97 99, 117, and 119. 

Carbon tetrachloride ................................................................................................. 117 119 and 121. 

Bromodichloromethane ............................................................................................. 83 127, 85, and 129. 

1,2-Dichloropropane ................................................................................................. 63 112, 65, and 114. 

trans-1,3-Dichloropropene ........................................................................................ 75 77. 

Trichloroethene ......................................................................................................... 130 95, 97, and 132. 

Benzene .................................................................................................................... 78 

Dibromochloromethane ............................................................................................ 127 129, 208, and 206. 

1,1,2-Trichloroethane ................................................................................................ 97 83, 85, 99, 132, and 134. 

cis-1,3-Dichloropropene ............................................................................................ 75 77. 

2-Chloroethylvinyl ether ............................................................................................ 106 63 and 65. 

Bromoform ................................................................................................................ 173 171, 175, 250, 252, 254, and 256. 

1,1,2,2-Tetrachloroethane ........................................................................................ 168 83, 85, 131, 133, and 166. 

Tetrachloroethene ..................................................................................................... 164 129, 131, and 166. 

Toluene ..................................................................................................................... 92 91. 

Chlorobenzene ......................................................................................................... 112 114. 

Ethyl benzene ........................................................................................................... 106 91.

1,3-Dichlorobenzene ................................................................................................. 146 148 and 111. 

1,2-Dichlorobenzene ................................................................................................. 146 148 and 111. 

1,4-Dichlorobenzene ................................................................................................. 146 148 and 111. 

TABLE 7—LCS (Q), DOC (S AND X), AND MS/MSD (P AND RPD) ACCEPTANCE CRITERIA 1

Analyte Range for Q (%) Limit for s (%) Range for X (%) Range for P (%) Limit for RPD 

Benzene ................................................. 65–135 33 75–125 37–151 61 

Benzene-d6 ............................................ .............................. .............................. .............................. 70–130 ..............................

Bromodichloromethane .......................... 65–135 34 50–140 35–155 56 

Bromoform ............................................. 70–130 25 57–156 45–169 42 

Bromomethane ...................................... 15–185 90 D–206 D–242 61 

2-Butanone-d5 ........................................ .............................. .............................. .............................. 60–140 ..............................

Carbon tetrachloride .............................. 70–130 26 65–125 70–140 41 

Chlorobenzene ....................................... 65–135 29 82–137 37–160 53 

Chloroethane ......................................... 40–160 47 42–202 14–230 78 

Chloroethane-d5 ..................................... .............................. .............................. .............................. 60–140 ..............................

2-Chloroethylvinyl ether ......................... D–225 130 D–252 D–305 71 

Chloroform ............................................. 70–135 32 68–121 51–138 54 

Chloroform-13C ...................................... .............................. .............................. .............................. 70–130 ..............................

Chloromethane ...................................... D–205 472 D–230 D–273 60 

Dibromochloromethane .......................... 70–135 30 69–133 53–149 50 

1,2-Dichlorobenzene .............................. 65–135 31 59–174 18–190 57 

1,2-Dichlorobenzene-d4 ......................... .............................. .............................. .............................. 70–130 ..............................

1,3-Dichlorobenzene .............................. 70–130 24 75–144 59–156 43 

1,4-Dichlorobenzene .............................. 65–135 31 59–174 18–190 57 

1,1-Dichloroethane ................................. 70–130 24 71–143 59–155 40 

1,2-Dichloroethane ................................. 70–130 29 72–137 49–155 49 

1,2-Dichloroethane-d4 ............................ .............................. .............................. .............................. 70–130 ..............................

1,1-Dichloroethene ................................. 50–150 40 19–212 D–234 32 

1,1-Dichloroethene-d2 ............................ .............................. .............................. .............................. 70–130 ..............................

trans-1,2-Dichloroethene ........................ 70–130 27 68–143 54–156 45 

1,2-Dichloropropane ............................... 35–165 69 19–181 D–210 55 

1,2-Dichloropropane-d6 .......................... .............................. .............................. .............................. 60–140 ..............................

cis-1,3-Dichloropropene ......................... 25–175 79 5–195 D–227 58 

trans-1,3-Dichloropropene ..................... 50–150 52 38–162 17–183 86 

trans-1,3-Dichloropropene-d4 ................. .............................. .............................. .............................. 70–130 ..............................

Ethyl benzene ........................................ 60–140 34 75–134 37–162 63 

2-Hexanone-d5 ....................................... .............................. .............................. .............................. 60–140 ..............................

Methylene chloride ................................. 60–140 192 D–205 D–221 28 

1,1,2,2-Tetrachloroethane ...................... 60–140 36 68–136 46–157 61 

1,1,2,2-Tetrachloroethane-d2 ................. .............................. .............................. .............................. 70–130 ..............................

Tetrachloroethene .................................. 70–130 23 65–133 64–148 39 

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TABLE 7—LCS (Q), DOC (S AND X), AND MS/MSD (P AND RPD) ACCEPTANCE CRITERIA 1—Continued 

Analyte Range for Q (%) Limit for s (%) Range for X (%) Range for P (%) Limit for RPD 

Toluene .................................................. 70–130 22 75–134 47–150 41 

Toluene-d8 ............................................. .............................. .............................. .............................. 70–130 ..............................

1,1,1-Trichloroethane ............................. 70–130 21 69–151 52–162 36 

1,1,2-Trichloroethane ............................. 70–130 27 75–136 52–150 45 

Trichloroethene ...................................... 65–135 29 75–138 70–157 48 

Trichlorofluoromethane .......................... 50–150 50 45–158 17–181 84 

Vinyl chloride ......................................... 5–195 100 D–218 D–251 66 

Vinyl chloride-d3 ..................................... .............................. .............................. .............................. 70–130 ..............................

1 Criteria were calculated using an LCS concentration of 20 μg/L 

Q = Percent recovery in calibration verification/LCS (Section 8.4) 

s = Standard deviation of percent recovery for four recovery measurements (Section 8.2.4) 

X = Average percent recovery for four recovery measurements (Section 8.2.4) 

P = Percent recovery for the MS or MSD (Section 8.3.3) 

D = Detected; result must be greater than zero 

Notes: 

1. Criteria for pollutants are based upon the method performance data in Reference 4. Where necessary, limits for recovery have been broadened to assure applicability to concentrations below those used to develop Table 7. 

2. Criteria for surrogates are from EPA CLP SOM01.2D. 

TABLE 8—RECOVERY AND PRECISION AS FUNCTIONS OF CONCENTRATION

Analyte Recovery, X′ 

(μg/L) 

Single analyst 

precision, sr′ 

(μg/L) 

Overall precision, S′ (μg/L) 

Benzene ......................................................................................................................................... 0.93C+2.00 ... 20.26 X ̄ ¥1.74 0.25 X ̄ ¥1.33 

Bromodichloromethane .................................................................................................................. 1.03C¥1.58 .. 0.15 X ̄ +0.59 .. 0.20 X ̄ +1.13 

Bromoform ..................................................................................................................................... 1.18C¥2.35 .. 0.12 X ̄ +0.36 .. 0.17 X ̄ +1.38 

Bromomethane a ............................................................................................................................ 1.00C ............ 0.43 X ̄ ........... 0.58 X ̄

Carbon tetrachloride ...................................................................................................................... 1.10C¥1.68 .. 0.12 X ̄ +0.25 .. 0.11 X ̄ +0.37 

Chlorobenzene .............................................................................................................................. 0.98C+2.28 ... 0.16 X ̄ ¥0.09 0.26 X ̄ ¥1.92 

Chloroethane ................................................................................................................................. 1.18C+0.81 ... 0.14 X ̄ +2.78 .. 0.29 X ̄ +1.75 

2-Chloroethylvinyl ether a ............................................................................................................... 1.00C ............ 0.62 X ̄ ........... 0.84 X ̄

Chloroform ..................................................................................................................................... 0.93C+0.33 ... 0.16 X ̄ +0.22 .. 0.18 X ̄ +0.16 

Chloromethane .............................................................................................................................. 1.03C+0.81 ... 0.37 X ̄ +2.14 .. 0.58 X ̄ +0.43 

Dibromochloromethane ................................................................................................................. 1.01C¥0.03 .. 0.17 X ̄ ¥0.18 0.17 X ̄ +0.49 

1,2-Dichlorobenzene b .................................................................................................................... 0.94C+4.47 ... 0.22 X ̄ ¥1.45 0.30 X ̄ ¥1.20 

1,3-Dichlorobenzene ...................................................................................................................... 1.06C+1.68 ... 0.14 X ̄ ¥0.48 0.18 X ̄ ¥0.82 

1,4-Dichlorobenzene b .................................................................................................................... 0.94C+4.47 ... 0.22 X ̄ ¥1.45 0.30 X ̄ ¥1.20 

1,1-Dichloroethane ........................................................................................................................ 1.05C+0.36 ... 0.13 X ̄ ¥0.05 0.16 X ̄ +0.47 

1,2-Dichloroethane ........................................................................................................................ 1.02C+0.45 ... 0.17 X ̄ ¥0.32 0.21 X ̄ ¥0.38 

1,1-Dichloroethene ........................................................................................................................ 1.12C+0.61 ... 0.17 X ̄ +1.06 .. 0.43 X ̄ ¥0.22 

trans-1,2,-Dichloroethene .............................................................................................................. 1.05C+0.03 ... 0.14 X ̄ +0.09 .. 0.19 X ̄ +0.17 

1,2-Dichloropropane a .................................................................................................................... 1.00C ............ 0.33 X ̄ ........... 0.45 X ̄

cis-1,3-Dichloropropene a ............................................................................................................... 1.00C ............ 0.38 X ̄ ........... 0.52 X ̄

trans-1,3-Dichloropropene a ........................................................................................................... 1.00C ............ 0.25 X ̄ ........... 0.34 X ̄

Ethyl benzene ................................................................................................................................ 0.98C+2.48 ... 0.14 X ̄ +1.00 .. 0.26 X ̄ ¥1.72 

Methylene chloride ........................................................................................................................ 0.87C+1.88 ... 0.15 X ̄ +1.07 .. 0.32 X ̄ +4.00 

1,1,2,2-Tetrachloroethane ............................................................................................................. 0.93C+1.76 ... 0.16 X ̄ +0.69 .. 0.20 X ̄ +0.41 

Tetrachloroethene .......................................................................................................................... 1.06C+0.60 ... 0.13 X ̄ ¥0.18 0.16 X ̄ ¥0.45 

Toluene .......................................................................................................................................... 0.98C+2.03 ... 0.15 X ̄ ¥0.71 0.22 X ̄ ¥1.71 

1,1,1-Trichloroethane ..................................................................................................................... 1.06C+0.73 ... 0.12 X ̄ ¥0.15 0.21 X ̄ ¥0.39 

1,1,2-Trichloroethane ..................................................................................................................... 0.95C+1.71 ... 0.14 X ̄ +0.02 .. 0.18 X ̄ +0.00 

Trichloroethene .............................................................................................................................. 1.04C+2.27 ... 0.13 X ̄ +0.36 .. 0.12 X ̄ +0.59 

Trichlorofluoromethane .................................................................................................................. 0.99C+0.39 ... 0.33 X ̄ ¥1.48 0.34 X ̄ ¥0.39 

Vinyl chloride ................................................................................................................................. 1.00C ............ 0.48 X ̄ ........... 0.65 X ̄

X′ = Expected recovery for one or more measurements of a sample containing a concentration of C, in μg/L. 

Sr′ = Expected single analyst standard deviation of measurements at an average concentration found of X ̄ , in μg/L. 

S′ = Expected interlaboratory standard deviation of measurements at an average concentration found of X ̄ , in μg/L. 

C = True value for the concentration, in μg/L. 

X = Average recovery found for measurements of samples containing a concentration of C, in μg/L. aEstimates 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. 

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19. Figures 

BILLING CODE 6560–50–P 

BILLING CODE 6560–50–C 


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20. Glossary 

These definitions and purposes are 

specific to this method, but have been 

conformed to common usage to the 

extent possible. 

20.1 Units of weight and measure 

and their abbreviations 

20.1.1 Symbols 

°C degrees Celsius 

mg microgram 

mL microliter 

< less than 

> greater than 

% percent 

20.1.2 Abbreviations (in alphabetical 

order) 

cm centimeter 

g gram 

h hour 

ID inside diameter 

in. inch 

L liter 

M Molecular ion 

m mass 

mg milligram 

min minute 

mL milliliter 

mm millimeter 

ms millisecond 

m/z mass-to-charge ratio 

N normal; gram molecular weight of 

solute divided by hydrogen 

equivalent of solute, per liter of 

solution 

ng nanogram 

pg picogram 

ppb part-per-billion 

ppm part-per-million 

ppt part-per-trillion 

psig pounds-per-square inch gauge 

v/v volume per unit volume 

w/v weight per unit volume 

20.2 Definitions and acronyms (in 

alphabetical order) 

Analyte—A compound tested for by 

this method. The analytes are listed in 

Tables 1 and 2. 

Analyte of interest—An analyte of 

interest is an analyte required to be 


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determined by a regulatory/control 

authority or in a permit, or by a client. 

Analytical batch—The set of samples 

analyzed on a given instrument during 

a 12-hour period that begins and ends 

with analysis of a calibration 

verification/LCS. See Section 8.4. 

Blank—An aliquot of reagent water 

that is treated exactly as a sample 

including exposure to all glassware, 

equipment, solvents, reagents, internal 

standards, and surrogates that are used 

with samples. The blank is used to 

determine if analytes or interferences 

are present in the laboratory 

environment, the reagents, or the 

apparatus. See Section 8.5. 

Calibration—The process of 

determining the relationship between 

the output or response of a measuring 

instrument and the value of an input 

standard. Historically, EPA has referred 

to a multi-point calibration as the 

‘‘initial calibration,’’ to differentiate it 

from a single-point calibration 

verification. 

Calibration standard—A solution 

prepared from stock solutions and/or a 

secondary standards and containing the 

analytes of interest, surrogates, and 

internal standards. The calibration 

standard is used to calibrate the 

response of the GC/MS instrument 

against analyte concentration. 

Calibration verification standard— 

The laboratory control sample (LCS) 

used to verify calibration. See Section 

8.4. 

Descriptor—In SIM, the beginning 

and ending retention times for the RT 

window, the m/z’s sampled in the RT 

window, and the dwell time at each m/ 

z. 

Extracted ion current profile (EICP)— 

The line described by the signal at a 

given m/z. 

Field duplicates—Two samples 

collected at the same time and place 

under identical conditions, and treated 

identically throughout field and 

laboratory procedures. Results of 

analyses of field duplicates provide an 

estimate of the precision associated with 

sample collection, preservation, and 

storage, as well as with laboratory 

procedures. 

Field blank—An aliquot of reagent 

water or other reference matrix that is 

placed in a sample container in the 

field, and treated as a sample in all 

respects, including exposure to 

sampling site conditions, storage, 

preservation, and all analytical 

procedures. The purpose of the field 

blank is to determine if the field or 

sample transporting procedures and 

environments have contaminated the 

sample. 

GC—Gas chromatograph or gas 

chromatography 

Internal standard—A compound 

added to a sample in a known amount 

and used as a reference for quantitation 

of the analytes of interest and 

surrogates. Internal standards are listed 

in Table 5. Also see Internal standard 

quantitation. 

Internal standard quantitation—A 

means of determining the concentration 

of an analyte of interest (Tables 1 and 

2) by reference to a compound added to 

a sample and not expected to be found 

in the sample. 

DOC—Initial demonstration of 

capability (DOC; Section 8.2); four 

aliquots of reagent water spiked with 

the analytes of interest and analyzed to 

establish the ability of the laboratory to 

generate acceptable precision and 

recovery. A DOC is performed prior to 

the first time this method is used and 

any time the method or instrumentation 

is modified. 

Laboratory control sample (LCS; 

laboratory fortified blank (LFB); ongoing precision and recovery sample; 

OPR)—An aliquot of reagent water 

spiked with known quantities of the 

analytes of interest and surrogates. The 

LCS is analyzed exactly like a sample. 

Its purpose is to assure that the results 

produced by the laboratory remain 

within the limits specified in this 

method for precision and recovery. In 

this method, the LCS is synonymous 

with a calibration verification sample 

(See Sections 7.4 and 8.4). 

Laboratory fortified sample matrix— 

See Matrix spike. 

Laboratory reagent blank—See Blank. 

Matrix spike (MS) and matrix spike 

duplicate (MSD) (laboratory fortified 

sample matrix and duplicate)—Two 

aliquots of an environmental sample to 

which known quantities of the analytes 

of interest and surrogates are added in 

the laboratory. The MS/MSD are 

prepared and analyzed exactly like a 

field sample. Their purpose is to 

quantify any additional bias and 

imprecision caused by the sample 

matrix. The background concentrations 

of the analytes in the sample matrix 

must be determined in a separate 

aliquot and the measured values in the 

MS/MSD corrected for background 

concentrations. 

May—This action, activity, or 

procedural step is neither required nor 

prohibited. 

May not—This action, activity, or 

procedural step is prohibited. 

Method blank (laboratory reagent 

blank)—See Blank. 

Method detection limit (MDL)—A 

detection limit determined by the 

procedure at 40 CFR part 136, appendix 

B. The MDLs determined by EPA in the 

original version of the method are listed 

in Table 1. As noted in Sec. 1.4, use the 

MDLs in Table 1 in conjunction with 

current MDL data from the laboratory 

actually analyzing samples to assess the 

sensitivity of this procedure relative to 

project objectives and regulatory 

requirements (where applicable). 

Minimum level (ML)—The term 

‘‘minimum level’’ refers to either the 

sample concentration equivalent to the 

lowest calibration point in a method or 

a multiple of the method detection limit 

(MDL), whichever is higher. Minimum 

levels may be obtained in several ways: 

They may be published in a method; 

they may be based on the lowest 

acceptable calibration point used by a 

laboratory; or they may be calculated by 

multiplying the MDL in a method, or 

the MDL determined by a laboratory, by 

a factor of 3. For the purposes of NPDES 

compliance monitoring, EPA considers 

the following terms to be synonymous: 

‘‘quantitation limit,’’ ‘‘reporting limit,’’ 

and ‘‘minimum level.’’ 

MS—Mass spectrometer or mass 

spectrometry. 

Must—This action, activity, or 

procedural step is required. 

m/z—The ratio of the mass of an ion 

(m) detected in the mass spectrometer to 

the charge (z) of that ion. 

Quality control sample (QCS)—A 

sample containing analytes of interest at 

known concentrations. The QCS is 

obtained from a source external to the 

laboratory or is prepared from standards 

obtained from a different source than 

the calibration standards. 

The purpose is to check laboratory 

performance using test materials that 

have been prepared independent of the 

normal preparation process. 

Reagent water—Water demonstrated 

to be free from the analytes of interest 

and potentially interfering substances at 

the MDLs for the analytes in this 

method. 

Regulatory compliance limit (or 

regulatory concentration limit)—A limit 

on the concentration or amount of a 

pollutant or contaminant specified in a 

nationwide standard, in a permit, or 

otherwise established by a regulatory/ 

control authority. 

Relative retention time (RRT)—The 

ratio of the retention time of an analyte 

to the retention time of its associated 

internal standard. RRT compensates for 

small changes in the GC temperature 

program that can affect the absolute 

retention times of the analyte and 

internal standard. RRT is a unitless 

quantity. 

Relative standard deviation (RSD)— 

The standard deviation times 100 

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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 

§ 1910.1200. United Nations Globally 

Harmonized System of Classification 

and Labelling of Chemicals (GHS), third 

revised edition, United Nations, 2009. 

Selected Ion Monitoring (SIM)—An 

MS technique in which a few m/z’s are 

monitored. When used with gas 

chromatography, the m/z’s monitored 

are usually changed periodically 

throughout the chromatographic run to 

correlate with the characteristic m/z’s 

for the analytes, surrogates, and internal 

standards as they elute from the 

chromatographic column. The 

technique is often used to increase 

sensitivity and minimize interferences. 

Signal-to-noise ratio (S/N)—The 

height of the signal as measured from 

the mean (average) of the noise to the 

peak maximum divided by the width of 

the noise. 

SIM—See Selection Ion Monitoring. 

Should—This action, activity, or 

procedural step is suggested but not 

required. 

Stock solution—A solution containing 

an analyte that is prepared using a 

reference material traceable to EPA, the 

National Institute of Science and 

Technology (NIST), or a source that will 

attest to the purity and authenticity of 

the reference material. 

Surrogate—A compound unlikely to 

be found in a sample, and which is 

spiked into sample in a known amount 

before purge-and-trap. The surrogate is 

quantitated with the same procedures 

used to quantitate the analytes of 

interest. The purpose of the surrogate is 

to monitor method performance with 

each sample. 

* * * * * 

Method 625.1—Base/Neutrals and 

Acids by GC/MS 

1. Scope and Application 

1.1 This method is for determination 

of semivolatile organic pollutants in 

industrial discharges and other 

environmental samples by gas 

chromatography combined with mass 

spectrometry (GC/MS), as provided 

under 40 CFR 136.1. This revision is 

based on a previous protocol (Reference 

1), on the basic revision promulgated 

October 26, 1984 (49 FR 43234), and on 

an interlaboratory method validation 

study (Reference 2). Although this 

method was validated through an 

interlaboratory study conducted more 

than 29 years ago, the fundamental 

chemistry principles used in this 

method remain sound and continue to 

apply. 

1.2 The analytes that may be 

qualitatively and quantitatively 

determined using this method and their 

CAS Registry numbers are listed in 

Tables 1 and 2. The method may be 

extended to determine the analytes 

listed in Table 3; however, extraction or 

gas chromatography of some of these 

analytes may make quantitative 

determination difficult. For examples, 

benzidine is subject to oxidative losses 

during solvent concentration. Under the 

alkaline conditions of the extraction, 

alpha-BHC, gamma-BHC, endosulfan I 

and II, and endrin are subject to 

decomposition. 

