40836 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

ENVIRONMENTAL PROTECTION 

AGENCY 

40 CFR Part 136 

[EPA–HQ–OW–2014–0797; FRL–9957–24– 

OW] 

RIN 2040–AF48 

Clean Water Act Methods Update Rule 

for the Analysis of Effluent 

AGENCY: Environmental Protection 

Agency (EPA). 

ACTION: Final rule. 

SUMMARY: This rule modifies the testing 

procedures approved for analysis and 

sampling under the Clean Water Act. 

The changes adopted in this final rule 

fall into the following categories: New 

and revised EPA methods (including 

new and/or revised methods published 

by voluntary consensus standard bodies 

(VCSB), such as ASTM International 

and the Standard Methods Committee); 

updated versions of currently approved 

methods; methods reviewed under the 

alternate test procedures (ATP) program; 

clarifications to the procedures for EPA 

approval of nationwide and limited use 

ATPs; and amendments to the 

procedure for determination of the 

method detection limit to address 

laboratory contamination and to better 

account for intra-laboratory variability. 

DATES: This regulation is effective on 

September 27, 2017. The incorporation 

by reference of certain publications 

listed in the rule is approved by the 

Director of the Federal Register as of 

September 27, 2017. For judicial review 

purposes, this final rule is promulgated 

as of 1:00 p.m. (Eastern time) on 

September 12, 2017 as provided at 40 

CFR 23.2 and 23.7. 

ADDRESSES: EPA has established a 

docket for this action under Docket ID 

No. EPA–HQ–OW–2014–0797. All 

documents in the docket are listed on 

the www.regulations.gov Web site. 

Although listed in the index, some 

information is not publicly available, 

e.g., confidential business information 

(CBI) or other information whose 

disclosure is restricted by statute. 

Certain other materials, such as 

copyrighted material are not placed on 

the Internet and will be publicly 

available only in hard copy form. 

Publicly available docket materials are 

available either electronically through 

www.regulations.gov or in hard copy at 

the Water Docket in EPA Docket Center, 

EPA/DC, EPA West William J. Clinton 

Building, Room 3334, 1301 Constitution 

Ave. NW., Washington, DC. The Public 

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

4:30 p.m., Monday through Friday, 

excluding legal holidays. The telephone 

number for the Public Reading Room is 

202–566–1744 and the telephone 

number for the Water Docket is 202– 

566–2426. 

FOR FURTHER INFORMATION CONTACT: 

Adrian Hanley, Engineering and 

Analysis Division (4303T), Office of 

Water, Environmental Protection 

Agency, 1200 Pennsylvania Ave. NW., 

Washington, DC 20460–0001; telephone: 

202–564–1564; email: hanley.adrian@

epa.gov. 

SUPPLEMENTARY INFORMATION: 

A. General Information 

1. Does this Action apply to me? 

EPA proposed the changes in this 

method update rule for public comment 

on February 19, 2015 (80 FR 8956). 

EPA Regions, as well as States, 

Territories and Tribes authorized to 

implement the National Pollutant 

Discharge Elimination System (NPDES) 

program, issue permits with conditions 

designed to ensure compliance with the 

technology-based and water qualitybased requirements of the Clean Water 

Act (CWA). These permits may include 

restrictions on the quantity of pollutants 

that may be discharged as well as 

pollutant measurement and reporting 

requirements. If EPA has approved a test 

procedure for analysis of a specific 

pollutant, the NPDES permittee must 

use an approved test procedure (or an 

approved alternate test procedure if 

specified by the permitting authority) 

for the specific pollutant when 

measuring the required waste 

constituent. Similarly, if EPA has 

established sampling requirements, 

measurements taken under an NPDES 

permit must comply with these 

requirements. Therefore, entities with 

NPDES permits will potentially be 

affected by the actions in this 

rulemaking. 

Entities potentially affected by the 

requirements of this rule include: 

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. 

This table is not exhaustive, but rather 

provides a guide for readers regarding 

entities likely to be affected by this 

action. This table lists types of entities 

that EPA is now aware of that could 

potentially be affected by this action. 

Other types of entities not listed in the 

table could also be affected. To 

determine whether your facility is 

affected by this action, you should 

carefully examine the applicability 

language at 40 CFR 122.1 (NPDES 

purpose and scope), 40 CFR 136.1 

(NPDES permits and CWA) and 40 CFR 

403.1 (pretreatment standards purpose 

and applicability). If you have questions 

regarding the applicability of this action 

to a particular entity, consult the 

appropriate person listed in the 

preceding FOR FURTHER INFORMATION

CONTACT section. 