Hexachlorocyclopentadiene is subject to 

thermal decomposition in the inlet of 

the gas chromatograph, chemical 

reaction in acetone solution, and 

photochemical decomposition. Nnitrosodiphenylamine and other 

nitrosoamines may decompose in the 

gas chromatographic inlet. EPA has 

provided other methods (e.g., Method 

607—Nitrosamines) for determination of 

some of these analytes. 

1.3 The large number of analytes in 

Tables 1–3 of this method makes testing 

difficult if all analytes are determined 

simultaneously. Therefore, it is 

necessary to determine and perform 

quality control (QC) tests for the 

‘‘analytes of interest’’ only. Analytes of 

interest are those required to be 

determined by a regulatory/control 

authority or in a permit, or by a client. 

If a list of analytes is not specified, the 

analytes in Tables 1 and 2 must be 

determined, at a minimum, and QC 

testing must be performed for these 

analytes. The analytes in Tables 1 and 

2, and some of the analytes in Table 3 

have been identified as Toxic Pollutants 

(40 CFR 401.15), expanded to a list of 

Priority Pollutants (40 CFR part 423, 

appendix A). 

1.4 In this revision to Method 625, 

the pesticides and polychlorinated 

biphenyls (PCBs) have been moved from 

Table 1 to Table 3 (Additional Analytes) 

to distinguish these analytes from the 

analytes required in quality control tests 

(Tables 1 and 2). QC acceptance criteria 

for pesticides and PCBs have been 

retained in Table 6 and may continue to 

be applied if desired, or if requested or 

required by a regulatory/control 

authority or in a permit. Method 608 

should be used for determination of 

pesticides and PCBs. Method 1668C 

may be useful for determination of PCBs 

as individual chlorinated biphenyl 

congeners, and Method 1699 may be 

useful for determination of pesticides. 

At the time of writing of this revision, 

Methods 1668C and 1699 had not been 

approved for use at 40 CFR part 136. 

The screening procedure for 2,3,7,8- 

tetrachlorodibenzo-p-dioxin (2,3,7,8– 

TCDD) contained in the version of 

Method 625 promulgated October 26, 

1984 (49 FR 43234) has been replaced 

with procedures for selected ion 

monitoring (SIM), and 2,3,7,8–TCDD 

may be determined using the SIM 

procedures. However, EPA Method 613 

or 1613B should be used for analytespecific determination of 2,3,7,8–TCDD 

because of the focus of these methods 

on this compound. Methods 613 and 

1613B are approved for use at 40 CFR 

part 136. 

1.5 Method detection limits (MDLs; 

Reference 3) for the analytes in Tables 

1, 2, and 3 are listed in those tables. 

These MDLs were determined in reagent 

water (Reference 4). Advances in 

analytical technology, particularly the 

use of capillary (open-tubular) columns, 

allowed laboratories to routinely 

achieve MDLs for the analytes in this 

method that are 2–10 times lower than 

those in the version promulgated in 

1984 (40 FR 43234). The MDL for an 

analyte in a specific wastewater may 

differ from those listed, depending upon 

the nature of interferences in the sample 

matrix. 

1.5.1 EPA has promulgated this 

method at 40 CFR part 136 for use in 

wastewater compliance monitoring 

under the National Pollutant Discharge 

Elimination System (NPDES). The data 

reporting practices described in Section 

15.2 are focused on such monitoring 

needs and may not be relevant to other 

uses of the method. 

1.5.2 This method includes 

‘‘reporting limits’’ based on EPA’s 

‘‘minimum level’’ (ML) concept (see the 

glossary in Section 22). Tables 1, 2, and 

3 contain MDL values and ML values for 

many of the analytes. The MDL for an 

analyte in a specific wastewater may 

differ from those listed in Tables 1, 2, 

and 3, depending upon the nature of 

interferences in the sample matrix. 

1.6 This method is performancebased. It may be modified to improve 

performance (e.g., to overcome 

interferences or improve the accuracy of 

results) provided all performance 

requirements are met. 

1.6.1 Examples of allowed method 

modifications are described at 40 CFR 

136.6. Other examples of allowed 

modifications specific to this method 

are described in Section 8.1.2. 

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1.6.2 Any modification beyond 

those expressly permitted at 40 CFR 

136.6 or in Section 8.1.2 of this method 

shall be considered a major 

modification subject to application and 

approval of an alternate test procedure 

under 40 CFR 136.4 and 136.5. 

1.6.3 For regulatory compliance, any 

modification must be demonstrated to 

produce results equivalent or superior 

to results produced by this method 

when applied to relevant wastewaters 

(Section 8.3). 

1.7 This method is restricted to use 

by or under the supervision of analysts 

experienced in the use of a gas 

chromatograph/mass spectrometer and 

in the interpretation of mass spectra. 

Each laboratory that uses this method 

must demonstrate the ability to generate 

acceptable results using the procedure 

in Section 8.2. 

1.8 Terms and units of measure used 

in this method are given in the glossary 

at the end of the method. 

2. Summary of Method 

2.1 A measured volume of sample, 

sufficient to meet an MDL or reporting 

limit, is serially extracted with 

methylene chloride at pH 11–13 and 

again at a pH less than 2 using a 

separatory funnel or continuous liquid/ 

liquid extractor. 

2.2 The extract is concentrated to a 

volume necessary to meet the required 

compliance or detection limit, and 

analyzed by GC/MS. Qualitative 

identification of an analyte in the 

extract is performed using the retention 

time and the relative abundance of two 

or more characteristic masses (m/z’s). 

Quantitative analysis is performed using 

the internal standard technique with a 

single characteristic m/z. 

3. Contamination and Interferences 

3.1 Solvents, reagents, glassware, 

and other sample processing labware 

may yield artifacts, elevated baselines, 

or matrix interferences causing 

misinterpretation of chromatograms and 

mass spectra. All materials used in the 

analysis must be demonstrated to be free 

from contamination and interferences 

by analyzing blanks initially and with 

each extraction batch (samples started 

through the extraction process in a 

given 12-hour period, to a maximum of 

20 samples—see Glossary for detailed 

definition), as described in Section 8.5. 

Specific selection of reagents and 

purification of solvents by distillation in 

all-glass systems may be required. 

Where possible, labware is cleaned by 

extraction or solvent rinse, or baking in 

a kiln or oven. 

3.2 Glassware must be scrupulously 

cleaned (Reference 5). Clean all 

glassware as soon as possible after use 

by rinsing with the last solvent used in 

it. Solvent rinsing should be followed 

by detergent washing with hot water, 

and rinses with tap water and reagent 

water. The glassware should then be 

drained dry, and heated at 400 °C for 

15–30 minutes. Some thermally stable 

materials, such as PCBs, may require 

higher temperatures and longer baking 

times for removal. Solvent rinses with 

pesticide quality acetone, hexane, or 

other solvents may be substituted for 

heating. Volumetric labware should not 

be heated above 90 °C. After drying and 

cooling, glassware should be sealed and 

stored in a clean environment to prevent 

any accumulation of dust or other 

contaminants. Store inverted or capped 

with solvent-rinsed or baked aluminum 

foil. 

3.3 Matrix interferences may be 

caused by contaminants co-extracted 

from the sample. The extent of matrix 

interferences will vary considerably 

from source to source, depending upon 

the nature and diversity of the industrial 

complex or municipality being sampled. 

Interferences extracted from samples 

high in total organic carbon (TOC) may 

result in elevated baselines, or by 

enhancing or suppressing a signal at or 

near the retention time of an analyte of 

interest. Analyses of the matrix spike 

and duplicate (Section 8.3) may be 

useful in identifying matrix 

interferences, and gel permeation 

chromatography (GPC; Section 11.1) and 

sulfur removal (Section 11.2) may aid in 

eliminating these interferences. EPA has 

provided guidance that may aid in 

overcoming matrix interferences 

(Reference 6). 

3.4 In samples that contain an 

inordinate number of interferences, the 

use of chemical ionization (CI) mass 

spectrometry may make identification 

easier. Tables 4 and 5 give characteristic 

CI m/z’s for many of the analytes 

covered by this method. The use of CI 

mass spectrometry to support electron 

ionization (EI) mass spectrometry is 

encouraged, but not required. 

4. Safety 

4.1 Hazards associated with each 

reagent used in this method have not 

been precisely defined; however, each 

chemical compound should be treated 

as a potential health hazard. From this 

viewpoint, exposure to these chemicals 

must be reduced to the lowest possible 

level by whatever means available. The 

laboratory is responsible for maintaining 

a current awareness file of OSHA 

regulations regarding the safe handling 

of the chemicals specified in this 

method. A reference file of safety data 

sheets (SDSs, OSHA, 29 CFR 

1910.1200(g)) should also be made 

available to all personnel involved in 

sample handling and chemical analysis. 

Additional references to laboratory 

safety are available and have been 

identified (References 7–9) for the 

information of the analyst. 

4.2 The following analytes covered 

by this method have been tentatively 

classified as known or suspected human 

or mammalian carcinogens: 

benzo(a)anthracene, benzidine, 3,3’- 

dichlorobenzidine, benzo(a)pyrene, 

alpha-BHC, beta-BHC, delta-BHC, 

gamma-BHC, Dibenz(a,h)-anthracene, 

N-nitrosodimethylamine, 4,4’-DDT, and 

PCBs. Other compounds in Table 3 may 

also be toxic. Primary standards of toxic 

compounds should be prepared in a 

chemical fume hood, and a NIOSH/ 

MESA approved toxic gas respirator 

should be worn when handling high 

concentrations of these compounds. 

4.3 This method allows the use of 

hydrogen as a carrier gas in place of 

helium (Section 5.6.1.2). The laboratory 

should take the necessary precautions in 

dealing with hydrogen, and should limit 

hydrogen flow at the source to prevent 

buildup of an explosive mixture of 

hydrogen in air. 

5. Apparatus and Materials 

Note: Brand names, suppliers, and part 

numbers are for illustration purposes only. 

No endorsement is implied. Equivalent 

performance may be achieved using 

equipment and materials other than those 

specified here. Demonstrating that the 

equipment and supplies used in the 

laboratory achieves the required performance 

is the responsibility of the laboratory. 

Suppliers for equipment and materials in this 

method may be found through an on-line 

search. Please do not contact EPA for 

supplier information. 

5.1 Sampling equipment, for 

discrete or composite sampling. 

5.1.1 Grab sample bottle—amber 

glass bottle large enough to contain the 

necessary sample volume, fitted with a 

fluoropolymer-lined screw cap. Foil 

may be substituted for fluoropolymer if 

the sample is not corrosive. If amber 

bottles are not available, protect samples 

from light. Unless pre-cleaned, the 

bottle and cap liner must be washed, 

rinsed with acetone or methylene 

chloride, and dried before use to 

minimize contamination. 

5.1.2 Automatic sampler 

(optional)—the sampler must 

incorporate a pre-cleaned glass sample 

container. Samples must be kept 

refrigerated at <6 °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, 

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however, the compressible tubing 

should be thoroughly rinsed with 

methanol, followed by repeated rinsings 

with reagent water to minimize the 

potential for contamination of the 

sample. An integrating flow meter is 

required to collect flow-proportioned 

composites. 

5.2 Glassware. 

5.2.1 Separatory funnel—Size 

appropriate to hold sample volume and 

extraction solvent volume, and 

equipped with fluoropolymer stopcock. 

5.2.2 Drying column— 

Chromatographic column, 

approximately 400 mm long by 19 mm 

ID, with coarse frit, or equivalent, 

sufficient to hold 15 g of anhydrous 

sodium sulfate. 

5.2.3 Concentrator tube, KudernaDanish—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, KudernaDanish—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, KudernaDanish—Three ball macro (Kontes 

503000–0121 or equivalent). 

5.2.6 Snyder column, KudernaDanish—Two-ball micro (Kontes 

569001–0219 or equivalent). 

5.2.7 Vials—10–15 mL, amber glass, 

with Teflon-lined screw cap. 

5.2.8 Continuous liquid-liquid 

extractor—Equipped with 

fluoropolymer or glass connecting joints 

and stopcocks requiring no lubrication. 

(Hershberg-Wolf Extractor, Ace Glass 

Company, Vineland, N.J., P/N 6848–20, 

or equivalent.) 

5.2.9 In addition to the glassware 

listed above, the laboratory should be 

equipped with all necessary pipets, 

volumetric flasks, beakers, and other 

glassware listed in this method and 

necessary to perform analyses 

successfully. 

5.3 Boiling chips—Approximately 

10/40 mesh, glass, silicon carbide, or 

equivalent. Heat to 400 °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 °C). The bath 

should be used in a hood. 

5.5 Balances. 

5.5.1 Analytical, capable of 

accurately weighing 0.1 mg. 

5.5.2 Top loading, capable of 

accurately weighing 10 mg. 

5.6 GC/MS system. 

5.6.1 Gas chromatograph (GC)—An 

analytical system complete with a 

temperature programmable gas 

chromatograph and all required 

accessories, including syringes and 

analytical columns. 

5.6.1.1 Injection port—Can be split, 

splitless, temperature programmable 

split/splitless (PTV), solvent-purge, 

large-volume, on-column, backflushed, 

or other. An autosampler is highly 

recommended because it injects 

volumes more precisely than volumes 

injected manually. 

5.6.1.2 Carrier gas—Helium or 

hydrogen. Data in the tables in this 

method were obtained using helium 

carrier gas. If hydrogen is used, 

analytical conditions may need to be 

adjusted for optimum performance, and 

calibration and all QC tests must be 

performed with hydrogen carrier gas. 

See Section 4.3 for precautions 

regarding the use of hydrogen as a 

carrier gas. 

5.6.2 GC column—See the footnotes 

to Tables 4 and 5. Other columns or 

column systems may be used provided 

all requirements in this method are met. 

5.6.3 Mass spectrometer—Capable of 

repetitively scanning from 35–450 

Daltons (amu) every two seconds or less, 

utilizing a 70 eV (nominal) electron 

energy in the electron impact ionization 

mode, and producing a mass spectrum 

which meets all the criteria in Table 9A 

or 9B when 50 ng or less of 

decafluorotriphenyl phosphine (DFTPP; 

CAS 5074–71–5; bis(pentafluorophenyl) 

phenyl phosphine) is injected into the 

GC. 

5.6.4 GC/MS interface—Any GC to 

MS interface that meets all performance 

requirements in this method may be 

used. 

5.6.5 Data system—A computer 

system must be interfaced to the mass 

spectrometer that allows the continuous 

acquisition and storage of mass spectra 

acquired throughout the 

chromatographic program. The 

computer must have software that 

allows searching any GC/MS data file 

for specific m/z’s (masses) and plotting 

m/z abundances versus time or scan 

number. This type of plot is defined as 

an extracted ion current profile (EICP). 

Software must also be available that 

allows integrating the abundance at any 

EICP between specified time or scan 

number limits. 

5.7 Automated gel permeation 

chromatograph (GPC). 

5.7.1 GPC column—150—700 mm 

long x 21–25 mm ID, packed with 70 g 

of SX–3 Biobeads; Bio-Rad Labs, or 

equivalent 

5.7.2 Pump, injection valve, UV 

detector, and other apparatus necessary 

to meet the requirements in this 

method. 

5.8 Nitrogen evaporation device— 

Equipped with a water bath than can be 

maintained at 30–45 °C; N-Evap, 

Organomation Associates, or equivalent. 

6. Reagents 

6.1 Reagent water—Reagent water is 

defined as water in which the analytes 

of interest and interfering compounds 

are not detected at the MDLs of the 

analytes of interest. 

6.2 Sodium hydroxide solution (10 

N)—Dissolve 40 g of NaOH (ACS) in 

reagent water and dilute to 100 mL. 

6.3 Sodium thiosulfate—(ACS) 

granular. 

6.4 Sulfuric acid (1+1)—Slowly add 

50 mL of H2SO4 (ACS, sp. gr. 1.84) to 

50 mL of reagent water. 

6.5 Acetone, methanol, methylene 

chloride, 2-propanol—High purity 

pesticide quality, or equivalent, 

demonstrated to be free of the analytes 

of interest and interferences (Section 3). 

Purification of solvents by distillation in 

all-glass systems may be required. 

6.6 Sodium sulfate—(ACS) granular, 

anhydrous, rinsed or Soxhlet extracted 

with methylene chloride (20 mL/g), 

baked at in a shallow tray at 450 °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 

mg/mL)—Stock standard solutions may 

be prepared from pure materials, or 

purchased as certified solutions. 

Traceability must be to the National 

Institute of Standards and Technology 

(NIST) or other national standard, when 

available. Stock solution concentrations 

alternate to those below may be used. 

Because of the toxicity of some of the 

compounds, primary dilutions should 

be prepared in a hood, and a NIOSH/

MESA approved toxic gas respirator 

should be worn when high 

concentrations of neat materials are 

handled. The following procedure may 

be used to prepare standards from neat 

materials. 

6.7.1 Prepare stock standard 

solutions by accurately weighing about 

0.0100 g of pure material. Dissolve the 

material in pesticide quality methanol 

or other suitable solvent and dilute to 

volume in a 10 mL volumetric flask. 

Larger volumes may be used at the 

convenience of the laboratory. When 

compound purity is assayed to be 96% 

or greater, the weight may be used 

without correction to calculate the 

concentration of the stock standard. 

Commercially prepared stock standards 

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may be used at any concentration if they 

are certified by the manufacturer or by 

an independent source. 

6.7.2 Transfer the stock standard 

solutions to fluoropolymer-sealed 

screw-cap bottles. Store at <6 °C and 

protect from light. Stock standard 

solutions should be checked frequently 

for signs of degradation or evaporation, 

especially just prior to preparing 

calibration standards from them. 

6.7.3 Replace purchased certified 

stock standard solutions per the 

expiration date. Replace stock standard 

solutions prepared by the laboratory or 

mixed with purchased solutions after 

one year, or sooner if comparison with 

QC check samples indicates a problem. 

6.8 Surrogate standard spiking 

solution 

6.8.1 Select a minimum of three 

surrogate compounds from Table 8 that 

most closely match the recovery of the 

analytes of interest. For example, if all 

analytes tested are considered acids, use 

surrogates that have similar chemical 

attributes. Other compounds may be 

used as surrogates so long as they do not 

interfere in the analysis. The deuterium 

and carbon-13 labeled compounds in 

Method 1625B are particularly useful 

because Method 1625B contains QC 

acceptance criteria for recovery of these 

compounds. If only one or two analytes 

are determined, one or two surrogates 

may be used. 

6.8.2 Prepare a solution containing 

each selected surrogate such that the 

concentration in the sample would 

match the concentration in the midpoint calibration standard. For example, 

if the midpoint of the calibration is 100 

mg/L, prepare the spiking solution at a 

concentration of 100 mg/mL in 

methanol. Addition of 1.00 mL of this 

solution to 1000 mL of sample will 

produce a concentration of 100 mg/L of 

the surrogate. Alternate volumes and 

concentrations appropriate to the 

response of the GC/MS instrument or for 

selective ion monitoring (SIM) may be 

used, if desired. 

6.8.3 Store the spiking solution at ≤ 

6°C in a fluoropolymer-sealed glass 

container. The solution should be 

checked frequently for stability. The 

solution must be replaced after one year, 

or sooner if comparison with quality 

control check standards indicates a 

problem. 

6.9 Internal standard spiking 

solution 

6.9.1 Select three or more internal 

standards similar in chromatographic 

behavior to the analytes of interest. 

Internal standards are listed in Table 8. 

Suggested internal standards are: 1,4- 

dichlorobenzene-d4; naphthalene-d8; 

acenaphthene-d10; phenanthrene-d10; 

chrysene-d12; and perylene-d12. The 

laboratory must demonstrate that 

measurement of the internal standards 

is not affected by method or matrix 

interferences (see also Section 7.3.4). 

6.9.2 Prepare the internal standards 

at a concentration of 10 mg/mL in 

methylene chloride or other suitable 

solvent. When 10 mL of this solution is 

spiked into a 1-mL extract, the 

concentration of the internal standards 

will be 100 mg/mL. A lower 

concentration appropriate to the 

response of the GC/MS instrument or for 

SIM may be used, if desired. 

6.9.3 To assure accurate analyte 

identification, particularly when SIM is 

used, it may be advantageous to include 

more internal standards than those 

suggested in Section 6.9.1. An analyte 

will be located most accurately if its 

retention time relative to an internal 

standard is in the range of 0.8 to 1.2. 

6.10 DFTPP standard—Prepare a 

solution of DFTPP in methanol or other 

suitable solvent such that 50 ng or less 

will be injected (see Section 13.2). An 

alternate concentration may be used to 

compensate for specific injection 

volumes or to assure that the operating 

range of the instrument is not exceeded, 

so long as the total injected is 50 ng or 

less. Include benzidine and 

pentachlorophenol in this solution such 

that ≤100 ng of benzidine and ≤50 ng of 

pentachlorophenol will be injected. 

6.11 Quality control check sample 

concentrate—See Section 8.2.1. 

6.12 GPC calibration solution 

6.12.1 Prepare a methylene chloride 

solution to contain corn oil, bis(2- 

ethylhexyl) phthalate (BEHP), perylene, 

and sulfur at the concentrations in 

Section 6.12.2, or at concentrations 

appropriate to the response of the 

detector. 

Note: Sulfur does not readily dissolve in 

methylene chloride, but is soluble in warm 

corn oil. The following procedure is 

suggested for preparation of the solution: 

6.12.2 Weigh 8 mg sulfur and 2.5 g 

corn oil into a 100-mL volumetric flask 

and warm to dissolve the sulfur. 

Separately weigh 100 mg BEHP and 2 

mg perylene and add to flask. Bring to 

volume with methylene chloride and 

mix thoroughly. 

6.12.3 Store the solution in an amber 

glass bottle with a fluoropolymer-lined 

screw cap at 0–6 °C. Protect from light. 

Refrigeration may cause the corn oil to 

precipitate. Before use, allow the 

solution to stand at room temperature 

until the corn oil dissolves, or warm 

slightly to aid in dissolution. Replace 

the solution every year, or more 

frequently if the response of a 

component changes. 

6.13 Sulfur removal—Copper foil or 

powder (bright, non-oxidized), or 

tetrabutylammonium sulfite (TBA 

sulfite). 

6.13.1 Copper foil, or powder— 

Fisher, Alfa Aesar 42455–18, 625 mesh, 

or equivalent. Cut copper foil into 

approximately 1-cm squares. Copper 

must be activated on each day it will be 

used, as follows: 

6.13.1.1 Place the quantity of copper 

needed for sulfur removal (Section 

11.2.1.3) in a ground-glass-stoppered 

Erlenmeyer flask or bottle. Cover the foil 

or powder with methanol. 

6.13.1.2 Add HCl dropwise (0.5–1.0 

mL) while swirling, until the copper 

brightens. 

6.13.1.3 Pour off the methanol/HCl 

and rinse 3 times with reagent water to 

remove all traces of acid, then 3 times 

with acetone, then 3 times with hexane. 

6.13.1.4 For copper foil, cover with 

hexane after the final rinse. Store in a 

stoppered flask under nitrogen until 

used. For the powder, dry on a rotary 

evaporator or under a stream of 

nitrogen. Store in a stoppered flask 

under nitrogen until used. 

6.13.2 Tetrabutylammonium sodium 

sulfite (TBA sodium sulfite). 

6.13.2.1 Tetrabutylammonium 

hydrogen sulfate, [CH3(CH2)3]4NHSO4. 

6.13.2.2 Sodium sulfite, Na2SO3. 

6.13.2.3 Dissolve approximately 3 g 

tetrabutylammonium hydrogen sulfate 

in 100 mL of reagent water in an amber 

bottle with fluoropolymer-lined screw 

cap. Extract with three 20-mL portions 

of hexane and discard the hexane 

extracts. 

6.13.2.4 Add 25 g sodium sulfite to 

produce a saturated solution. Store at 

room temperature. Replace after 1 

month. 

7. Calibration 

7.1 Establish operating conditions 

equivalent to those in the footnote to 

Table 4 or 5 for the base/neutral or acid 

fraction, respectively. If a combined 

base/neutral/acid fraction will be 

analyzed, use the conditions in the 

footnote to Table 4. Alternative 

temperature program and flow rate 

conditions may be used. It is necessary 

to calibrate the GC/MS for the analytes 

of interest (Section 1.3) only. 

7.2 Internal standard calibration 

7.2.1 Prepare calibration standards 

for the analytes of interest and 

surrogates at a minimum of five 

concentration levels by adding 

appropriate volumes of one or more 

stock standards to volumetric flasks. 

One of the calibration standards should 

be at a concentration near the ML for the 

analyte in Table 1, 2, or 3. The ML value 

may be rounded to a whole number that 

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is more convenient for preparing the 

standard, but must not exceed the ML 

values listed in Table 1, 2, or 3 for those 

analytes which list ML values. 

Alternatively, the laboratory may 

establish the ML for each analyte based 

on the concentration of the lowest 

calibration standard in a series of 

standards obtained from a commercial 

vendor, again, provided that the ML 

values do not exceed the MLs in Tables 

1, 2, or 3, and provided that the 

resulting calibration meets the 

acceptance criteria in Section 7.2.3, 

based on the RSD, RSE, or R2. 

The other concentrations should 

correspond to the expected range of 

concentrations found in real samples or 

should define the working range of the 

GC/MS system for full-scan and/or SIM 

operation, as appropriate. A minimum 

of six concentration levels is required 

for a second order, non-linear (e.g., 

quadratic; ax2 + bx + c) calibration. 

Calibrations higher than second order 

are not allowed. To each calibration 

standard or standard mixture, add a 

known constant volume of the internal 

standard solution (Section 6.9), and 

dilute to volume with methylene 

chloride. 

Note: The large number of analytes in 

Tables 1 through 3 may not be soluble or 

stable in a single solution; multiple solutions 

may be required if a large number of analytes 

are to be determined simultaneously. 

7.2.1.1 Prior to analysis of the 

calibration standards, inject the DFTPP 

standard (Section 6.10) and adjust the 

scan rate of the mass spectrometer to 

produce a minimum of 5 mass spectra 

across the DFTPP GC peak. Adjust 

instrument conditions until the DFTPP 

criteria in Table 9A or 9B are met. 

Calculate peak tailing factors for 

benzidine and pentachlorophenol. 

Calculation of the tailing factor is 

illustrated in Figure 1. The tailing factor 

for benzidine and pentachlorophenol 

must be <2; otherwise, adjust 

instrument conditions and either 

replace the column or break off a short 

section of the front end of the column, 

and repeat the test. 

Note: The DFTPP spectrum may be 

evaluated by summing the intensities of the 

m/z’s across the GC peak, subtracting the 

background at each m/z in a region of the 

chromatogram within 20 scans of but not 

including any part of, the DFTPP peak. The 

DFTPP spectrum may also be evaluated by 

fitting a Gaussian to each m/z and using the 

intensity at the maximum for each Gaussian 

or by integrating the area at each m/z and 

using the integrated areas. Other means may 

be used for evaluation of the DFTPP 

spectrum so long as the spectrum is not 

distorted to meet the criteria in Table 9A or 

9B. 

7.2.1.2 Analyze the mid-point 

combined base/neutral and acid 

calibration standard and enter or review 

the retention time, relative retention 

time, mass spectrum, and quantitation 

m/z in the data system for each analyte 

of interest, surrogate, and internal 

standard. If additional analytes (Table 3) 

are to be quantified, include these 

analytes in the standard. The mass 

spectrum for each analyte must be 

comprised of a minimum of 2 m/z’s 

(Tables 4 and 5); 3 to 5 m/z’s assure 

more reliable analyte identification. 

Suggested quantitation m/z’s are shown 

in Tables 4 and 5 as the primary m/z. 

If an interference occurs at the primary 

m/z, use one of the secondary m/z’s or 

an alternate m/z. A single m/z only is 

required for quantitation. 

7.2.1.3 For SIM operation, determine 

the analytes in each descriptor, the 

quantitation and qualifier m/z’s for each 

analyte (the m/z’s can be the same as for 

full-scan operation; Section 7.2.1.2), the 

dwell time on each m/z for each analyte, 

and the beginning and ending retention 

time for each descriptor. Analyze the 

verification standard in scan mode to 

verify m/z’s and establish the retention 

times for the analytes. There must be a 

minimum of two m/z’s for each analyte 

to assure analyte identification. To 

maintain sensitivity and capture enough 

scans (≥5) across each chromatographic 

peak, there should be no more than 10 

m/z’s in a descriptor. For example, for 

a descriptor with 10 m/z’s and a 

chromatographic peak width of 5 sec, a 

dwell time of 100 ms at each m/z would 

result in a scan time of 1 second and 

provide 5 scans across the GC peak. The 

quantitation m/z will usually be the 

most intense peak in the mass spectrum. 

The quantitation m/z and dwell time 

may be optimized for each analyte. 

However, if a GC peak spans two (or 

more) descriptors, the dwell time and 

cycle time (scans/sec) should be set to 

the same value in both segments in 

order to maintain equivalent response. 

The acquisition table used for SIM must 

take into account the mass defect 

(usually less than 0.2 Daltons) that can 

occur at each m/z being monitored. 

7.2.1.4 For combined scan and SIM 

operation, set up the scan segments and 

descriptors to meet requirements in 

Sections 7.2.1.1–7.2.1.3. 

7.2.2 Analyze each calibration 

standard according to Section 12 and 

tabulate the area at the quantitation m/ 

z against concentration for each analyte 

of interest, surrogate, and internal 

standard. If an interference is 

encountered, use a secondary m/z 

(Table 4 or 5) for quantitation. Calculate 

a response factor (RF) for each analyte 

of interest at each concentration using 

Equation 1. 

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 

(mg/mL). 

Cs = Concentration of the analyte of interest 

or surrogate (mg/mL). 

7.2.3 Calculate the mean (average) 

and relative standard deviation (RSD) of 

the responses factors. If the RSD is less 

than 35%, the RF can be assumed to be 

invariant and the average RF can be 

used for calculations. Alternatively, the 

results can be used to fit a linear or 

quadratic regression of response ratios, 

As/Ais, vs. concentration ratios Cs/Cis. 

If used, the regression must be weighted 

inversely proportional to concentration. 

The coefficient of determination (R2; 

Reference 10) of the weighted regression 

must be greater than 0.920. 

Alternatively, the relative standard error 

(Reference 11) may be used as an 

acceptance criterion. As with the RSD, 

the RSE must be less than 35%. If an 

RSE less than 35% cannot be achieved 

for a quadratic regression, system 

performance is unacceptable and the 

system must be adjusted and recalibrated. 

Note: Using capillary columns and current 

instrumentation, it is quite likely that a 

laboratory can calibrate the target analytes in 

this method and achieve a linearity metric 

(either RSD or RSE) well below 35%. 

Therefore, laboratories are permitted to use 

more stringent acceptance criteria for 

calibration than described here, for example, 

to harmonize their application of this method 

with those from other sources. 

7.3 Calibration verification—The RF 

or calibration curve must be verified 

immediately after calibration and at the 

beginning of each 12-hour shift, by 

analysis of a mid-point calibration 

standard (Section 7.2.1). The standard(s) 


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must be obtained from a second 

manufacturer or a manufacturer’s batch 

prepared independently from the batch 

used for calibration. Traceability must 

be to a national standard, when 

available. The concentration of the 

standard should be near the mid-point 

of the calibration. Include the surrogates 

(Section 6.8) in this solution. It is 

necessary to verify calibration for the 

analytes of interest (Section 1.3) only. 

Note: The 12-hour shift begins after the 

DFTPP (Section 13.1) and DDT/endrin tests 

(if DDT and endrin are to be determined), 

and after analysis of the calibration 

verification standard. The 12-hour shift ends 

12 hours later. The DFTPP and DDT/endrin 

tests are outside of the 12-hour shift. 

7.3.1 Analyze the calibration 

verification standard(s) beginning in 

Section 12. Calculate the percent 

recovery of each analyte. Compare the 

recoveries for the analytes of interest 

against the acceptance criteria for 

recovery (Q) in Table 6, and the 

recoveries for the surrogates against the 

acceptance criteria in Table 8. If 

recovery of the analytes of interest and 

surrogates meet acceptance criteria, 

system performance is acceptable and 

analysis of samples may continue. If any 

individual recovery is outside its limit, 

system performance is unacceptable for 

that analyte. 

Note: The large number of analytes in 

Tables 6 and 8 present a substantial 

probability that one or more will fail 

acceptance criteria when all analytes are 

tested simultaneously. 

7.3.2 When one or more analytes fail 

acceptance criteria, analyze a second 

aliquot of the calibration verification 

standard and compare only those 

analytes that failed the first test (Section 

7.3.1) with their respective acceptance 

criteria. If these analytes now pass, 

system performance is acceptable and 

analysis of samples may continue. A 

repeat failure of any analyte that failed 

the first test, however, will confirm a 

general problem with the measurement 

system. If this occurs, repair the system 

(Section 7.2.1.1) and repeat the test 

(Section 7.3.1), or prepare a fresh 

calibration standard and repeat the test. 

If calibration cannot be verified after 

maintenance or injection of the fresh 

calibration standard, re-calibrate the 

instrument. 

Note: If it is necessary to perform a repeat 

verification test frequently; i.e., perform two 

tests in order to pass, it may be prudent to 

perform two injections in succession and 

review the results, rather than perform one 

injection, review the results, then perform 

the second injection if results from the first 

injection fail. To maintain the validity of the 

test and re-test, system maintenance and/or 

adjustment is not permitted between the 

injections. 

7.3.3 Many of the analytes in Table 

3 do not have QC acceptance criteria in 

Table 6, and some of the surrogates in 

Table 8 do not have acceptance criteria. 

If calibration is to be verified and other 

QC tests are to be performed for these 

analytes, acceptance criteria must be 

developed and applied. EPA has 

provided guidance for development of 

QC acceptance criteria (References 12 

and 13). 

7.3.4 Internal standard responses— 

Verify that detector sensitivity has not 

changed by comparing the response of 

each internal standard in the calibration 

verification standard (Section 7.3) to the 

response of the respective internal 

standard in the midpoint calibration 

standard (Section 7.2.1). The peak areas 

or heights of the internal standards in 

the calibration verification standard 

must be within 50% to 200% (1⁄2 to 2x) 

of their respective peak areas or heights 

in the mid-point calibration standard. If 

not, repeat the calibration verification 

test using a fresh calibration verification 

standard (7.3), or perform and document 

system repair. Subsequent to repair, 

repeat the calibration verification test 

(Section 7.3.1). If the responses are still 

not within 50% to 200%, re-calibrate 

the instrument (Section 7.2.2) and 

repeat the calibration verification test. 

8. Quality Control 

8.1 Each laboratory that uses this 

method is required to operate a formal 

quality assurance program. The 

minimum requirements of this program 

consist of an initial demonstration of 

laboratory capability and ongoing 

analysis of spiked samples and blanks to 

evaluate and document data quality (40 

CFR 136.7). The laboratory must 

maintain records to document the 

quality of data generated. Results of 

ongoing performance tests are compared 

with established QC acceptance criteria 

to determine if the results of analyses 

meet performance requirements of this 

method. When results of spiked samples 

do not meet the QC acceptance criteria 

in this method, a quality control check 

sample (laboratory control sample; LCS) 

must be analyzed to confirm that the 

measurements were performed in an incontrol 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 

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vendor of the SPE materials) but any 

laboratory using that specific SPE 

material must have the results of the 

study available. This includes a full data 

package with the raw data that will 

allow an independent reviewer to verify 

each determination and calculation 

performed by the laboratory (see Section 

8.1.2.2.5, items a–q). 

8.1.2.1.2 Sample matrices on which 

MS/MSD tests must be performed for 

nationwide use of an allowed 

modification: 

(a) Effluent from a POTW. 

(b) ASTM D5905 Standard 

Specification for Substitute Wastewater. 

(c) Sewage sludge, if sewage sludge 

will be in the permit. 

(d) ASTM D1141 Standard 

Specification for Substitute Ocean 

Water, if ocean water will be in the 

permit. 

(e) Untreated and treated wastewaters 

up to a total of nine matrix types (see 

http://water.epa.gov/scitech/wastetech/

guide/industry.cfm) for a list of 

industrial categories with existing 

effluent guidelines). 

At least one of the above wastewater 

matrix types must have at least one of 

the following characteristics: 

(i) Total suspended solids greater than 

40 mg/L. 

(ii) Total dissolved solids greater than 

100 mg/L. 

(iii) Oil and grease greater than 20 mg/ 

L. 

(iv) NaCl greater than 120 mg/L. 

(v) CaCO3 greater than 140 mg/L. 

The interim acceptance criteria for 

MS, MSD recoveries that do not have 

recovery limits specified in Table 6, and 

recoveries for surrogates that do not 

have recovery limits specified in Table 

8, must be no wider than 60–140%, and 

the relative percent difference (RPD) of 

the concentrations in the MS and MSD 

that do not have RPD limits specified in 

Table 6 must be less than 30%. 

Alternatively, the laboratory may use 

the laboratory’s in-house limits if they 

are tighter. 

(f) A proficiency testing (PT) sample 

from a recognized provider, in addition 

to tests of the nine matrices (Section 

8.1.2.1.1). 

8.1.2.2 The laboratory is required to 

maintain records of modifications made 

to this method. These records include 

the following, at a minimum: 

8.1.2.2.1 The names, titles, street 

addresses, telephone numbers, and 

email addresses of the analyst(s) that 

performed the analyses and 

modification, and of the quality control 

officer that witnessed and will verify the 

analyses and modifications. 

8.1.2.2.2 A list of analytes, by name 

and CAS Registry Number. 

8.1.2.2.3 A narrative stating 

reason(s) for the modifications. 

8.1.2.2.4 Results from all quality 

control (QC) tests comparing the 

modified method to this method, 

including: 

(a) Calibration (Section 7). 

(b) Calibration verification (Section 7). 

(c) Initial demonstration of capability 

(Section 8.2). 

(d) Analysis of blanks (Section 8.5). 

(e) Matrix spike/matrix spike 

duplicate analysis (Section 8.3). 

(f) Laboratory control sample analysis 

(Section 8.4). 

8.1.2.2.5 Data that will allow an 

independent reviewer to validate each 

determination by tracing the instrument 

output (peak height, area, or other 

signal) to the final result. These data are 

to include: 

(a) Sample numbers and other 

identifiers. 

(b) Extraction dates. 

(c) Analysis dates and times. 

(d) Analysis sequence/run 

chronology. 

(e) Sample weight or volume (Section 

10). 

(f) Extract volume prior to each 

cleanup step (Sections 10 and 11). 

(g) Extract volume after each cleanup 

step (Section 11). 

(h) Final extract volume prior to 

injection (Sections 10 and 12). 

(i) Injection volume (Section 12.2.3). 

(j) Sample or extract dilution (Section 

12.2.3.2). 

(k) Instrument and operating 

conditions. 

(l) Column (dimensions, material, 

etc). 

(m) Operating conditions 

(temperature program, flow rate, etc). 

(n) Detector (type, operating 

conditions, etc). 

(o) Chromatograms, mass spectra, and 

other recordings of raw data. 

(p) Quantitation reports, data system 

outputs, and other data to link the raw 

data to the results reported. 

(q) A written Standard Operating 

Procedure (SOP). 

8.1.2.2.6 Each individual laboratory 

wishing to use a given modification 

must perform the start-up tests in 

Section 8.1.2 (e.g., DOC, MDL), with the 

modification as an integral part of this 

method prior to applying the 

modification to specific discharges. 

Results of the DOC must meet the QC 

acceptance criteria in Table 6 for the 

analytes of interest (Section 1.3), and 

the MDLs must be equal to or lower 

than the MDLs in Tables 4 and 5 for the 

analytes of interest. 

8.1.3 Before analyzing samples, the 

laboratory must analyze a blank to 

demonstrate that interferences from the 

analytical system, labware, and 

reagents, are under control. Each time a 

batch of samples is extracted or reagents 

are changed, a blank must be extracted 

and analyzed as a safeguard against 

laboratory contamination. Requirements 

for the blank are given in Section 8.5. 

8.1.4 The laboratory must, on an 

ongoing basis, spike and analyze a 

minimum of one sample, in duplicate, 

with the samples in an extraction batch 

(Section 3.1). The laboratory must also 

spike and analyze, in duplicate, a 

minimum of 5% of all samples from a 

given site or discharge to monitor and 

evaluate method and laboratory 

performance on the sample matrix. The 

batch and site/discharge samples may 

be the same. The procedure for spiking 

and analysis is given in Section 8.3. 

8.1.5 The laboratory must, on an 

ongoing basis, demonstrate through 

analysis of a quality control check 

sample (laboratory control sample, LCS; 

on-going precision and recovery sample, 

OPR) that the measurement system is in 

control. This procedure is given in 

Section 8.4. 

8.1.6 The laboratory should 

maintain performance records to 

document the quality of data that is 

generated. This procedure is given in 

Section 8.9. 

8.1.7 The large number of analytes 

tested in performance tests in this 

method present a substantial probability 

that one or more will fail acceptance 

criteria when many analytes are tested 

simultaneously, and a re-test is allowed 

if this situation should occur. If, 

however, continued re-testing results in 

further repeated failures, the laboratory 

should document the failures (e.g., as 

qualifiers on results) and either avoid 

reporting results for analytes that failed 

or report the problem and failures with 

the data. Failure to report does not 

relieve a discharger or permittee of 

reporting timely results. 

8.2 Initial demonstration of 

capability (DOC)—To establish the 

ability to generate acceptable recovery 

and precision, the laboratory must 

perform the DOC in Sections 8.2.1 

through 8.2.6 for the analytes of interest. 

The laboratory must also establish 

MDLs for the analytes of interest using 

the MDL procedure at 40 CFR part 136, 

appendix B. The laboratory’s MDLs 

must be equal to or lower than those 

listed in Tables 1, 2, or 3 or lower than 

one third the regulatory compliance 

limit, whichever is greater. For MDLs 

not listed in Tables 4 and 5, the 

laboratory must determine the MDLs 

using the MDL procedure at 40 CFR 136, 

Appendix B under the same conditions 

used to determine the MDLs for the 

analytes listed in Tables 1, 2, and 3. All 

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procedures used in the analysis, 

including cleanup procedures, must be 

included in the DOC. 

8.2.1 For the DOC, a QC check 

sample concentrate containing each 

analyte of interest (Section 1.3) is 

prepared in a water-miscible solvent. 

The QC check sample concentrate must 

be prepared independently from those 

used for calibration, but may be from 

the same source as the second-source 

standard used for calibration 

verification (Section 7.3). The 

concentrate should produce 

concentrations of the analytes of interest 

in water at the mid-point of the 

calibration range, and may be at the 

same concentration as the LCS (Section 

8.4). Multiple solutions may be 

required. 

Note: QC check sample concentrates are no 

longer available from EPA. 

8.2.2 Using a pipet or micro-syringe, 

prepare four LCSs by adding an 

appropriate volume of the concentrate 

to each of four 1–L aliquots of reagent 

water, and mix well. The volume of 

reagent water must be the same as the 

volume that will be used for the sample, 

blank (Section 8.5), and MS/MSD 

(Section 8.3). A concentration of 100 mg/ 

L was used to develop the QC 

acceptance criteria in Table 6. Also add 

an aliquot of the surrogate spiking 

solution (Section 6.8). Also add an 

aliquot of the surrogate spiking solution 

(Section 6.8) to the reagent-water 

aliquots. 

8.2.3 Extract and analyze the four 

LCSs according to the method beginning 

in Section 10. 

8.2.4 Calculate the average percent 

recovery (x) and the standard deviation 

of the percent recovery(s) for each 

analyte using the four results. 

8.2.5 For each analyte, compare s 

and (x) with the corresponding 

acceptance criteria for precision and 

recovery in Table 6. For analytes in 

Table 3 not listed in Table 6, DOC QC 

acceptance criteria must be developed 

by the laboratory. EPA has provided 

guidance for development of QC 

acceptance criteria (References 12 and 

13). If s and (x) for all analytes of 

interest meet the acceptance criteria, 

system performance is acceptable and 

analysis of blanks and samples may 

begin. If any individual s exceeds the 

precision limit or any individual (x) 

falls outside the range for recovery, 

system performance is unacceptable for 

that analyte. 

Note: The large number of analytes in 

Tables 1–3 present a substantial probability 

that one or more will fail at least one of the 

acceptance criteria when many or all analytes 

are determined simultaneously. Therefore, 

the analyst is permitted to conduct a ‘‘re-test’’ 

as described in Sec. 8.2.6. 

8.2.6 When one or more of the 

analytes tested fail at least one of the 

acceptance criteria, repeat the test for 

only the analytes that failed. If results 

for these analytes pass, system 

performance is acceptable and analysis 

of samples and blanks may proceed. If 

one or more of the analytes again fail, 

system performance is unacceptable for 

the analytes that failed the acceptance 

criteria. Correct the problem and repeat 

the test (Section 8.2). See Section 8.1.7 

for disposition of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between this pair 

of tests. 

8.3 Matrix spike and matrix spike 

duplicate (MS/MSD)—The laboratory 

must, on an ongoing basis, spike at least 

5% of the samples from each sample 

site being monitored in duplicate to 

assess accuracy (recovery and 

precision). The data user should 

identify the sample and the analytes of 

interest (Section 1.3) to be spiked. If 

direction cannot be obtained, the 

laboratory must spike at least one 

sample per extraction batch of up to 20 

samples with the analytes in Tables 1 

and 2. Spiked sample results should be 

reported only to the data user whose 

sample was spiked, or as requested or 

required by a regulatory/control 

authority. 

8.3.1 If, as in compliance 

monitoring, the concentration of a 

specific analyte will be checked against 

a regulatory concentration limit, the 

concentration of the spike should be at 

that limit; otherwise, the concentration 

of the spike should be one to five times 

higher than the background 

concentration determined in Section 

8.3.2, at or near the midpoint of the 

calibration range, or at the concentration 

in the LCS (Section 8.4) whichever 

concentration would be larger. 

8.3.2 Analyze one sample aliquot to 

determine the background concentration 

(B) of the each analyte of interest. If 

necessary, prepare a new check sample 

concentrate (Section 8.2.1) appropriate 

for the background concentration. Spike 

and analyze two additional sample 

aliquots, and determine the 

concentration after spiking (A1 and A2) 

of each analyte. Calculate the percent 

recoveries (P1 and P2) as 100 (A1¥B)/T 

and 100 (A2¥B)/T, where T is the 

known true value of the spike. Also 

calculate the relative percent difference 

(RPD) between the concentrations (A1

and A2) as 200⎢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 6. A laboratory may 

develop and apply QC acceptance 

criteria more restrictive than the criteria 

in Table 6, if desired. 

8.3.3.1 If any individual P falls 

outside the designated range for 

recovery in either aliquot, or the RPD 

limit is exceeded, the result for the 

analyte in the unspiked sample is 

suspect and may not be reported or used 

for permitting or regulatory compliance 

purposes. See Section 8.1.7 for 

disposition of failures. 

8.3.3.2 The acceptance criteria in 

Table 6 were calculated to include an 

allowance for error in measurement of 

both the background and spike 

concentrations, assuming a spike to 

background ratio of 5:1. This error will 

be accounted for to the extent that the 

spike to background ratio approaches 

5:1 (Reference 14). If spiking is 

performed at a concentration lower than 

100 mg/L, the laboratory must use either 

the QC acceptance criteria in Table 6, or 

optional QC acceptance criteria 

calculated for the specific spike 

concentration. To use the optional 

acceptance criteria: (1) Calculate 

recovery (X′) using the equation in Table 

7, substituting the spike concentration 

(T) for C; (2) Calculate overall precision 

(S′) using the equation in Table 7, 

substituting X′ for x; (3) Calculate the 

range for recovery at the spike 

concentration as (100 X′/T) ± 2.44(100 

S′/T)% (Reference 14). For analytes in 

Table 3 not listed in Table 6, QC 

acceptance criteria must be developed 

by the laboratory. EPA has provided 

guidance for development of QC 

acceptance criteria (References 12 and 

13). 

8.3.4 After analysis of a minimum of 

20 MS/MSD samples for each target 

analyte and surrogate, the laboratory 

must calculate and apply in-house QC 

limits for recovery and RPD of future 

MS/MSD samples (Section 8.3). The QC 

limits for recovery are calculated as the 

mean observed recovery ± 3 standard 

deviations, and the upper QC limit for 

RPD is calculated as the mean RPD plus 

3 standard deviations of the RPDs. The 

in-house QC limits must be updated at 

least every two years and re-established 

after any major change in the analytical 

instrumentation or process. At least 

80% of the analytes tested in the MS/ 

MSD must have in-house QC acceptance 

criteria that are tighter than those in 

Table 6. If an in-house QC limit for the 

RPD is greater than the limit in Table 6, 

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then the limit in Table 6 must be used. 

Similarly, if an in-house lower limit for 

recovery is below the lower limit in 

Table 6, then the lower limit in Table 6 

must be used, and if an in-house upper 

limit for recovery is above the upper 

limit in Table 6, then the upper limit in 

Table 6 must be used. The laboratory 

must evaluate surrogate recovery data in 

each sample against its in-house 

surrogate recovery limits. The laboratory 

may use 60–140% as interim acceptance 

criteria for surrogate recoveries until inhouse limits are developed. 

8.4 Laboratory control sample 

(LCS)—A QC check sample (laboratory 

control sample, LCS; on-going precision 

and recovery sample, OPR) containing 

each analyte of interest (Section 1.3) and 

surrogate must be prepared and 

analyzed with each extraction batch of 

up to 20 samples to demonstrate 

acceptable recovery of the analytes of 

interest from a clean sample matrix. 

8.4.1 Prepare the LCS by adding QC 

check sample concentrate (Section 

8.2.1) to reagent water. Include all 

analytes of interest (Section 1.3) in the 

LCS. The LCS may be the same sample 

prepared for the DOC (Section 8.2.1). 

The volume of reagent water must be 

the same as the volume used for the 

sample, blank (Section 8.5), and MS/

MSD (Section 8.3). Also add an aliquot 

of the surrogate spiking solution 

(Section 6.8). The concentration of the 

analytes in reagent water should be the 

same as the concentration in the DOC 

(Section 8.2.2). 

8.4.2 Analyze the LCS prior to 

analysis of field samples in the 

extraction batch. Determine the 

concentration (A) of each analyte. 

Calculate the percent recovery (PS) as 

100 (A/T)%, where T is the true value 

of the concentration in the LCS. 

8.4.3 Compare the percent recovery 

(PS) for each analyte with its 

corresponding QC acceptance criterion 

in Table 6. For analytes of interest in 

Table 3 not listed in Table 6, use the QC 

acceptance criteria developed for the 

MS/MSD (Section 8.3.3.2). If the 

recoveries for all analytes of interest fall 

within their respective QC acceptance 

criteria, analysis of blanks and field 

samples may proceed. If any individual 

PS falls outside the range, proceed 

according to Section 8.4.4. 

Note: The large number of analytes in 

Tables 1–3 present a substantial probability 

that one or more will fail the acceptance 

criteria when all analytes are tested 

simultaneously. Because a re-test is allowed 

in event of failure (Sections 8.1.7 and 8.4.3), 

it may be prudent to extract and analyze two 

LCSs together and evaluate results of the 

second analysis against the QC acceptance 

criteria only if an analyte fails the first test. 

8.4.4 Repeat the test only for those 

analytes that failed to meet the 

acceptance criteria (PS). If these 

analytes now pass, system performance 

is acceptable and analysis of blanks and 

samples may proceed. Repeated failure, 

however, will confirm a general 

problem with the measurement system. 

If this occurs, repeat the test using a 

fresh LCS (Section 8.2.2) or an LCS 

prepared with a fresh QC check sample 

concentrate (Section 8.2.1), or perform 

and document system repair. 

Subsequent to repair, repeat the LCS test 

(Section 8.4). If failure of the LCS 

indicates a systemic problem with 

samples in the batch, re-extract and reanalyze the samples in the batch. See 

Section 8.1.7 for disposition of repeated 

failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between the pair 

of tests. 

8.4.5 After analysis of 20 LCS 

samples, the laboratory must calculate 

and apply in-house QC limits for 

recovery to future LCS samples (Section 

8.4). Limits for recovery in the LCS are 

calculated as the mean recovery ±3 

standard deviations. A minimum of 

80% of the analytes tested for in the 

LCS must have QC acceptance criteria 

tighter than those in Table 6. Many of 

the analytes and surrogates may not 

contain recommended acceptance 

criteria. The laboratory should use 60– 

140% as interim acceptance criteria for 

recoveries of spiked analytes and 

surrogates that do not have recovery 

limits specified in Table 8, until inhouse LCS and surrogate limits are 

developed. If an in-house lower limit for 

recovery is lower than the lower limit in 

Table 6, the lower limit in Table 6 must 

be used, and if an in-house upper limit 

for recovery is higher than the upper 

limit in Table 6, the upper limit in Table 

6 must be used. 

8.5 Blank—A blank must be 

extracted and analyzed with each 

extraction batch to demonstrate that the 

reagents and equipment used for 

preparation and analysis are free from 

contamination. 

8.5.1 Spike the surrogates into the 

blank. Extract and concentrate the blank 

using the same procedures and reagents 

used for the samples, LCS, and MS/MSD 

in the batch. Analyze the blank 

immediately after analysis of the LCS 

(Section 8.4) and prior to analysis of the 

MS/MSD and samples to demonstrate 

freedom from contamination. 

8.5.2 If any analyte of interest is 

found in the blank: 1) At a 

concentration greater than the MDL for 

the analyte, 2) at a concentration greater 

than one-third the regulatory 

compliance limit, or 3) at a 

concentration greater than one-tenth the 

concentration in a sample in the 

extraction batch, whichever is greater, 

analysis of samples must be halted and 

samples affected by the blank must be 

re-extracted and the extracts reanalyzed. Samples must be associated 

with an uncontaminated blank before 

they may be reported or used for 

permitting or regulatory compliance 

purposes. 

8.6 Internal standards responses. 

8.6.1 Calibration verification—The 

responses (GC peak heights or areas) of 

the internal standards in the calibration 

verification must be within 50% to 

200% (1⁄2 to 2x) of their respective 

responses in the mid-point calibration 

standard. If they are not, repeat the 

calibration verification (Section 7.4) test 

or perform and document system repair. 

Subsequent to repair, repeat the 

calibration verification. If the responses 

are still not within 50% to 200%, recalibrate the instrument (Section 7) and 

repeat the calibration verification/LCS 

test. 

8.6.2 Samples, blanks, LCSs, and 

MS/MSDs—The responses (GC peak 

heights or areas) of the internal 

standards in each sample, blank, and 

MS/MSD must be within 50% to 200% 

(1⁄2 to 2x) of its respective response in 

the most recent LCS. If, as a group, all 

internal standards are not within this 

range, perform and document system 

repair, repeat the calibration 

verification/LCS test (Section 8.4), and 

re-analyze the affected samples. If a 

single internal standard is not within 

the 50% to 200% range, use an alternate 

internal standard for quantitation of the 

analyte referenced to the affected 

internal standard. 

8.7 Surrogate recoveries—Spike the 

surrogates into all samples, blanks, 

LCSs, and MS/MSDs. Compare 

surrogate recoveries against the QC 

acceptance criteria in Table 8 and/or 

those developed in Section 7.3.3. If any 

recovery fails its criteria, attempt to find 

and correct the cause of the failure. 

Surrogate recoveries from the blank and 

LCS may be used as pass/fail criteria by 

the laboratory or as required by a 

regulatory authority, or may be used to 

diagnose problems with the analytical 

system. 

8.8 DDT and endrin decomposition 

(breakdown)—If DDT and/or endrin are 

to be analyzed using this method, a 

DDT/endrin decomposition test must be 

performed to reliably quantify these two 

pesticides. The DDT/endrin 

decomposition test to be used is in EPA 

Method 608A or 1656. 

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8.9 As part of the QC program for 

the laboratory, control charts or 

statements of accuracy for wastewater 

samples must be assessed and records 

maintained (40 CFR 136.7(c)(1)(viii)). 

After analysis of five or more spiked 

wastewater samples as in Section 8.3, 

calculate the average percent recovery 

(x) and the standard deviation of the 

percent recovery (sp). Express the 

accuracy assessment as a percent 

interval from x ¥2sp to x +2sp. For 

example, if x = 90% and sp = 10%, the 

accuracy interval is expressed as 70– 

110%. Update the accuracy assessment 

for each analyte on a regular basis (e.g., 

after each 5–10 new accuracy 

measurements). 

8.10 It is recommended that the 

laboratory adopt additional quality 

assurance practices for use with this 

method. The specific practices that are 

most productive depend upon the needs 

of the laboratory and the nature of the 

samples. Field duplicates may be 

analyzed to assess the precision of 

environmental measurements. 

Whenever possible, the laboratory 

should analyze standard reference 

materials and participate in relevant 

performance evaluation studies. 

9. Sample Collection, Preservation, and 

Handling 

9.1 Collect samples as grab samples 

in glass bottles or in refrigerated bottles 

using automatic sampling equipment. 

Collect 1–L of ambient waters, effluents, 

and other aqueous samples. If the 

sensitivity of the analytical system is 

sufficient, a smaller volume (e.g., 250 

mL), but no less than 100 mL, may be 

used. Conventional sampling practices 

(Reference 15) should be followed, 

except that the bottle must not be prerinsed 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 

°C from the time of collection until 

extraction, but do not freeze. If residual 

chlorine is present, add 80 mg of 

sodium thiosulfate per liter of sample 

and mix well. Any method suitable for 

field use may be employed to test for 

residual chlorine (Reference 16). Do not 

add excess sodium thiosulfate. If 

sodium thiosulfate interferes in the 

determination of the analytes, an 

alternate preservative (e.g., ascorbic acid 

or sodium sulfite) may be used. 

9.3 All samples must be extracted 

within 7 days of collection and sample 

extracts must be analyzed within 40 

days of extraction. 

10. Extraction 

10.1 This section contains 

procedures for separatory funnel liquidliquid extraction (SFLLE) and 

continuous liquid-liquid extraction 

(CLLE). SFLLE is faster, but may not be 

as effective as CLLE for recovery of 

polar analytes such as phenol. SFLLE is 

labor intensive and may result in 

formation of emulsions that are difficult 

to break. CLLE is less labor intensive, 

avoids emulsion formation, but requires 

more time (18–24 hours) and more hood 

space, and may require more solvent. 

The procedures assume base-neutral 

extraction followed by acid extraction. 

For some matrices and analytes of 

interest, improved results may be 

obtained by acid-neutral extraction 

followed by base extraction. A single 

acid or base extraction may also be 

performed. If an extraction scheme 

alternate to base-neutral followed by 

acid extraction is used, all QC tests must 

be performed and all QC acceptance 

criteria must be met with that extraction 

scheme as an integral part of this 

method. 

10.2 Separatory funnel liquid-liquid 

extraction (SFLLE) and extract 

concentration 

10.2.1 The SFLLE procedure below 

assumes a sample volume of 1 L. When 

a different sample volume is extracted, 

adjust the volume of methylene chloride 

accordingly. 

10.2.2 Mark the water meniscus on 

the side of the sample bottle for later 

determination of sample volume. Pour 

the entire sample into the separatory 

funnel. Pipet the surrogate standard 

spiking solution (Section 6.8) into the 

separatory funnel. If the sample will be 

used for the LCS or MS or MSD, pipet 

the appropriate check sample 

concentrate (Section 8.2.1 or 8.3.2) into 

the separatory funnel. Mix well. Check 

the pH of the sample with wide-range 

pH paper and adjust to pH 11–13 with 

sodium hydroxide solution. 

10.2.3 Add 60 mL of methylene 

chloride to the sample bottle, seal, and 

shake for approximately 30 seconds to 

rinse the inner surface. Transfer the 

solvent to the separatory funnel and 

extract the sample by shaking the funnel 

for two minutes with periodic venting to 

release excess pressure. Allow the 

organic layer to separate from the water 

phase for a minimum of 10 minutes. If 

the emulsion interface between layers is 

more than one-third the volume of the 

solvent layer, the analyst must employ 

mechanical techniques to complete the 

phase separation. The optimum 

technique depends upon the sample, 

but may include stirring, filtration of the 

emulsion through glass wool, 

centrifugation, or other physical 

methods. Collect the methylene chloride 

extract in a flask. If the emulsion cannot 

be broken (recovery of <80% of the 

methylene chloride), transfer the 

sample, solvent, and emulsion into a 

continuous extractor and proceed as 

described in Section 10.3. 

10.2.4 Add a second 60-mL volume 

of methylene chloride to the sample 

bottle and repeat the extraction 

procedure a second time, combining the 

extracts in the Erlenmeyer flask. 

Perform a third extraction in the same 

manner. 

10.2.5 Adjust the pH of the aqueous 

phase to less than 2 using sulfuric acid. 

Serially extract the acidified aqueous 

phase three times with 60 mL aliquots 

of methylene chloride. Collect and 

combine the extracts in a flask in the 

same manner as the base/neutral 

extracts. 

Note: Base/neutral and acid extracts may 

be combined for concentration and analysis 

provided all QC tests are performed and all 

QC acceptance criteria met for the analytes of 

interest with the combined extract as an 

integral part of this method, and provided 

that the analytes of interest are as reliably 

identified and quantified as when the 

extracts are analyzed separately. If doubt 

exists as to whether identification and 

quantitation will be affected by use of a 

combined extract, the fractions must be 

analyzed separately. 

10.2.6 For each fraction or the 

combined fractions, assemble a 

Kuderna-Danish (K–D) concentrator by 

attaching a 10-mL concentrator tube to 

a 500-mL evaporative flask. Other 

concentration devices or techniques 

may be used in place of the K–D 

concentrator so long as the requirements 

in Section 8.2 are met. 

10.2.7 For each fraction or the 

combined fractions, pour the extract 

through a solvent-rinsed drying column 

containing about 10 cm of anhydrous 

sodium sulfate, and collect the extract 

in the K–D concentrator. Rinse the 

Erlenmeyer flask and column with 20– 

30 mL of methylene chloride to 

complete the quantitative transfer. 

10.2.8 Add one or two clean boiling 

chips and attach a three-ball Snyder 

column to the evaporative flask for each 

fraction (Section 10.2.7). Pre-wet the 

Snyder column by adding about 1 mL of 

methylene chloride to the top. Place the 

K–D apparatus on a hot water bath (60– 

65 °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 

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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 twoball 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 °C) so that the concentrator tube 

is partially immersed in hot water. 

Adjust the vertical position of the 

apparatus and the water temperature as 

required to complete the concentration 

in 5–10 minutes. At the proper rate of 

distillation the balls of the column will 

actively chatter but the chambers will 

not flood with condensed solvent. When 

the apparent volume of liquid reaches 

about 1 mL or other determined amount, 

remove the K–D apparatus from the 

water bath and allow it to drain and 

cool for at least 10 minutes. Remove the 

Snyder column and rinse the flask and 

its lower joint into the concentrator tube 

with approximately 0.2 mL of or 

methylene chloride. Adjust the final 

volume to 1.0 mL or a volume 

appropriate to the sensitivity desired 

(e.g., to meet lower MDLs or for selected 

ion monitoring). Record the volume, 

stopper the concentrator tube and store 

refrigerated if further processing will 

not be performed immediately. If the 

extracts will be stored longer than two 

days, they should be transferred to 

fluoropolymer-lined screw-cap vials and 

labeled base/neutral or acid fraction as 

appropriate. Mark the level of the 

extract on the vial so that solvent loss 

can be detected. 

10.2.10 Nitrogen evaporation and 

solvent exchange—Extracts may be 

concentrated for analysis using nitrogen 

evaporation in place of micro K–D 

concentration (Section 10.2.9). Extracts 

that have been cleaned up using sulfur 

removal (Section 12.2) and are ready for 

analysis are exchanged into methylene 

chloride. 

10.2.10.1 Transfer the vial 

containing the sample extract to the 

nitrogen evaporation (blowdown) device 

(Section 5.8). Lower the vial into the 

water bath and begin concentrating. If 

the more volatile analytes (Section 1.2) 

are to be concentrated, use room 

temperature for concentration; 

otherwise, a slightly elevated (e.g., 30– 

45 °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 mL, add 2 to 

3 mL of methylene chloride and 

continue concentrating to 

approximately 100 mL. Repeat the 

addition of solvent and concentrate 

once more. Adjust the final extract 

volume to be consistent with the 

volume extracted and the sensitivity 

desired. 

10.2.10.3 For extracts that have been 

cleaned up by GPC and that are to be 

concentrated to a nominal volume of 1 

mL, adjust the final volume to 

compensate the GPC loss. For a 50% 

GPC loss, concentrate the extract to 1/ 

2000 of the volume extracted. For 

example, if the volume extracted is 950 

mL, adjust the final volume to 0.48 mL. 

For extracts that have not been cleaned 

up by GPC and are to be concentrated 

to a nominal volume of 1.0 mL, adjust 

the final extract volume to 1/1000 of the 

volume extracted. For example, if the 

volume extracted is 950 mL, adjust the 

final extract volume to 0.95 mL. 

Note: The difference in the volume fraction 

for an extract cleaned up by GPC accounts for 

the loss in GPC cleanup. Also, by preserving 

the ratio between the volume extracted and 

the final extract volume, the concentrations 

and detection limits do not need to be 

adjusted for differences in the volume 

extracted and the extract volume. 

10.2.11 Transfer the concentrated 

extract to a vial with fluoropolymerlined 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 °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, 

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while stirring, adjust the pH of the 

aqueous phase to less than 2 using 

sulfuric acid. Extract for 18–24 hours. A 

shorter or longer extraction time may be 

used if all QC acceptance criteria are 

met. Test and, if necessary, adjust the 

pH of the water during the second or 

third hour of the extraction. After 

extraction, allow the apparatus to cool, 

then detach the distilling flask. Dry, 

concentrate, and seal the extract per 

Sections 10.2.6 through 10.2.11. 

Determine the sample volume per 

Section 10.2.12. 

11. Extract Cleanup 

Note: Cleanup may not be necessary for 

relatively clean samples (e.g., treated 

effluents, groundwater, drinking water). If 

particular circumstances require the use of a 

cleanup procedure, the laboratory may use 

any or all of the procedures below or any 

other appropriate procedure. Before using a 

cleanup procedure, the laboratory must 

demonstrate that the requirements of Section 

8.1.2 can be met using the cleanup procedure 

as an integral part of this method. 

11.1 Gel permeation 

chromatography (GPC). 

11.1.1 Calibration. 

11.1.1.1 Load the calibration 

solution (Section 6.12) into the sample 

loop. 

11.1.1.2 Inject the calibration 

solution and record the signal from the 

detector. The elution pattern will be 

corn oil, bis(2-ethylhexyl) phthalate, 

pentachlorophenol, perylene, and 

sulfur. 

11.1.1.3 Set the ‘‘dump time’’ to 

allow >85% removal of the corn oil and 

>85% collection of the phthalate. 

11.1.1.4 Set the ‘‘collect time’’ to the 

peak minimum between perylene and 

sulfur. 

11.1.1.5 Verify calibration with the 

calibration solution after every 20 or 

fewer extracts. Calibration is verified if 

the recovery of the pentachlorophenol is 

greater than 85%. If calibration is not 

verified, recalibrate using the calibration 

solution, and re-extract and clean up the 

preceding extracts using the calibrated 

GPC system. 

11.1.2 Extract cleanup—GPC 

requires that the column not be 

overloaded. The column specified in 

this method is designed to handle a 

maximum of 0.5 g of high molecular 

weight material in a 5-mL extract. If the 

extract is known or expected to contain 

more than 0.5 g, the extract is split into 

fractions for GPC and the fractions are 

combined after elution from the column. 

The solids content of the extract may be 

obtained gravimetrically by evaporating 

the solvent from a 50-mL aliquot. 

11.1.2.1 Filter the extract or load 

through the filter holder to remove 

particulates. Load the extract into the 

sample loop. The maximum capacity of 

the column is 0.5–1.0 g. If necessary, 

split the extract into multiple aliquots to 

prevent column overload. 

11.1.2.2 Elute the extract using the 

calibration data determined in Section 

11.1.1. Collect the eluate in the K–D 

apparatus reserved in Section 10.2.8. 

11.1.3 Concentrate the cleaned up 

extract per Sections 10.2.8 and 10.2.9 or 

10.2.10. 

11.1.4 Rinse the sample loading tube 

thoroughly with methylene chloride 

between extracts to prepare for the next 

sample. 

11.1.5 If a particularly dirty extract 

is encountered, run a methylene 

chloride blank through the system to 

check for carry-over. 

11.2 Sulfur removal. 

Note: Separate procedures using copper or 

TBA sulfite are provided in this section for 

sulfur removal. They may be used separately 

or in combination, if desired. 

11.2.1 Removal with copper 

(Reference 17). 

Note: If (1) an additional compound (Table 

3) is to be determined; (2) sulfur is to be 

removed; (3) copper will be used for sulfur 

removal; and (4) a sulfur matrix is known or 

suspected to be present, the laboratory must 

demonstrate that the additional compound 

can be successfully extracted and treated 

with copper in the sulfur matrix. Some of the 

additional compounds (Table 3) are known 

not to be amenable to sulfur removal with 

copper (e.g. Atrazine and Diazinon). 

11.2.1.1 Quantitatively transfer the 

extract from Section 10.2.8 to a 40- to 

50-mL flask or bottle. If there is 

evidence of water in the concentrator 

tube after the transfer, rinse the tube 

with small portions of hexane:acetone 

(40:60) and add to the flask or bottle. 

Mark and set aside the concentrator tube 

for use in re-concentrating the extract. 

11.2.1.2 Add 10–20 g of granular 

anhydrous sodium sulfate to the flask. 

Swirl to dry the extract. 

11.2.1.3 Add activated copper 

(Section 6.13.1.4) and allow to stand for 

30–60 minutes, swirling occasionally. If 

the copper does not remain bright, add 

more and swirl occasionally for another 

30–60 minutes. 

11.2.1.4 After drying and sulfur 

removal, quantitatively transfer the 

extract to a nitrogen-evaporation vial or 

tube and proceed to Section 10.2.10 for 

nitrogen evaporation and solvent 

exchange, taking care to leave the 

sodium sulfate and copper in the flask. 

11.2.2 Removal with TBA sulfite. 

11.2.2.1 Using small volumes of 

hexane, quantitatively transfer the 

extract to a 40- to 50-mL centrifuge tube 

with fluoropolymer-lined screw cap. 

11.2.2.2 Add 1–2 mL of TBA sulfite 

reagent (Section 6.13.2.4), 2–3 mL of 2- 

propanol, and approximately 0.7 g of 

sodium sulfite (Section 6.13.2.2) crystals 

to the tube. Cap and shake for 1–2 

minutes. If the sample is colorless or if 

the initial color is unchanged, and if 

clear crystals (precipitated sodium 

sulfite) are observed, sufficient sodium 

sulfite is present. If the precipitated 

sodium sulfite disappears, add more 

crystalline sodium sulfite in 

approximately 0.5 g portions until a 

solid residue remains after repeated 

shaking. 

11.2.2.3 Add 5–10 mL of reagent 

water and shake for 1–2 minutes. 

Centrifuge to settle the solids. 

11.2.2.4 Quantitatively transfer the 

hexane (top) layer through a small 

funnel containing a few grams of 

granular anhydrous sodium sulfate to a 

nitrogen-evaporation vial or tube and 

proceed to Section 10.2.10 for nitrogen 

evaporation and solvent exchange. 

12. Gas Chromatography/Mass 

Spectrometry 

12.1 Establish the operating 

conditions in Table 4 or 5 for analysis 

of a base/neutral or acid extract, 

respectively. For analysis of a combined 

extract (Section 10.2.5, note), use the 

operating conditions in Table 4. 

Included in these tables are retention 

times and MDLs that can be achieved 

under these conditions. Examples of the 

separations achieved are shown in 

Figure 2 for the combined extract. 

Alternative columns or chromatographic 

conditions may be used if the 

requirements of Section 8.2 are met. 

Verify system performance per Section 

13. 

12.2 Analysis of a standard or 

extract. 

12.2.1 Bring the standard or 

concentrated extract (Section 10.2.9 or 

10.2.11) to room temperature and verify 

that any precipitate has redissolved. 

Verify the level on the extract and bring 

to the mark with solvent if required. 

12.2.2 Add the internal standard 

solution (Section 6.9) to the extract. Mix 

thoroughly. 

12.2.3 Inject an appropriate volume 

of the sample extract or standard 

solution using split, splitless, solvent 

purge, large-volume, or on-column 

injection. If the sample is injected 

manually the solvent-flush technique 

should be used. The injection volume 

depends upon the technique used and 

the ability to meet MDLs or reporting 

limits for regulatory compliance. 

Injected volumes must be the same for 

standards and sample extracts. Record 

the volume injected to two significant 

figures. 

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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 °C 

protected from light in screw-cap vials 

equipped with un-pierced 

fluoropolymer-lined septa. 

13. Performance tests 

13.1 At the beginning of each 12- 

hour shift during which standards or 

extracts will be analyzed, perform the 

tests in Sections 13.2–13.7 to verify 

system performance. If DDT and/or 

endrin are to be determined, perform 

the decomposition test in Section 13.8. 

If an extract is concentrated for greater 

sensitivity (e.g., by SIM), all tests must 

be performed at levels consistent with 

the reduced extract volume. 

13.2 DFTPP—Inject the DFTPP 

standard (Section 6.10) and verify that 

the criteria for DFTPP in Section 7.2.1.1 

and Table 9A (Reference 18) for a 

quadrupole MS, or Table 9B (Reference 

19) for a time-of-flight MS, are met. It is 

not necessary to meet DFTPP criteria for 

SIM operation. 

13.3 GC resolution—There must be a 

valley between benzo(b)fluoranthene 

and benzo(k)fluoranthene at m/z 252, 

and the height of the valley must not 

exceed 25 percent of the shorter of the 

two peaks. 

13.4 Calibration verification—Verify 

calibration per Sections 7.3 and Table 6. 

13.5 Peak tailing—Verify the tailing 

factor specifications are met per Section 

7.2.1.1. 

13.6 Laboratory control sample and 

blank—Analyze the extracts of the LCS 

and blank at the beginning of analyses 

of samples in the extraction batch 

(Section 3.1). The LCS must meet the 

requirements in Section 8.4, and the 

blank must meet the requirements in 

Section 8.5 before sample extracts may 

be analyzed. 

13.7 Matrix spike/matrix spike 

duplicate—Analyze the background 

sample for the MS/MSD and the MS and 

MSD after the blank (Section 8.3.2). 

Results for the MS/MSD must meet the 

requirements in Section 8.3 before a 

result for an analyte in any unspiked 

sample in the batch may be reported or 

used for permitting or regulatory 

compliance purposes. 

13.8 DDT/endrin decomposition 

test—If DDT and/or endrin analytes of 

interest, the DDT/endrin test (Section 

8.8) must be performed and the QC 

acceptance criteria must be met before 

analyzing samples for DDT and/or 

endrin. 

14. Qualitative Identification 

14.1 Identification is accomplished 

by comparison of data from analysis of 

a sample or blank with data stored in 

the GC/MS data system (Sections 5.6.5 

and 7.2.1.2, and Tables 4 and 5). 

Identification of an analyte is confirmed 

per Sections 14.1.1 through 14.1.4. 

14.1.1 The signals for all 

characteristic m/z’s stored in the data 

system for each analyte of interest must 

be present and must maximize within 

the same two consecutive scans. 

14.1.2 Based on the relative 

retention time (RRT), the RRT for the 

analyte must be within ±0.06 of the RRT 

of the analyte in the calibration 

verification run at the beginning of the 

shift (Section 7.3 or 13.4). Relative 

retention time is used to establish the 

identification window because it 

compensates for small changes in the 

GC temperature program whereas the 

absolute retention time does not (see 

Section 6.9.3). 

Note: RRT is a unitless quantity (see Sec. 

20.2), although some procedures refer to 

‘‘RRT units’’ in providing the specification 

for the agreement between the RRT values in 

the sample and the calibration verification or 

other standard. 

14.1.3 Either (1) the background 

corrected EICP areas, or (2) the corrected 

relative intensities of the mass spectral 

peaks at the GC peak maximum, must 

agree within 50% to 200% (1⁄2 to 2 

times) for all m/z’s in the reference mass 

spectrum stored in the data system 

(Section 7.2.1.2), or from a reference 

library. For example, if a peak has an 

intensity of 20% relative to the base 

peak, the analyte is identified if the 

intensity of the peak in the sample is in 

the range of 10% to 40% of the base 

peak. 

14.1.4 The m/z’s present in the 

acquired mass spectrum for the sample 

that are not present in the reference 

mass spectrum must be accounted for by 

contaminant or background m/z’s. A 

reference library may be helpful to 

identify and account for background or 

contaminant m/z’s. If the acquired mass 

spectrum is contaminated, or if 

identification is ambiguous, an 

experienced spectrometrist (Section 1.7) 

must determine the presence or absence 

of the compound. 

14.2 Structural isomers that have 

very similar mass spectra can be 

identified only if the resolution between 

authentic isomers in a standard mix is 

acceptable. Acceptable resolution is 

achieved if the baseline to valley height 

between the isomers is less than 50% of 

the height of the shorter of the two 

peaks. Otherwise, structural isomers are 

identified as isomeric pairs. 

15. Calculations 

15.1 When an analyte has been 

identified, quantitation of that analyte is 

based on the integrated abundance from 

the EICP of the primary characteristic 

m/z in Table 4 or 5. Calculate the 

concentration in the extract using the 

response factor (RF) determined in 

Section 7.2.2 and Equation 2. If the 

concentration of an analyte exceeds the 

calibration range, dilute the extract by 

the minimum amount to bring the 

concentration into the calibration range, 

and re-analyze the extract. Determine a 

dilution factor (DF) from the amount of 

the dilution. For example, if the extract 

is diluted by a factor of 2, DF = 2. 

Where: 

Cex = Concentration of the analyte in the 

extract, in mg/mL, and the other terms are 

as defined in Equation 1. 

Calculate the concentration of the 

analyte in the sample using the 

concentration in the extract, the extract 

volume, the sample volume, and the 

dilution factor, per Equation 3: 


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Where: 

Cs = Concentration of the analyte in the 

sample 

Cex = Concentration of the analyte in the 

extract, in mg/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 mg/L without correction for 

recovery. (Other units may be used if 

required by in a permit.) Report all QC 

data with the sample results. 

15.2.2 Reporting level 

Unless otherwise specified in by a 

regulatory authority or in a discharge 

permit, results for analytes that meet the 

identification criteria are reported down 

to the concentration of the ML 

established by the laboratory through 

calibration of the instrument (see 

Section 7.3.2 and the glossary for the 

derivation of the ML). EPA considers 

the terms ‘‘reporting limit,’’ 

‘‘quantitation limit,’’ and ‘‘minimum 

level’’ to be synonymous. 

15.2.2.1 Report a result for each 

analyte in each sample, blank, or 

standard at or above the ML to 3 

significant figures. Report a result for 

each analyte found in each sample 

below the ML as ‘‘ML,’’ or as required 

by the regulatory authority or permit. 

Results are reported without blank 

subtraction unless requested or required 

by a regulatory authority or in a permit. 

In this case, both the sample result and 

the blank results must be reported 

together. 

15.2.2.2 In addition to reporting 

results for samples and blanks 

separately, the concentration of each 

analyte in a blank associated with the 

sample may be subtracted from the 

result for that sample, but only if 

requested or required by a regulatory 

authority or in a permit. In this case, 

both the sample result and the blank 

results must be reported together. 

15.2.2.3 Report a result for an 

analyte found in a sample or extract that 

has been diluted at the least dilute level 

at which the area at the quantitation m/ 

z is within the calibration range (i.e., 

above the ML for the analyte) and the 

MS/MSD recovery and RPD are within 

their respective QC acceptance criteria 

(Table 6). This may require reporting 

results for some analytes from different 

analyses. 

15.2.3 Results from tests performed 

with an analytical system that is not in 

control (i.e., that does not meet 

acceptance criteria for all of QC tests in 

this method) must not be reported or 

otherwise used for permitting or 

regulatory compliance purposes, but do 

not relieve a discharger or permittee of 

reporting timely results. If the holding 

time would be exceeded for a reanalysis 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 

mg/L (Reference 2). Single operator 

precision, overall precision, and method 

accuracy were found to be directly 

related to the concentration of the 

analyte and essentially independent of 

the sample matrix. Linear equations to 

describe these relationships are 

presented in Table 7. 

16.2 As noted in Sec. 1.1, this 

method was validated through an 

interlaboratory study conducted more 

than 29 years ago. However, the 

fundamental chemistry principles used 

in this method remain sound and 

continue to apply. 

16.3 A chromatogram of the 

combined acid/base/neutral calibration 

standard is shown in Figure 2. 

17. Pollution Prevention 

17.1 Pollution prevention 

encompasses any technique that reduces 

or eliminates the quantity or toxicity of 

waste at the point of generation. Many 

opportunities for pollution prevention 

exist in laboratory operations. EPA has 

established a preferred hierarchy of 

environmental management techniques 

that places pollution prevention as the 

management option of first choice. 

Whenever feasible, the laboratory 

should use pollution prevention 

techniques to address waste generation. 

When wastes cannot be reduced at the 

source, the Agency recommends 

recycling as the next best option. 

17.2 The analytes in this method are 

used in extremely small amounts and 

pose little threat to the environment 

when managed properly. Standards 

should be prepared in volumes 

consistent with laboratory use to 

minimize the disposal of excess 

volumes of expired standards. This 

method utilizes significant quantities of 

methylene chloride. Laboratories are 

encouraged to recover and recycle this 

and other solvents during extract 

concentration. 

17.3 For information about pollution 

prevention that may be applied to 

laboratories and research institutions, 

consult Less is Better: Laboratory 

Chemical Management for Waste 

Reduction, available from the American 

Chemical Society’s Department of 

Governmental Relations and Science 

Policy, 1155 16th Street NW., 

Washington, DC 20036, 202/872–4477. 

18. Waste Management 

18.1 The laboratory is responsible 

for complying with all Federal, State, 

and local regulations governing waste 

management, particularly the hazardous 

waste identification rules and land 

disposal restrictions, and to protect the 

air, water, and land by minimizing and 

controlling all releases from fume hoods 

and bench operations. Compliance is 

also required with any sewage discharge 

permits and regulations. An overview of 

requirements can be found in 

Environmental Management Guide for 

Small Laboratories (EPA 233–B–98– 

001). 

18.2 Samples at pH <2, or pH >12 

are hazardous and must be neutralized 

before being poured down a drain, or 

must be handled and disposed of as 

hazardous waste. 

18.3 Many analytes in this method 

decompose above 500 °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. 


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19. References 

1. ‘‘Sampling and Analysis Procedures 

for Screening of Industrial Effluents 

for Priority Pollutants,’’ U.S. 

Environmental Protection Agency, 

Environmental Monitoring and 

Support Laboratory, Cincinnati, 

Ohio 45268, March 1977, Revised 

April 1977. 

2. ‘‘EPA Method Study 30, Method 625, 

Base/Neutrals, Acids, and 

Pesticides,’’ EPA 600/4–84–053, 

National Technical Information 

Service, PB84–206572, Springfield, 

Virginia 22161, June 1984. 

3. 40 CFR part 136, appendix B. 

4. Olynyk, P., Budde, W.L. and 

Eichelberger, J.W. ‘‘Method 

Detection Limit for Methods 624 

and 625,’’ Unpublished report, May 

14, 1980. 

5. Annual Book of ASTM Standards, 

Volume 11.02, D3694–96, 

‘‘Standard Practices for Preparation 

of Sample Containers and for 

Preservation of Organic 

Constituents,’’ American Society for 

Testing and Materials, Philadelphia. 

6. Solutions to Analytical Chemistry 

Problems with Clean Water Act 

Methods, EPA 821–R–07–002, 

March 2007. 

7. ‘‘Carcinogens-Working With 

Carcinogens,’’ Department of 

Health, Education, and Welfare, 

Public Health Service, Center for 

Disease Control, National Institute 

for Occupational Safety and Health, 

Publication No. 77–206, August 

1977. 

8. ‘‘OSHA Safety and Health Standards, 

General Industry,’’ (29 CFR part 

1910), Occupational Safety and 

Health Administration, OSHA 2206 

(Revised, January 1976). 

9. ‘‘Safety in Academic Chemistry 

Laboratories,’’ American Chemical 

Society Publication, Committee on 

Chemical Safety, 7th Edition, 2003. 

10. http://en.wikipedia.org/wiki/

Coefficient_of_determination 

(accessed on 09/10/2013). 

11. 40 CFR 136.6(b)(4)(x). 

12. 40 CFR 136.6(b)(2)(i). 

13. Protocol for EPA Approval of New 

Methods for Organic and Inorganic 

Analytes in Wastewater and 

Drinking Water (EPA–821–B–98– 

003) March 1999. 

14. Provost, L.P. and Elder, R.S. 

‘‘Interpretation of Percent Recovery 

Data,’’ American Laboratory, 15, 

58–63 (1983). (The value 2.44 used 

in the equation in Section 8.3.3 is 

two times the value 1.22 derived in 

this report.) 

15. ASTM Annual Book of Standards, 

Part 31, D3370–76. ‘‘Standard 

Practices for Sampling Water,’’ 

American Society for Testing and 

Materials, Philadelphia. 

16. 40 CFR 136.3(a), Table IB, 

Chlorine—Total Residual. 

17. ‘‘Manual of Analytical Methods for 

the Analysis of Pesticides in Human 

and Environmental Samples,’’ EPA– 

600/8–80–038, U.S. Environmental 

Protection Agency, Health Effects 

Research Laboratory, Research 

Triangle Park, North Carolina. 

18. Eichelberger, J.W., Harris, L.E., and 

Budde, W.L. ‘‘Reference Compound 

to Calibrate Ion Abundance 

Measurement in Gas 

Chromatography-Mass 

Spectrometry,’’ Analytical 

Chemistry, 47, 995 (1975). 

19. Letter of approval of acceptance 

criteria for DFTPP for time-of-flight 

mass spectrometers from William 

A. Telliard and Herb Brass of EPA 

to Jack Cochran of LECO 

Corporation, February 9, 2005. 

20. Tables. 

TABLE 1—NON PESTICIDE/PCB BASE/NEUTRAL EXTRACTABLES 1

Analyte CAS Registry MDL 4 ML 5

Acenaphthene .............................................................................................................................. 83–32–9 1.9 5.7 

Acenaphthylene ........................................................................................................................... 208–96–8 3.5 10.5 

Anthracene ................................................................................................................................... 120–12–7 1.9 5.7 

Benzidine 2 ................................................................................................................................... 92–87–5 44 132 

Benzo(a)anthracene .................................................................................................................... 56–55–3 7.8 23.4 

Benzo(a)pyrene ........................................................................................................................... 50–32–8 2.5 7.5 

Benzo(b)fluoranthene .................................................................................................................. 205–99–2 4.8 14.4 

Benzo(k)fluoranthene ................................................................................................................... 207–08–9 2.5 7.5 

Benzo(ghi)perylene ...................................................................................................................... 191–24–2 4.1 12.3 

Benzyl butyl phthalate ................................................................................................................. 85–68–7 2.5 7.5 

bis(2-Chloroethoxy)methane ........................................................................................................ 111–91–1 5.3 15.9 

bis(2-Ethylhexyl)phthalate ............................................................................................................ 117–81–7 2.5 7.5 

bis(2-Chloroisopropyl) ether (2,2′-Oxybis(1-chloropropane)) ...................................................... 108–60–1 5.7 17.1 

4-Bromophenyl phenyl ether ....................................................................................................... 101–55–3 1.9 5.7 

2-Chloronaphthalene ................................................................................................................... 91–58–7 1.9 5.7 

4-Chlorophenyl phenyl ether ....................................................................................................... 7005–72–3 4.2 12.6 

Chrysene ...................................................................................................................................... 218–01–9 2.5 7.5 

Dibenz(a,h)anthracene ................................................................................................................ 53–70–3 2.5 7.5 

Di-n-butylphthalate ....................................................................................................................... 84–74–2 2.5 7.5 

3,3′-Dichlorobenzidine ................................................................................................................. 91–94–1 16.5 49.5 

Diethyl phthalate .......................................................................................................................... 84–66–2 1.9 5.7 

Dimethyl phthalate ....................................................................................................................... 131–11–3 1.6 4.8 

2,4-Dinitrotoluene ......................................................................................................................... 121–14–2 5.7 17.1 

2,6-Dinitrotoluene ......................................................................................................................... 606–20–2 1.9 5.7 

Di-n-octylphthalate ....................................................................................................................... 117–84–0 2.5 7.5 

Fluoranthene ................................................................................................................................ 206–44–0 2.2 6.6 

Fluorene ....................................................................................................................................... 86–73–7 1.9 5.7 

Hexachlorobenzene ..................................................................................................................... 118–74–1 1.9 5.7 

Hexachlorobutadiene ................................................................................................................... 87–68–3 0.9 2.7 

Hexachloroethane ........................................................................................................................ 67–72–1 1.6 4.8 

Indeno(1,2,3-cd)pyrene ................................................................................................................ 193–39–5 3.7 11.1 

Isophorone ................................................................................................................................... 78–59–1 2.2 6.6 

Naphthalene ................................................................................................................................. 91–20–3 1.6 4.8 

Nitrobenzene ................................................................................................................................ 98–95–3 1.9 5.7 

N-Nitrosodi-n-propylamine 3 ......................................................................................................... 621–64–7 — — 

Phenanthrene .............................................................................................................................. 85–01–8 5.4 16.2 

Pyrene .......................................................................................................................................... 129–00–0 1.9 5.7 

1,2,4-Trichlorobenzene ................................................................................................................ 120–82–1 1.9 5.7 

1All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A). 

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2 Included for tailing factor testing. 

3See Section 1.2. 

4 MDL values from the 1984 promulgated version of Method 624. 

5 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 2—ACID EXTRACTABLES 1

Analyte CAS Registry MDL 3 ML 4

4-Chloro-3-methylphenol ............................................................................................................. 59–50–7 3.0 9.0 

2-Chlorophenol ............................................................................................................................ 95–57–8 3.3 9.9 

2,4-Dichlorophenol ....................................................................................................................... 120–83–2 2.7 8.1 

2,4-Dimethylphenol ...................................................................................................................... 105–67–9 2.7 8.1 

2,4-Dinitrophenol .......................................................................................................................... 51–28–5 42 126 

2-Methyl-4,6-dinitrophenol ........................................................................................................... 534–52–1 24 72 

2-Nitrophenol ............................................................................................................................... 88–75–5 3.6 10.8 

4-Nitrophenol ............................................................................................................................... 100–02–7 2.4 7.2 

Pentachlorophenol 2 ..................................................................................................................... 87–86–5 3.6 10.8 

Phenol .......................................................................................................................................... 108–95–2 1.5 4.5 

2,4,6-Trichlorophenol ................................................................................................................... 88–06–2 2.7 8.1 

1All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A). 

2See Section 1.2; included for tailing factor testing. 

3 MDL values from the 1984 promulgated version of Method 624. 

4 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1 2

Analyte CAS Registry MDL 6 ML 7

Acetophenone .............................................................................................................................. 98–86–2 

2-Acetylaminofluorene ................................................................................................................. 53–96–3 

1-Acetyl-2-thiourea ....................................................................................................................... 591–08–2 

Alachlor ........................................................................................................................................ 15972–60–8 

Aldrin 3 .......................................................................................................................................... 309–00–2 1.9 5.7 

Ametryn ........................................................................................................................................ 834–12–8 

2-Aminoanthraquinone ................................................................................................................. 117–79–3 

Aminoazobenzene ....................................................................................................................... 60–09–3 

4-Aminobiphenyl .......................................................................................................................... 92–67–1 

3-Amino-9-ethylcarbazole ............................................................................................................ 132–32–1 

Anilazine ...................................................................................................................................... 101–05–3 

Aniline .......................................................................................................................................... 62–53–3 

o-Anisidine ................................................................................................................................... 90–04–0 

Aramite ......................................................................................................................................... 140–57–8 

Atraton ......................................................................................................................................... 1610–17–9 

Atrazine ........................................................................................................................................ 1912–24–9 

Azinphos-methyl .......................................................................................................................... 86–50–0 

Barban ......................................................................................................................................... 101–27–9 

Benzanthrone ............................................................................................................................... 82–05–3 

Benzenethiol ................................................................................................................................ 108–98–5 

Benzidine 3 4 ................................................................................................................................. 92–87–5 44 132 

Benzoic acid ................................................................................................................................ 65–85–0 

2,3-Benzofluorene ........................................................................................................................ 243–17–4 

p-Benzoquinone ........................................................................................................................... 106–51–4 

Benzyl alcohol .............................................................................................................................. 100–51–6 

alpha-BHC 3 4 ............................................................................................................................... 319–84–6 

beta-BHC 3 ................................................................................................................................... 319–85–7 3.1 9.3 

gamma-BHC (Lindane) 3 4 ............................................................................................................ 58–89–8 4.2 12.6 

delta-BHC 3 .................................................................................................................................. 319–86–8 

Biphenyl ....................................................................................................................................... 92–52–4 

Bromacil ....................................................................................................................................... 314–40–9 

2-Bromochlorobenzene ................................................................................................................ 694–80–4 

3-Bromochlorobenzene ................................................................................................................ 108–39–2 

Bromoxynil ................................................................................................................................... 1689–84–5 

Butachlor ...................................................................................................................................... 2318–4669 

Butylate ........................................................................................................................................ 2008–41–5 

n-C10 (n-decane) ......................................................................................................................... 124–18–5 

n-C12 (n-undecane) ..................................................................................................................... 112–40–2 

n-C14 (n-tetradecane) ................................................................................................................. 629–59–4 

n-C16 (n-hexadecane) ................................................................................................................. 544–76–3 

n-C18 (n-octadecane) .................................................................................................................. 593–45–3 

n-C20 (n-eicosane) ...................................................................................................................... 112–95–8 

n-C22 (n-docosane) ..................................................................................................................... 629–97–0 

n-C24 (n-tetracosane) .................................................................................................................. 646–31–1 

n-C26 (n-hexacosane) ................................................................................................................. 630–01–3 

n-C28 (n-octacosane) .................................................................................................................. 630–02–4 

n-C30 (n-triacontane) ................................................................................................................... 638–68–6 

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9062 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1 2—Continued 

Analyte CAS Registry MDL 6 ML 7

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 

Chlordane3 5 ................................................................................................................................. 57–74–9 

bis(2-Chloroethyl) ether 3 4 ........................................................................................................... 111–44–4 5.7 17.1 

Chloroneb .................................................................................................................................... 2675–77–6 

4-Chloroaniline ............................................................................................................................. 106–47–8 

Chlorobenzilate ............................................................................................................................ 510–15–6 

Chlorfenvinphos ........................................................................................................................... 470–90–6 

4-Chloro-2-methylaniline .............................................................................................................. 95–69–2 

3-(Chloromethyl)pyridine hydrochloride ....................................................................................... 6959–48–4 

4-Chloro-2-nitroaniline ................................................................................................................. 89–63–4 

Chlorpropham .............................................................................................................................. 101–21–3 

Chlorothalonil ............................................................................................................................... 1897–45–6 

1-Chloronaphthalene ................................................................................................................... 90–13–1 

3-Chloronitribenzene .................................................................................................................... 121–73–3 

4-Chloro-1,2-phenylenediamine ................................................................................................... 95–83–0 

4-Chloro-1,3-phenylenediamine ................................................................................................... 5131–60–2 

2-Chlorobiphenyl .......................................................................................................................... 2051–60–7 

Chlorpyrifos .................................................................................................................................. 2921–88–2 

Coumaphos .................................................................................................................................. 56–72–4 

m+p-Cresol .................................................................................................................................. 65794–96–9 

o-Cresol ....................................................................................................................................... 95–48–7 

p-Cresidine ................................................................................................................................... 120–71–8 

Crotoxyphos ................................................................................................................................. 7700–17–6 

2-Cyclohexyl-4,6-dinitro-phenol ................................................................................................... 131–89–5 

Cyanazine .................................................................................................................................... 21725–46–2 

Cycloate ....................................................................................................................................... 1134–23–2 

p-Cymene .................................................................................................................................... 99–87–6 

Dacthal (DCPA) ........................................................................................................................... 1861–32–1 

4,4′-DDD 3 .................................................................................................................................... 72–54–8 2.8 8.4 

4,4′-DDE3 .................................................................................................................................... 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 

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Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 9063 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1 2—Continued 

Analyte CAS Registry MDL 6 ML 7

Dimethyl sulfone .......................................................................................................................... 67–71–0 

1,2-Dinitrobenzene ....................................................................................................................... 528–29–0 

1,3-Dinitrobenzene ....................................................................................................................... 99–65–0 

1,4-Dinitrobenzene ....................................................................................................................... 100–25–4 

Dinocap ........................................................................................................................................ 39300–45–3 

Dinoseb ........................................................................................................................................ 88–85–7 

Diphenylamine ............................................................................................................................. 122–39–4 

Diphenyl ether .............................................................................................................................. 101–84–8 

1,2-Diphenylhydrazine ................................................................................................................. 122–66–7 

Diphenamid .................................................................................................................................. 957–51–7 

Diphenyldisulfide .......................................................................................................................... 882–33–7 

Disulfoton ..................................................................................................................................... 298–04–4 

Disulfoton sulfoxide ...................................................................................................................... 2497–07–6 

Disulfoton sulfone ........................................................................................................................ 2497–06–5 

Endosulfan I 3 4 ............................................................................................................................. 959–98–8 

Endosulfan II 3 4 ............................................................................................................................ 33213–65–9 

Endosulfan sulfate 3 ..................................................................................................................... 1031–07–8 5.6 16.8 

Endrin 3 4 ...................................................................................................................................... 72–20–8 

Endrin aldehyde 3 4 ....................................................................................................................... 7421–93–4 

Endrin ketone 3 4 .......................................................................................................................... 53494–70–5 

EPN .............................................................................................................................................. 2104–64–5 

EPTC ........................................................................................................................................... 759–94–4 

Ethion ........................................................................................................................................... 563–12–2 

Ethoprop ...................................................................................................................................... 13194–48–4 

Ethyl carbamate ........................................................................................................................... 51–79–6 

Ethyl methanesulfonate ............................................................................................................... 65–50–0 

Ethylenethiourea .......................................................................................................................... 96–45–7 

Etridiazole .................................................................................................................................... 2593–15–9 

Ethynylestradiol-3-methyl ether ................................................................................................... 72–33–3 

Famphur ....................................................................................................................................... 52–85–7 

Fenamiphos ................................................................................................................................. 22224–92–6 

Fenarimol ..................................................................................................................................... 60168–88–9 

Fensulfothion ............................................................................................................................... 115–90–2 

Fenthion ....................................................................................................................................... 55–38–9 

Fluchloralin ................................................................................................................................... 33245–39–5 

Fluridone ...................................................................................................................................... 59756–60–4 

Heptachlor 3 ................................................................................................................................. 76–44–8 1.9 5.7 

Heptachlor epoxide 3 .................................................................................................................... 1024–57–3 2.2 6.6 

2,2′,3,3′,4,4′,6-Heptachlorobiphenyl ............................................................................................ 52663–71–5 

2,2′,4,4′,5′,6-Hexachlorobiphenyl ................................................................................................. 60145–22–4 

Hexachlorocyclopentadiene 3 4 ..................................................................................................... 77–47–4 

Hexachlorophene ......................................................................................................................... 70–30–4 

Hexachloropropene ...................................................................................................................... 1888–71–7 

Hexamethylphosphoramide ......................................................................................................... 680–31–9 

Hexanoic acid .............................................................................................................................. 142–62–1 

Hexazinone .................................................................................................................................. 51235–04–2 

Hydroquinone ............................................................................................................................... 123–31–9 

Isodrin .......................................................................................................................................... 465–73–6 

2-Isopropylnapthalene ................................................................................................................. 2027–17–0 

Isosafrole ..................................................................................................................................... 120–58–1 

Kepone ......................................................................................................................................... 143–50–0 

Leptophos .................................................................................................................................... 21609–90–5 

Longifolene .................................................................................................................................. 475–20–7 

Malachite green ........................................................................................................................... 569–64–2 

Malathion ..................................................................................................................................... 121–75–5 

Maleic anhydride .......................................................................................................................... 108–31–6 

Merphos ....................................................................................................................................... 150–50–5 

Mestranol ..................................................................................................................................... 72–33–3 

Methapyrilene .............................................................................................................................. 91–80–5 

Methoxychlor ................................................................................................................................ 72–43–5 

2-Methylbenzothioazole ............................................................................................................... 120–75–2 

3-Methylcholanthrene .................................................................................................................. 56–49–5 

4,4′-Methylenebis(2-chloroaniline) ............................................................................................... 101–14–4 

4,4′-Methylenebis(N,N-dimethylaniline) ....................................................................................... 101–61–1 

4,5-Methylenephenanthrene ........................................................................................................ 203–64–5 

1-Methylfluorene .......................................................................................................................... 1730–37–6 

Methyl methanesulfonate ............................................................................................................. 66–27–3 

2-Methylnaphthalene ................................................................................................................... 91–57–6 

Methylparaoxon ........................................................................................................................... 950–35–6 

Methyl parathion .......................................................................................................................... 298–00–0 

1-Methylphenanthrene ................................................................................................................. 832–69–9 

2-(Methylthio)benzothiazole ......................................................................................................... 615–22–5 

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9064 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1 2—Continued 

Analyte CAS Registry MDL 6 ML 7

Metolachlor .................................................................................................................................. 5218–45–2 

Metribuzin .................................................................................................................................... 21087–64–9 

Mevinphos .................................................................................................................................... 7786–34–7 

Mexacarbate ................................................................................................................................ 315–18–4 

MGK 264 ...................................................................................................................................... 113–48–4 

Mirex ............................................................................................................................................ 2385–85–5 

Molinate ....................................................................................................................................... 2212–67–1 

Monocrotophos ............................................................................................................................ 6923–22–4 

Naled ............................................................................................................................................ 300–76–5 

Napropamide ............................................................................................................................... 15299–99–7 

1,4-Naphthoquinone .................................................................................................................... 130–15–4 

1-Naphthylamine .......................................................................................................................... 134–32–7 

2-Naphthylamine .......................................................................................................................... 91–59–8 

1,5-Naphthalenediamine .............................................................................................................. 2243–62–1 

Nicotine ........................................................................................................................................ 54–11–5 

5-Nitroacenaphthene ................................................................................................................... 602–87–9 

2-Nitroaniline ................................................................................................................................ 88–74–4 

3-Nitroaniline ................................................................................................................................ 99–09–2 

4-Nitroaniline ................................................................................................................................ 100–01–6 

5-Nitro-o-anisidine ........................................................................................................................ 99–59–2 

4-Nitrobiphenyl ............................................................................................................................. 92–93–3 

Nitrofen ........................................................................................................................................ 1836–75–5 

5-Nitro-o-toluidine ........................................................................................................................ 99–55–8 

Nitroquinoline-1-oxide .................................................................................................................. 56–57–5 

N-Nitrosodi-n-butylamine 4 ........................................................................................................... 924–16–3 

N-Nitrosodiethylamine 4 ............................................................................................................... 55–18–5 

N-Nitrosodimethylamine 3 4 .......................................................................................................... 62–75–9 

N-Nitrosodiphenylamine 3 4 .......................................................................................................... 86–30–6 

N-Nitrosomethylethylamine 4 ........................................................................................................ 10595–95–6 

N-Nitrosomethylphenylamine 4 ..................................................................................................... 614–00–6 

N-Nitrosomorpholine 4 .................................................................................................................. 59–89–2 

N-Nitrosopiperidine 4 .................................................................................................................... 100–75–5 

N-Nitrosopyrrolidine 4 ................................................................................................................... 930–55–2 

trans-Nonachlor ........................................................................................................................... 39765–80–5 

Norflurazon .................................................................................................................................. 27314–13–2 

2,2′,3,3′,4,5′,6,6′-Octachlorobiphenyl .......................................................................................... 40186–71–8 

Octamethyl pyrophosphoramide .................................................................................................. 152–16–9 

4,4’-Oxydianiline .......................................................................................................................... 101–80–4 

Parathion ...................................................................................................................................... 56–38–2 

PCB–1016 3 5 ............................................................................................................................... 12674–11–2 

PCB–1221 3 5 ............................................................................................................................... 11104–28–2 30 90 

PCB–1232 3 5 ............................................................................................................................... 11141–16–5 

PCB–1242 3 5 ............................................................................................................................... 53469–21–9 

PCB–1248 3 5 ............................................................................................................................... 12672–29–6 

PCB–1254 3 5 ............................................................................................................................... 11097–69–1 36 108 

PCB–1260 3 5 ............................................................................................................................... 11098–82–5 

PCB–1268 3 5 ............................................................................................................................... 11100–14–4 

Pebulate ....................................................................................................................................... 1114–71–2 

Pentachlorobenzene .................................................................................................................... 608–93–5 

Pentachloronitrobenzene ............................................................................................................. 82–68–8 

2,2′,3,4′,6-Pentachlorobiphenyl ................................................................................................... 68194–05–8 

Pentachloroethane ....................................................................................................................... 76–01–7 

Pentamethylbenzene ................................................................................................................... 700–12–9 

Perylene ....................................................................................................................................... 198–55–0 

Phenacetin ................................................................................................................................... 62–44–2 

cis-Permethrin .............................................................................................................................. 61949–76–6 

trans-Permethrin .......................................................................................................................... 61949–77–7 

Phenobarbital ............................................................................................................................... 50–06–6 

Phenothiazene ............................................................................................................................. 92–84–2 

1,4-Phenylenediamine ................................................................................................................. 624–18–0 

1-Phenylnaphthalene ................................................................................................................... 605–02–7 

2-Phenylnaphthalene ................................................................................................................... 612–94–2 

Phorate ........................................................................................................................................ 298–02–2 

Phosalone .................................................................................................................................... 2310–18–0 

Phosmet ....................................................................................................................................... 732–11–6 

Phosphamidon ............................................................................................................................. 13171–21–6 

Phthalic anhydride ....................................................................................................................... 85–44–9 

alpha-Picoline (2-Methylpyridine) ................................................................................................ 109–06–8 

Piperonyl sulfoxide ....................................................................................................................... 120–62–7 

Prometon ..................................................................................................................................... 1610–18–0 

Prometryn .................................................................................................................................... 7287–19–6 

Pronamide .................................................................................................................................... 23950–58–5 

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Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 9065 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1 2—Continued 

Analyte CAS Registry MDL 6 ML 7

Propachlor .................................................................................................................................... 1918–16–7 

Propazine ..................................................................................................................................... 139–40–2 

Propylthiouracil ............................................................................................................................ 51–52–5 

Pyridine ........................................................................................................................................ 110–86–1 

Resorcinol (1,3-Benzenediol) ...................................................................................................... 108–46–3 

Safrole .......................................................................................................................................... 94–59–7 

Simazine ...................................................................................................................................... 122–34–9 

Simetryn ....................................................................................................................................... 1014–70–6 

Squalene ...................................................................................................................................... 7683–64–9 

Stirofos ......................................................................................................................................... 22248–79–9 

Strychnine .................................................................................................................................... 57–24–9 

Styrene ......................................................................................................................................... 100–42–5 

Sulfallate ...................................................................................................................................... 95–06–7 

Tebuthiuron .................................................................................................................................. 34014–18–1 

Terbacil ........................................................................................................................................ 5902–51–2 

Terbufos ....................................................................................................................................... 13071–79–9 

Terbutryn ...................................................................................................................................... 886–50–0 

alpha-Terpineol ............................................................................................................................ 98–55–5 

1,2,4,5-Tetrachlorobenzene ......................................................................................................... 95–94–3 

2,2′,4,4′-Tetrachlorobiphenyl ....................................................................................................... 2437–79–8 

2,3,7,8-Tetrachlorodibenzo-p-dioxin ............................................................................................ 1746–01–6 

2,3,4,6-Tetrachlorophenol ............................................................................................................ 58–90–2 

Tetrachlorvinphos ........................................................................................................................ 22248–79–9 

Tetraethyl dithiopyrophosphate ................................................................................................... 3689–24–5 

Tetraethyl pyrophosphate ............................................................................................................ 107–49–3 

Thianaphthene (2,3-Benzothiophene) ......................................................................................... 95–15–8 

Thioacetamide ............................................................................................................................. 62–55–5 

Thionazin ..................................................................................................................................... 297–97–2 

Thiophenol (Benzenethiol) ........................................................................................................... 108–98–5 

Thioxanthone ............................................................................................................................... 492–22–8 

Toluene-1,3-diisocyanate ............................................................................................................. 26471–62–5 

Toluene-2,4-diisocyanate ............................................................................................................. 584–84–9 

o-Toluidine ................................................................................................................................... 95–53–4 

Toxaphene 3 5 ............................................................................................................................... 8001–35–2 

Triadimefon .................................................................................................................................. 43121–43–3 

1,2,3-Trichlorobenzene ................................................................................................................ 87–61–6 

2,4,5-Trichlorobiphenyl ................................................................................................................ 15862–07–4 

2,3,6-Trichlorophenol ................................................................................................................... 933–75–5 

2,4,5-Trichlorophenol ................................................................................................................... 95–95–4 

Tricyclazole .................................................................................................................................. 41814–78–2 

Trifluralin ...................................................................................................................................... 1582–09–8 

1,2,3-Trimethoxybenzene ............................................................................................................ 634–36–6 

2,4,5-Trimethylaniline ................................................................................................................... 137–17–7 

Trimethyl phosphate .................................................................................................................... 512–56–1 

Triphenylene ................................................................................................................................ 217–59–4 

Tripropyleneglycolmethyl ether .................................................................................................... 20324–33–8 

1,3,5-Trinitrobenzene ................................................................................................................... 99–35–4 

Tris(2,3-dibromopropyl) phosphate .............................................................................................. 126–72–7 

Tri-p-tolyl phosphate .................................................................................................................... 78–32–0 

O,O,O-Triethyl phosphorothioate ................................................................................................. 126–68–1 

Trithiane ....................................................................................................................................... 291–29–4 

Vernolate ...................................................................................................................................... 1929–77–7 

1 Compounds that have been demonstrated amenable to extraction and gas chromatography. 

2 Determine each analyte in the fraction that gives the most accurate result. 

3Priority Pollutant (40 CFR part 423, appendix A). 

4See Section 1.2. 

5These compounds are mixtures of various isomers. 

6 MDL values from the 1984 promulgated version of Method 624. 

7 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 4—CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC M/Z’S FOR BASE/NEUTRAL EXTRACTABLES

Analyte 

Retention 

time 

(sec) 1

Characteristic m/z’s 

Electron impact ionization Chemical ionization 

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 

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9066 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

TABLE 4—CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC M/Z’S FOR BASE/NEUTRAL EXTRACTABLES—Continued 

Analyte 

Retention 

time 

(sec) 1

Characteristic m/z’s 

Electron impact ionization Chemical ionization 

Primary Second Second Methane Methane Methane 

N-Nitrosodi-n-propylamine ....................... 830 130 42 101 

Nitrobenzene ............................................ 849 77 123 65 124 152 164 

Isophorone ............................................... 889 82 95 138 139 167 178 

bis(2-Chloroethoxy) methane ................... 939 93 95 123 65 107 137 

1,2,4-Trichlorobenzene ............................ 958 180 182 145 181 183 209 

Naphthalene ............................................. 967 128 129 127 129 157 169 

Hexachlorobutadiene ............................... 1006 225 223 227 223 225 227 

Hexachlorocyclopentadiene ..................... 1142 237 235 272 235 237 239 

2-Chloronaphthalene ................................ 1200 162 164 127 163 191 203 

Acenaphthylene ....................................... 1247 152 151 153 152 153 181 

Dimethyl phthalate ................................... 1273 163 194 164 151 163 164 

2,6-Dinitrotoluene ..................................... 1300 165 89 121 183 211 223 

Acenaphthene .......................................... 1304 154 153 152 154 155 183 

2,4-Dinitrotoluene ..................................... 1364 165 63 182 183 211 223 

Fluorene ................................................... 1401 166 165 167 166 167 195 

4-Chlorophenyl phenyl ether .................... 1409 204 206 141 

Diethyl phthalate ...................................... 1414 149 177 150 177 223 251 

N-Nitrosodiphenylamine ........................... 1464 169 168 167 169 170 198 

4-Bromophenyl phenyl ether .................... 1498 248 250 141 249 251 277 

alpha-BHC ................................................ 1514 183 181 109 

Hexachlorobenzene ................................. 1522 284 142 249 284 286 288 

beta-BHC ................................................. 1544 183 181 109 

gamma-BHC ............................................ 1557 181 183 109 

Phenanthrene ........................................... 1583 178 179 176 178 179 207 

Anthracene ............................................... 1592 178 179 176 178 179 207 

delta-BHC ................................................. 1599 183 109 181 

Heptachlor ................................................ 1683 100 272 274 

Di-n-butyl phthalate .................................. 1723 149 150 104 149 205 279 

Aldrin ........................................................ 1753 66 263 220 

Fluoranthene ............................................ 1817 202 101 100 203 231 243 

Heptachlor epoxide .................................. 1820 353 355 351 

gamma-Chlordane ................................... 1834 373 375 377 

Pyrene ...................................................... 1852 202 101 100 203 231 243 

Benzidine 2 ............................................... 1853 184 92 185 185 213 225 

alpha-Chlordane ....................................... 1854 373 375 377 

Endosulfan I ............................................. 1855 237 339 341 

4,4′-DDE .................................................. 1892 246 248 176 

Dieldrin ..................................................... 1907 79 263 279 

Endrin ....................................................... 1935 81 263 82 

Endosulfan II ............................................ 2014 237 339 341 

4,4′-DDD .................................................. 2019 235 237 165 

Endrin aldehyde ....................................... 2031 67 345 250 

Butyl benzyl phthalate .............................. 2060 149 91 206 149 299 327 

Endosulfan sulfate ................................... 2068 272 387 422 

4,4′-DDT ................................................... 2073 235 237 165 

Chrysene .................................................. 2083 228 226 229 228 229 257 

3,3′-Dichlorobenzidine .............................. 2086 252 254 126 

Benzo(a)anthracene ................................. 2090 228 229 226 228 229 257 

bis(2-Ethylhexyl) phthalate ....................... 2124 149 167 279 149 

Di-n-octyl phthalate .................................. 2240 149 43 57 

Benzo(b)fluoranthene ............................... 2286 252 253 125 252 253 281 

Benzo(k)fluoranthene ............................... 2293 252 253 125 252 253 281 

Benzo(a)pyrene ........................................ 2350 252 253 125 252 253 281 

Indeno(1,2,3-cd) pyrene ........................... 2650 276 138 277 276 277 305 

Dibenz(a,h)anthracene ............................. 2660 278 139 279 278 279 307 

Benzo(ghi)perylene .................................. 2750 276 138 277 276 277 305 

Toxaphene ............................................... .................... 159 231 233 

PCB 1016 ................................................. .................... 224 260 294 

PCB 1221 ................................................. .................... 190 224 260 

PCB 1232 ................................................. .................... 190 224 260 

PCB 1242 ................................................. .................... 224 260 294 

PCB 1248 ................................................. .................... 294 330 262 

PCB 1254 ................................................. .................... 294 330 362 

PCB 1260 ................................................. .................... 330 362 394 

1 Column: 30 m × 0.25 mm ID; 94% methyl, 5% phenyl, 1% vinyl bonded phase fused silica capillary. 

Conditions: 5 min at 30 °C; 30–280 at 8 °C per min; isothermal at 280 °C until benzo(ghi)perylene elutes. 

Gas velocity: 30 cm/sec at 30 °C (at constant pressure). 2See Section 1.2; included for tailing factor testing. 

mstockstill on DSK4VPTVN1PROD with PROPOSALS2

Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 9067 

TABLE 5—CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC M/Z’S FOR ACID EXTRACTABLES

Analyte 

Retention 

time 

(sec) 1

Characteristic m/z’s 

Electron impact ionization Chemical ionization 

Primary Second Second Methane Methane Methane 

2-Chlorophenol ......................................... 705 128 64 130 129 131 157 

Phenol ...................................................... 700 94 65 66 95 123 135 

2-Nitrophenol ............................................ 900 139 65 109 140 168 122 

2,4-Dimethylphenol .................................. 924 122 107 121 123 151 163 

2,4-Dichlorophenol ................................... 947 162 164 98 163 165 167 

4-Chloro-3-methylphenol .......................... 1091 142 107 144 143 171 183 

2,4,6-Trichlorophenol ............................... 1165 196 198 200 197 199 201 

2,4-Dinitrophenol ...................................... 1325 184 63 154 185 213 225 

4-Nitrophenol ............................................ 1354 65 139 109 140 168 122 

2-Methyl-4,6-dinitrophenol ....................... 1435 198 182 77 199 227 239 

Pentachlorophenol ................................... 1561 266 264 268 267 265 269 

Column: 30 m × 0.25 mm ID; 94% methyl, 5% phenyl, 1% vinyl bonded phase fused silica capillary. 

Conditions: 5 min at 30 °C; 30–250 at 8 °C per min; isothermal at 280 °C until pentachlorophenol elutes. 

Gas velocity: 30 cm/sec at 30 °C (at constant pressure). 

TABLE 6—QC ACCEPTANCE CRITERIA—METHOD 625 1

Analyte Range for Q 

(%) 2

Limit for s 

(%) 3

Range for X ̄

(%) 3

Range for 

P, Ps

(%) 3

Limit for 

RPD 

(%) 

Acenaphthene .......................................................................................... 70–130 29 60–132 47–145 48 

Acenaphthylene ....................................................................................... 60–130 45 54–126 33–145 74

Aldrin ........................................................................................................ 7–152 39 7–152 D–166 81 

Anthracene ............................................................................................... 58–130 40 43–120 27–133 66 

Benzo(a)anthracene ................................................................................ 42–133 32 42–133 33–143 53 

Benzo(b)fluoranthene .............................................................................. 42–140 43 42–140 24–159 71 

Benzo(k)fluoranthene ............................................................................... 25–146 38 25–146 11–162 63 

Benzo(a)pyrene ....................................................................................... 32–148 43 32–148 17–163 72

Benzo(ghi)perylene .................................................................................. 13–195 61 D–195 D–219 97 

Benzyl butyl phthalate ............................................................................. 43–140 36 D–140 D–152 60 

beta-BHC ................................................................................................. 42–131 37 42–131 24–149 61

delta-BHC ................................................................................................ D–130 77 D–120 D–120 129 

bis(2-Chloroethyl)ether ............................................................................. 52–130 65 43–126 12–158 108

bis(2-Chloroethoxy)methane .................................................................... 52–164 32 49–165 33–184 54 

bis(2-Chloroisopropyl) ether ..................................................................... 63–139 46 63–139 36–166 76 

bis(2-Ethylhexyl) phthalate ....................................................................... 43–137 50 29–137 8–158 82 

4-Bromophenyl phenyl ether .................................................................... 70–130 26 65–120 53–127 43 

2-Chloronaphthalene ............................................................................... 70–130 15 65–120 60–120 24 

4-Chlorophenyl phenyl ether .................................................................... 57–145 36 38–145 25–158 61 

Chrysene .................................................................................................. 44–140 53 44–140 17–168 87 

4,4′-DDD .................................................................................................. D–135 56 D–135 D–145 93 

4,4′-DDE .................................................................................................. 19–130 46 19–120 4–136 77

4,4′-DDT ................................................................................................... D–171 81 D–171 D–203 135

Dibenz(a,h)anthracene ............................................................................ 13–200 75 D–200 D–227 126 

Di-n-butyl phthalate .................................................................................. 52–130 28 8–120 1–120 47 

3,3′-Dichlorobenzidine ............................................................................. 18–213 65 8–213 D–262 108 

Dieldrin ..................................................................................................... 70–130 38 44–119 29–136 62 

Diethyl phthalate ...................................................................................... 47–130 60 D–120 D–120 100 

Dimethyl phthalate ................................................................................... 50–130 110 D–120 D–120 183

2,4-Dinitrotoluene ..................................................................................... 53–130 25 48–127 39–139 42 

2,6-Dinitrotoluene ..................................................................................... 68–137 29 68–137 50–158 48 

Di-n-octyl phthalate .................................................................................. 21–132 42 19–132 4–146 69 

Endosulfan sulfate ................................................................................... D–130 42 D–120 D–120 70 

Endrin aldehyde ....................................................................................... D–189 45 D–189 D–209 75 

Fluoranthene ............................................................................................ 47–130 40 43–121 26–137 66 

Fluorene ................................................................................................... 70–130 23 70–120 59–121 38 

Heptachlor ................................................................................................ D–172 44 D–172 D–192 74 

Heptachlor epoxide .................................................................................. 70–130 61 71–120 26–155 101

Hexachlorobenzene ................................................................................. 38–142 33 8–142 D–152 55 

Hexachlorobutadiene ............................................................................... 68–130 38 38–120 24–120 62 

Hexachloroethane .................................................................................... 55–130 32 55–120 40–120 52 

Indeno(1,2,3-cd)pyrene ............................................................................ 13–151 60 D–151 D–171 99 

Isophorone ............................................................................................... 52–180 56 47–180 21–196 93 

Naphthalene ............................................................................................. 70–130 39 36–120 21–133 65 

Nitrobenzene ............................................................................................ 54–158 37 54–158 35–180 62 

N-Nitrosodi-n-propylamine ....................................................................... 59–170 52 14–198 D–230 87 

PCB–1260 ................................................................................................ 19–130 77 19–130 D–164 128 

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TABLE 6—QC ACCEPTANCE CRITERIA—METHOD 625 1—Continued 

Analyte Range for Q 

(%) 2

Limit for s 

(%) 3

Range for X ̄

(%) 3

Range for 

P, Ps

(%) 3

Limit for 

RPD 

(%) 

Phenanthrene .......................................................................................... 67–130 24 65–120 54–120 39 

Pyrene ...................................................................................................... 70–130 30 70–120 52–120 49 

1,2,4-Trichlorobenzene ............................................................................ 61–130 30 57–130 44–142 50 

4-Chloro-3-methylphenol .......................................................................... 68–130 44 41–128 22–147 73 

2-Chlorophenol ........................................................................................ 55–130 37 36–120 23–134 61 

2,4-Dichlorophenol ................................................................................... 64–130 30 53–122 39–135 50

2,4-Dimethylphenol .................................................................................. 58–130 35 42–120 32–120 58 

2,4-Dinitrophenol ...................................................................................... 39–173 79 D–173 D–191 132 

2-Methyl-4,6-dinitrophenol ....................................................................... 56–130 122 53–130 D–181 203 

2-Nitrophenol ........................................................................................... 61–163 33 45–167 29–182 55 

4-Nitrophenol ........................................................................................... 35–130 79 13–129 D–132 131 

Pentachlorophenol ................................................................................... 42–152 52 38–152 14–176 86 

Phenol ...................................................................................................... 48–130 39 17–120 5–120 64 

2,4,6-Trichlorophenol ............................................................................... 69–130 35 52–129 37–144 58 

1Acceptance 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. 2Test concentration = 100 μg/mL. 3Test concentration = 100 μg/L. 

Q = Calibration verification (Sections 7.3.1 and 13.4). 

s = Standard deviation for four recovery measurements in the DOC test (Section 8.2.4). 

X ̄ = Average recovery for four recovery measurements in the DOC test (Section 8.2.4). 

P, Ps = MS/MSD recovery (Section 8.3.2, Section 8.4.2). 

RPD = MS/MSD relative percent difference (RPD; Section 8.3.3). 

D = Detected; result must be greater than zero. 

TABLE 7—PRECISION AND RECOVERY AS FUNCTIONS OF CONCENTRATION—METHOD 625 1

Analyte Recovery, X′ 

(μg/L) 

Single analyst 

precision, sr′ 

(μg/L) 

Overall 

precision, S′ 

(μg/L) 

Acenaphthene ................................................................................................................................ 0.96C+0.19 ... 0.15 × ¥0.12 0.21 × ¥0.67 

Acenaphthylene ............................................................................................................................. 0.89C+0.74 ... 0.24 × ¥1.06 0.26 × ¥0.54 

Aldrin .............................................................................................................................................. 0.78C+1.66 ... 0.27 × ¥1.28 0.43 × +1.13 

Anthracene .................................................................................................................................... 0.80C+0.68 ... 0.21 × ¥0.32 0.27 × ¥0.64 

Benzo(a)anthracene ...................................................................................................................... 0.88C¥0.60 .. 0.15 × +0.93 0.26 × ¥0.28 

Benzo(b)fluoranthene .................................................................................................................... 0.93C¥1.80 .. 0.22 × +0.43 0.29 × +0.96 

Benzo(k)fluoranthene .................................................................................................................... 0.87C¥1.56 .. 0.19 × +1.03 0.35 × +0.40 

Benzo(a)pyrene ............................................................................................................................. 0.90C¥0.13 .. 0.22 × +0.48 0.32 × +1.35 

Benzo(ghi)perylene ........................................................................................................................ 0.98C¥0.86 .. 0.29 × +2.40 0.51 × ¥0.44 

Benzyl butyl phthalate ................................................................................................................... 0.66C¥1.68 .. 0.18 × +0.94 0.53 × +0.92 

beta-BHC ....................................................................................................................................... 0.87C¥0.94 .. 0.20 × ¥0.58 0.30 × ¥1.94 

delta-BHC ...................................................................................................................................... 0.29C¥1.09 .. 0.34 × +0.86 0.93 × ¥0.17 

bis(2-Chloroethyl)ether .................................................................................................................. 0.86C¥1.54 .. 0.35 × ¥0.99 0.35 × +0.10 

bis(2-Chloroethoxy)methane ......................................................................................................... 1.12C¥5.04 .. 0.16 × +1.34 0.26 × +2.01 

bis(2-Chloroisopropyl)ether ........................................................................................................... 1.03C¥2.31 .. 0.24 × +0.28 0.25 × +1.04 

bis(2-Ethylhexyl)phthalate ............................................................................................................. 0.84C¥1.18 .. 0.26 × +0.73 0.36 × +0.67 

4-Bromophenyl phenyl ether ......................................................................................................... 0.91C¥1.34 .. 0.13 × +0.66 0.16 × +0.66 

2-Chloronaphthalene ..................................................................................................................... 0.89C+0.01 ... 0.07 × +0.52 0.13 × +0.34 

4-Chlorophenyl phenyl ether ......................................................................................................... 0.91C+0.53 ... 0.20 × ¥0.94 0.30 × ¥0.46 

Chrysene ....................................................................................................................................... 0.93C¥1.00 .. 0.28 × +0.13 0.33 × ¥0.09 

4,4′-DDD ........................................................................................................................................ 0.56C¥0.40 .. 0.29 × ¥0.32 0.66 × ¥0.96 

4,4′-DDE ........................................................................................................................................ 0.70C¥0.54 .. 0.26 × ¥1.17 0.39 × ¥1.04 

4,4′-DDT ........................................................................................................................................ 0.79C¥3.28 .. 0.42 × +0.19 0.65 × ¥0.58 

Dibenz(a,h)anthracene .................................................................................................................. 0.88C+4.72 ... 0.30 × +8.51 0.59 × +0.25 

Di-n-butyl phthalate ....................................................................................................................... 0.59C+0.71 ... 0.13 × +1.16 0.39 × +0.60 

3,3′-Dichlorobenzidine ................................................................................................................... 1.23C¥12.65 0.28 × +7.33 0.47 × +3.45 

Dieldrin ........................................................................................................................................... 0.82C¥0.16 .. 0.20 × ¥0.16 0.26 × ¥0.07 

Diethyl phthalate ............................................................................................................................ 0.43C+1.00 ... 0.28 × +1.44 0.52 × +0.22 

Dimethyl phthalate ......................................................................................................................... 0.20C+1.03 ... 0.54 × +0.19 1.05 × ¥0.92 

2,4-Dinitrotoluene .......................................................................................................................... 0.92C¥4.81 .. 0.12 × +1.06 0.21 × +1.50 

2,6-Dinitrotoluene .......................................................................................................................... 1.06C¥3.60 .. 0.14 × +1.26 0.19 × +0.35 

Di-n-octyl phthalate ........................................................................................................................ 0.76C¥0.79 .. 0.21 × +1.19 0.37 × +1.19 

Endosulfan sulfate ......................................................................................................................... 0.39C+0.41 ... 0.12 × +2.47 0.63 × ¥1.03 

Endrin aldehyde ............................................................................................................................. 0.76C¥3.86 .. 0.18 × +3.91 0.73 × ¥0.62 

Fluoranthene .................................................................................................................................. 0.81C+1.10 ... 0.22 × +0.73 0.28 × ¥0.60 

Fluorene ......................................................................................................................................... 0.90C¥0.00 .. 0.12 × +0.26 0.13 × +0.61 

Heptachlor ..................................................................................................................................... 0.87C¥2.97 .. 0.24 × ¥0.56 0.50 × ¥0.23 

Heptachlor epoxide ........................................................................................................................ 0.92C¥1.87 .. 0.33 × ¥0.46 0.28 × +0.64 

Hexachlorobenzene ....................................................................................................................... 0.74C+0.66 ... 0.18 × ¥0.10 0.43 × ¥0.52 

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TABLE 7—PRECISION AND RECOVERY AS FUNCTIONS OF CONCENTRATION—METHOD 625 1—Continued 

Analyte Recovery, X′ 

(μg/L) 

Single analyst 

precision, sr′ 

(μg/L) 

Overall 

precision, S′ 

(μg/L) 

Hexachlorobutadiene ..................................................................................................................... 0.71C¥1.01 .. 0.19 × +0.92 0.26 × +0.49 

Hexachloroethane .......................................................................................................................... 0.73C¥0.83 .. 0.17 × +0.67 0.17 × +0.80 

Indeno(1,2,3-cd)pyrene ................................................................................................................. 0.78C¥3.10 .. 0.29 × +1.46 0.50 × +0.44 

Isophorone ..................................................................................................................................... 1.12C+1.41 ... 0.27 × +0.77 0.33 × +0.26 

Naphthalene .................................................................................................................................. 0.76C+1.58 ... 0.21 × ¥0.41 0.30 × ¥0.68 

Nitrobenzene ................................................................................................................................. 1.09C¥3.05 .. 0.19 × +0.92 0.27 × +0.21 

N-Nitrosodi-n-propylamine ............................................................................................................. 1.12C¥6.22 .. 0.27 × +0.68 0.44 × +0.47 

PCB-1260 ...................................................................................................................................... 0.81C¥10.86 0.35 × +3.61 0.43 × +1.82 

Phenanthrene ................................................................................................................................ 0.87C¥0.06 .. 0.12 × +0.57 0.15 × +0.25 

Pyrene ........................................................................................................................................... 0.84C¥0.16 .. 0.16 × +0.06 0.15 × +0.31 

1,2,4-Trichlorobenzene .................................................................................................................. 0.94C¥0.79 .. 0.15 × +0.85 0.21 × +0.39 

4-Chloro-3-methylphenol ............................................................................................................... 0.84C+0.35 ... 0.23 × +0.75 0.29 × +1.31 

2-Chlorophenol .............................................................................................................................. 0.78C+0.29 ... 0.18 × +1.46 0.28 × 0.97 

2,4-Dichlorophenol ......................................................................................................................... 0.87C+0.13 ... 0.15 × +1.25 0.21 × +1.28 

2,4-Dimethylphenol ........................................................................................................................ 0.71C+4.41 ... 0.16 × +1.21 0.22 × +1.31 

2,4-Dinitrophenol ........................................................................................................................... 0.81C¥18.04 0.38 × +2.36 0.42 × +26.29 

2-Methyl-4,6-Dinitrophenol ............................................................................................................ 1.04C¥28.04 0.05 × +42.29 0.26 × +23.10 

2-Nitrophenol ................................................................................................................................. 1.07C¥1.15 .. 0.16 × +1.94 0.27 × +2.60 

4-Nitrophenol ................................................................................................................................. 0.61C¥1.22 .. 0.38 × +2.57 0.44 × +3.24 

Pentachlorophenol ......................................................................................................................... 0.93C+1.99 ... 0.24 × +3.03 0.30 × +4.33 

Phenol ............................................................................................................................................ 0.43C+1.26 ... 0.26 × +0.73 0.35 × +0.58 

2,4,6-Trichlorophenol ..................................................................................................................... 0.91C¥0.18 .. 0.16 × +2.22 0.22 × +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 μg/L. 

sr′ = Expected single analyst standard deviation of measurements at an average concentration found of ×, in μg/L. 

S′ = Expected interlaboratory standard deviation of measurements at an average concentration found of ×, in μg/L. 

C = True value for the concentration, in μg/L. 

× = Average recovery found for measurements of samples containing a concentration of C, in μg/L. 

TABLE 8—SUGGESTED INTERNAL AND SURROGATE STANDARDS

Base/neutral fraction 

Range for surrogate recovery 

(%) 1

Calibration 

verification 

Recovery from 

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 

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TABLE 8—SUGGESTED INTERNAL AND SURROGATE STANDARDS—Continued 

Base/neutral fraction 

Range for surrogate recovery 

(%) 1

Calibration 

verification 

Recovery from 

samples 

2-Fluorophenol. 

4-Methylphenol-d8 ................................................................................................................................................ 25–111 25–111 

2-Nitrophenol-d4 ................................................................................................................................................... 61–163 37–163 

4-Nitrophenol-d4 ................................................................................................................................................... 35–287 6–500 

Pentafluorophenol. 

2-Perfluoromethylphenol. 

Phenol-d5 ............................................................................................................................................................. 48–208 8–424 

1 Recovery from samples is the wider of the criteria in the CLP SOW for organics or in Method 1625. 

TABLE 9A—DFTPP KEY M/Z’S AND

ABUNDANCE CRITERIA FOR

QUADRUPOLE INSTRUMENTS 1

m/z Abundance criteria 

51 30–60 percent of m/z 198. 

68 Less than 2 percent of m/z 69. 

70 Less than 2 percent of m/z 69. 

127 40–60 percent of base peak m/z 

198. 

197 Less than 1 percent of m/z 198. 

198 Base peak, 100 percent relative 

abundance. 

199 5–9 percent of m/z 198. 

275 10–30 percent of m/z 198. 

365 Greater than 1 percent of m/z 198. 

441 Present but less than m/z 443. 

442 40–100 percent of m/z 198. 

443 17–23 percent of m/z 442. 

1 Criteria in these tables are for quadrupole 

and time-of-flight instruments. Alternative tuning criteria may be used for other instruments, 

provided method performance is not adversely 

affected. 

TABLE 9B—DFTPP KEY M/Z’S AND

ABUNDANCE CRITERIA FOR TIME-OFFLIGHT 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. 

TABLE 9B—DFTPP KEY M/Z’S AND

ABUNDANCE CRITERIA FOR TIME-OFFLIGHT INSTRUMENTS 1—Continued 

m/z Abundance criteria 

443 15–24 percent of m/z 442. 

1 Criteria in these tables are for quadrupole 

and time-of-flight instruments. Alternative tuning criteria may be used for other instruments, 

provided method performance is not adversely 

affected. 

21. Figures 

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E 

0 

TAILING FACTOR:: !f. 

AB 

Example calculation: Peak Height= DE= 100 mm 

10% Peak Height= BD = 10 mm 

Peak Width at 10% Peak Height= AC = 23 mm 

AB=11 mm 

BC=12 mm 

Therefore: T ai I i ng Factor = !! = 1.1 

11 

Figure 1 Tailing factor calculation 
9072 Federal Register / Vol. 80, No. 33 / Thursday, February 19, 2015 / Proposed Rules 

BILLING CODE 6560–50–C 

22. Glossary 

These definitions and purposes are 

specific to this method but have been 

conformed to common usage to the 

extent possible. 

22.1 Units of weight and measure 

and their abbreviations 

22.1.1 Symbols 

ßC degrees Celsius 

mg microgram 

mL microliter 

< less than 

> greater than 

≤ less than or equal to 

% percent 

22.1.2 Abbreviations (in alphabetical 

order) 

cm centimeter 

g gram 

h hour 

ID inside diameter 

in. inch 

L liter 

M Molecular ion 

m mass or meter 

mg milligram 

min minute 

mL milliliter 

mm millimeter 

ms millisecond 

m/z mass-to-charge ratio 

N normal; gram molecular weight of 

solute divided by hydrogen 

equivalent of solute, per liter of 

solution 

ng nanogram 

pg picogram 

ppb part-per-billion 

ppm part-per-million 

ppt part-per-trillion 

psig pounds-per-square inch gauge 

22.2 Definitions and acronyms (in 

alphabetical order) 

Analyte—A compound or mixture of 

compounds (e.g., PCBs) tested for by 

this method. The analytes are listed in 

Tables 1–3. 

Batch—See Extraction 

Blank—An aliquot of reagent water 

that is treated exactly as a sample 

including exposure to all glassware, 

equipment, solvents, reagents, internal 

standards, and surrogates that are used 

with samples. The blank is used to 

determine if analytes or interferences 

are present in the laboratory 

environment, the reagents, or the 

apparatus. 

Calibration—The process of 

determining the relationship between 

the output or response of a measuring 

instrument and the value of an input 

standard. Historically, EPA has referred 

to a multi-point calibration as the 

‘‘initial calibration,’’ to differentiate it 

from a single-point calibration 

verification. 

Calibration standard—A solution 

prepared from stock solutions and/or a 

secondary standards and containing the 

analytes of interest, surrogates, and 

internal standards. The calibration 

standard is used to calibrate the 

response of the GC/MS instrument 

against analyte concentration. 

Calibration verification standard— 

The mid-point calibration standard used 

to verify calibration. See Sections 7.3 

and 13.4. 

Descriptor—In SIM, the beginning 

and ending retention times for the RT 

window, the m/z’s sampled in the RT 

window, and the dwell time at each m/ 

z. 

Extracted ion current profile (EICP)— 

The line described by the signal at a 

given m/z. 

Extraction Batch—A set of up to 20 

field samples (not including QC 

samples) started through the extraction 

process on a given 12-hour shift 

(Section 3.1). Each extraction batch 

must be accompanied by a blank 

(Section 8.5), a laboratory control 


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sample (LCS, Section 8.4), and a matrix 

spike and duplicate (MS/MSD; Section 

8.3), resulting in a minimum of five 

analyses (1 sample, 1 blank, 1 LCS, 1 

MS, and 1 MSD) and a maximum of 24 

analyses (20 field samples, 1 blank, 1 

LCS, 1 MS, and 1 MSD) for the batch. 

If greater than 20 samples are to be 

extracted in a 12-hour shift, the samples 

must be separated into extraction 

batches of 20 or fewer samples. 

Field Duplicates—Two samples 

collected at the same time and place 

under identical conditions, and treated 

identically throughout field and 

laboratory procedures. Results of 

analyses the field duplicates provide an 

estimate of the precision associated with 

sample collection, preservation, and 

storage, as well as with laboratory 

procedures. 

Field blank—An aliquot of reagent 

water or other reference matrix that is 

placed in a sample container in the 

field, and treated as a sample in all 

respects, including exposure to 

sampling site conditions, storage, 

preservation, and all analytical 

procedures. The purpose of the field 

blank is to determine if the field or 

sample transporting procedures and 

environments have contaminated the 

sample. 

GC—Gas chromatograph or gas 

chromatography 

Internal standard—A compound 

added to an extract or standard solution 

in a known amount and used as a 

reference for quantitation of the analytes 

of interest and surrogates. In this 

method the internal standards are stable 

isotopically labeled analogs of selected 

method analytes (Table 8). Also see 

Internal standard quantitation. 

Internal standard quantitation—A 

means of determining the concentration 

of an analyte of interest (Tables 1–3) by 

reference to a compound not expected 

to be found in a sample. 

DOC—Initial demonstration of 

capability (Section 8.2); four aliquots of 

reagent water spiked with the analytes 

of interest and analyzed to establish the 

ability of the laboratory to generate 

acceptable precision and recovery. A 

DOC is performed prior to the first time 

this method is used and any time the 

method or instrumentation is modified. 

Laboratory Control Sample (LCS; 

laboratory fortified blank; Section 8.4)— 

An aliquot of reagent water spiked with 

known quantities of the analytes of 

interest and surrogates. The LCS is 

analyzed exactly like a sample. Its 

purpose is to assure that the results 

produced by the laboratory remain 

within the limits specified in this 

method for precision and recovery. 

Laboratory fortified sample matrix— 

See Matrix spike 

Laboratory reagent blank—A blank 

run on laboratory reagents; e.g., 

methylene chloride (Section 11.1.5). 

Matrix spike (MS) and matrix spike 

duplicate (MSD) (laboratory fortified 

sample matrix and duplicate)—Two 

aliquots of an environmental sample to 

which known quantities of the analytes 

of interest and surrogates are added in 

the laboratory. The MS/MSD are 

prepared and analyzed exactly like a 

field sample. Their purpose is to 

quantify any additional bias and 

imprecision caused by the sample 

matrix. The background concentrations 

of the analytes in the sample matrix 

must be determined in a separate 

aliquot and the measured values in the 

MS/MSD corrected for background 

concentrations. 

May—This action, activity, or 

procedural step is neither required nor 

prohibited. 

May not—This action, activity, or 

procedural step is prohibited. 

Method blank—See blank. 

Method detection limit (MDL)—A 

detection limit determined by the 

procedure at 40 CFR 136, Appendix B. 

The MDLs determined by EPA in the 

original version of the method are listed 

in Tables 1, 2 and 3. As noted in Sec. 

1.5, use the MDLs in Tables 1, 2, and 3 

in conjunction with current MDL data 

from the laboratory actually analyzing 

samples to assess the sensitivity of this 

procedure relative to project objectives 

and regulatory requirements (where 

applicable). 

Minimum level (ML)—The term 

‘‘minimum level’’ refers to either the 

sample concentration equivalent to the 

lowest calibration point in a method or 

a multiple of the method detection limit 

(MDL), whichever is higher. Minimum 

levels may be obtained in several ways: 

They may be published in a method; 

they may be based on the lowest 

acceptable calibration point used by a 

laboratory; or they may be calculated by 

multiplying the MDL in a method, or 

the MDL determined by a laboratory, by 

a factor of 3. For the purposes of NPDES 

compliance monitoring, EPA considers 

the following terms to be synonymous: 

‘‘quantitation limit,’’ ‘‘reporting limit,’’ 

and ‘‘minimum level.’’ 

MS—Mass spectrometer or mass 

spectrometry, or matrix spike (a QC 

sample type). 

MSD—Matrix spike duplicate (a QC 

sample type). 

Must—This action, activity, or 

procedural step is required. 

m/z—The ratio of the mass of an ion 

(m) detected in the mass spectrometer to 

the charge (z) of that ion. 

Preparation blank—See blank. 

Quality control check sample (QCS)— 

See Laboratory Control Sample. 

Reagent water—Water demonstrated 

to be free from the analytes of interest 

and potentially interfering substances at 

the MDLs for the analytes in this 

method. 

Regulatory compliance limit (or 

regulatory concentration limit)—A limit 

on the concentration or amount of a 

pollutant or contaminant specified in a 

nationwide standard, in a permit, or 

otherwise established by a regulatory/

control authority. 

Relative retention time (RRT)—The 

ratio of the retention time of an analyte 

to the retention time of its associated 

internal standard. RRT compensates for 

small changes in the GC temperature 

program that can affect the absolute 

retention times of the analyte and 

internal standard. RRT is a unitless 

quantity. 

Relative standard deviation (RSD)— 

The standard deviation times 100 

divided by the mean. Also termed 

‘‘coefficient of variation.’’ 

RF—Response factor. See Section 

7.2.2. 

RSD—See relative standard deviation. 

Safety Data Sheet (SDS)—Written 

information on a chemical’s toxicity, 

health hazards, physical properties, fire, 

and reactivity, including storage, spill, 

and handling precautions that meet the 

requirements of OSHA, 29 CFR 

1910.1200(g) and appendix D to 

§ 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. 

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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. 

* * * * * 

■ 9. Revise Appendix B to part 136 to 

read as follows: 

Appendix B to Part 136—Definition and 

Procedure for the Determination of the 

Method Detection Limit—Revision 2 

Definition 

The method detection limit (MDL) is 

defined as the minimum measured 

concentration of a substance that can be 

reported with 99% confidence that the 

measured concentration is distinguishable 

from method blank results. 

Scope and Application 

The MDL procedure is designed to be a 

straightforward technique for estimation of 

the detection limit for a broad variety of 

physical and chemical methods. The 

procedure requires a complete, specific, and 

well defined analytical method. It is essential 

that all sample processing steps used by the 

laboratory be included in the determination 

of the method detection limit. 

Procedure 

(1) Estimate the Initial MDL using one of 

the following: 

(a) The mean plus three times the standard 

deviation of a set of method blanks. 

(b) The concentration value that 

corresponds to an instrument signal/noise in 

the range of 3 to 5. 

(c) The concentration equivalent of three 

times the standard deviation of replicate 

instrumental measurements of spiked blanks. 

(d) That region of the standard curve where 

there is a significant change in sensitivity, 

i.e., a break in the slope of the standard 

curve. 

(e) Instrumental limitations. 

(f) Previously determined MDL. 

It is recognized that the experience of the 

analyst is important to this process. However, 

the analyst should include some or all of the 

above considerations in the initial estimate of 

the MDL. 

(2) Determine the Initial MDL 

(a) Select a spiking level, typically 2–10 

times the estimated MDL in section 1. 

Spiking levels in excess of 10 times the 

estimated detection limit may be required for 

analytes with very poor recovery (e.g., an 

analyte with 10% recovery, spiked at 100 

micrograms/L, mean recovery, 10 

micrograms/L; MDL may calculate at 3 

micrograms/L. So, in this case the spiking 

level is 33×MDL, but spiking lower may 

result in no recovery at all). 

(b) Process a minimum of 7 spiked blank 

samples and 7 method blank samples 

through all steps of the method, including 

any sample preservation. Both preparation 

and analysis of these samples must include 

at least three batches on three separate 

calendar dates. Existing data may be used if 

compliant with the requirements for at least 

3 batches and generated within the last 2 

years. 

(i) If there are multiple instruments that 

will be assigned the same MDL, then the 

samples must be distributed across all of the 

instruments. 

(ii) A minimum of two spiked samples and 

two method blank samples prepared and 

analyzed on different calendar dates is 

required for each instrument. 

(c) Evaluate the spiking level: If any result 

for any individual analyte from the spiked 

blank samples does not meet the method 

qualitative identification criteria or does not 

provide a numerical result greater than zero 

then repeat the spikes at a higher 

concentration. Qualitative identification 

criteria are a set of rules or guidelines for 

establishing the identification or presence of 

an analyte using a measurement system. 

Qualitative identification does not ensure 

that quantitative results for the analyte can be 

obtained. 

(d) Make all computations according to the 

defined method with final results in the 

method reporting units. 

(i) Calculate the sample standard deviation 

(S) of the replicate spiked blank 

measurements and the sample standard 

deviation of the replicate method blank 

measurements from all instruments. 

(ii) Compute the MDLs (MDL based on 

spiked blanks) as follows: 

MDLS = t(n¥1, 1¥∝=0.99) SS

Where: 

MDLs = the method detection limit based on 

spiked blanks 

t(n¥1, 1¥α=0.99) = the Student’s t-value 

appropriate for a the single tailed 99th 

percentile t statistic and a standard 

deviation estimate with n-1 degrees of 

freedom. See Table 1. 

Ss = sample standard deviation of the 

replicate spiked blank sample analyses. 

(iii) Compute the MDLb (MDL based 

on method blanks) as follows: 

(A) If none of the method blanks give 

numerical results for an individual 

analyte, the MDLb does not apply. A 

numerical result includes both positive 

and negative results, including results 

below the current MDL, but not results 

of ND (not detected) commonly 

observed when a peak is not present in 

chromatographic analysis. 

(B) If some (but not all) of the method 

blanks for an individual analyte give 

numerical results, set the MDLb equal to 

the highest method blank result. If more 

than 100 method blanks are available, 

set MDLb to the level that is no less than 

the 99th percentile of the blank results. 

For ‘‘n’’ method blanks where n ≥ 100, 

sort the method blanks in rank order. 

The (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 164×0.99 = 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, calculate the MDLb as: 

MDLb = X ̄ + t(n¥1, 1¥∝=0.99) Sb

Where: 

MDLb = the MDL based on method blanks 

X ̄ = mean of the method blank results 

t(n¥1, 1¥α=0.99) = the Student’s t-value 

appropriate for the single tailed 99th 

percentile t statistic and a standard 

deviation estimate with n¥1 degrees of 

freedom. See Addendum Table 1. 

Sb = sample standard deviation of the 

replicate blank sample analyses. 

(e) Set the greater of MDLs or MDLb

as the initial MDL. 

(3) Ongoing Data Collection 

(a) During any quarter in which 

samples are being analyzed, prepare and 

analyze a minimum of two spiked 

blanks on each instrument, in separate 

batches if available, using the same 

spiking concentration used in Section 2. 

If any analytes are repeatedly not 

detected in the quarterly spike sample 

analysis, this is an indication that the 

spiking level is not high enough and 

should be adjusted upward. 

(b) Ensure that at least 7 spiked blanks 

and 7 method blanks are completed for 

the annual verification. 

(c) At least once per year, re-evaluate 

the spiking level. 

(i) If more than 5% of the spiked 

blanks do not return positive numerical 

results that meet all method qualitative 

identification criteria, then the spiking 

level must be increased and the initial 

MDL re-determined following the 

procedure in Section 2. 

(d) If the method is altered in a way 

that can be reasonably expected to 

change the detection limit, then redetermine the initial MDL according to 

Section 2, and the ongoing data 

collection restarted. 

(4) Ongoing Annual Verification 

(a) At least once per year, re-calculate 

MDLs and MDLb from the collected 

spiked blank and method blank results 

using the equations in section 2. 

(b) Include data generated within the 

last 2 years, but only data with the same 

spiking level. 

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(c) Include the initial MDL spiked 

blanks if within two years. 

(d) Only use data associated with 

acceptable calibrations and batch QC. 

Include all routine data, with the 

exception of batches that are rejected 

and the associated samples reanalyzed. 

If the method has been altered in a way 

that can be reasonably expected to 

change the detection limit, use only data 

collected after the change. 

(e) The verified MDL is the greater of 

the MDLs or MDLb. If the verified MDL 

is within a factor of 3 of the existing 

MDL, and fewer than 3% of the method 

blank results (for the individual analyte) 

have numerical results above the 

existing MDL, then the existing MDL 

may optionally be left unchanged. 

Otherwise, adjust the MDL to the new 

verification MDL. 

Addendum: Determination of the MDL 

For a Specific Matrix 

MDLs may be determined in specific 

sample matrices as well as in reagent 

water. 

(1) Analyze the sample matrix to 

determine the native concentration of 

the analyte(s) of interest. 

(2) If the native concentration is at a 

signal to noise ratio of approximately 5– 

20, determine the matrix specific MDL 

according to Section 2, ‘‘Determine the 

initial MDL’’ without spiking additional 

analyte. 

(3) Calculate MDLb using method 

blanks, not the sample matrix. 

(4) If the signal to noise is less than 

5, the analyte(s) should be spiked to 

obtain a concentration that will give 

results with a signal to noise of 

approximately 10–20. 

(5) If the analytes(s) of interest have 

signal to noise greater than 

approximately 20, then the resulting 

MDL is likely to be biased high. 

TABLE 1—SINGLE TAILED 99TH PERCENTILE T STATISTIC

Number of 

replicates 

Degrees of 

freedom 

(n¥1) 

t (n¥1, 0.99)

7 ............................................................................................................................................................................... 6 3.143 

8 ............................................................................................................................................................................... 7 2.998 

9 ............................................................................................................................................................................... 8 2.896 

10 ............................................................................................................................................................................. 9 2.821 

11 ............................................................................................................................................................................. 10 2.764 

16 ............................................................................................................................................................................. 15 2.602 

21 ............................................................................................................................................................................. 20 2.528 

26 ............................................................................................................................................................................. 25 2.485 

31 ............................................................................................................................................................................. 30 2.457 

61 ............................................................................................................................................................................. 60 2.390 

100 ........................................................................................................................................................................... 100 2.326 

Documentation 

The analytical method used must be 

specifically identified by number or title 

and the MDL for each analyte expressed 

in the appropriate method reporting 

units. Data and calculations used to 

establish the MDL must be able to be 

reconstructed upon request. 

The sample matrix used to determine 

the MDL must also be identified with 

MDL value. Document the mean spiked 

and recovered analyte levels with the 

MDL. 

[FR Doc. 2015–02841 Filed 2–18–15; 8:45 am] 

BILLING CODE 6560–50–P 

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