B. What process governs judicial review 

of this rule? 

Under Section 509(b)(1) of the Clean 

Water Act (CWA), judicial review of this 

CWA rule may be obtained by filing a 

petition for review in a United States 

Circuit Court of Appeals within 120 

days from the date of promulgation of 

this rule. For judicial review purposes, 

this final rule is promulgated as of 1 

p.m. (Eastern time) on September 12, 

2017 as provided at 40 CFR 23.2. 

Section 509(b)(2) provides that any rule 

(or requirements of any rule) for which 

review could have been obtained under 

Section 509(b)(1) may also not be 

challenged later in civil or criminal 

proceedings for enforcement. 

C. Abbreviations and Acronyms Used in 

the Preamble and Final Rule Text 

4AAP: 4-Aminoantipyrine 

AA: Atomic Absorption 

ADMI: American Dye Manufacturers Institute 

AOAC: AOAC International 

ASTM: ASTM International 

ATP: Alternate Test Procedure 

BOD5: 5-day Biochemical Oxygen Demand 

test 

CAS: Chemical Abstract Services 

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CATC: Cyanide Amenable to Chlorination 

CFR: Code of Federal Regulations 

CIE/UV: Capillary Ion Electrophoresis/

Ultraviolet 

COD: Chemical Oxygen Demand 

CWA: Clean Water Act 

DPD: N,N-diethyl-p-phenylenediamine 

DPD–FAS: N,N-diethyl-p-phenylenediamine 

with ferrous ammonium sulfate 

EDTA: Ethylenediamine tetraacetic acid 

EPA: Environmental Protection Agency 

FLAA: Flame Atomic Absorption 

Spectroscopy 

GC: Gas Chromatograph/Chromatography 

GC/HSD: Gas chromatography/halogenspecific detector 

GC/MS: Gas chromatography/mass 

spectrometry 

HEM: Hexane extractable material 

HPLC: High performance liquid 

chromatography 

HRGC: High Resolution Gas Chromatography 

HRMS: High Resolution Mass Spectrometry 

HSD: Halogen-specific detector 

ICP: Inductively coupled plasma 

ICP/AES: Inductively Coupled PlasmaAtomic Emission Spectroscopy 

ICP/MS: Inductively Coupled Plasma-Mass 

Spectrometry 

LCS: Laboratory Control Sample 

MDL: Method Detection Limit 

MS: Mass Spectrometry 

MPN: Most Probable Number 

MS/MSD: Matrix Spike/Matrix Spike 

Duplicate 

NARA: National Archives and Records 

Administration 

NPDES: National Pollutant Discharge 

Elimination System 

NIST: National Institute of Standards and 

Technology 

PAH: Polynuclear aromatic hydrocarbons 

POTW: Publicly Owned Treatment Works 

QA: Quality Assurance 

QC: Quality Control 

RRT: Relative retention time 

SDDC: Silver diethyldithiocarbamate 

SGT–HEM: Silica gel treated-hexane 

extractable material 

SM: Standard Methods 

SPADNS: Common name for fluoride dye 

reagent which is a mixture of chemicals 

STGFAA: Stabilized Temperature Graphite 

Furnace Atomic Absorption Spectroscopy 

TKN: Total Kjeldahl Nitrogen 

TOC: Total Organic Carbon 

USGS: United States Geological Survey 

UV: Ultraviolet 

VCSB: Voluntary Consensus Standards Body 

WET: Whole Effluent Toxicity 

Table of Contents 

I. Statutory Authority 

II. Summary of Final Rule 

A. New Versions of Previously Approved 

EPA Methods in 40 CFR 136.3 and 

Appendix A 

B. Methods Incorporated by Reference 

C. New Standard Methods and New 

Versions of Approved Standard Methods 

in 40 CFR 136.3 

D. New Versions of Approved ASTM 

Methods in 40 CFR 136.3 

E. New United States Geological Survey 

(USGS) Methods in 40 CFR 136.3 

F. New ATPs in 40 CFR 136.3 

G. Changes to 40 CFR Part 136 To Align 

With 40 CFR Part 122 

H. Corrections to 40 CFR Part 136 

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

to Required Containers, Preservation 

Techniques, and Holding Times 

J. Clarifications/Corrections to ATP 

Procedures in 40 CFR 136.4, 136.5 and 

Allowed Modifications in 40 CFR 136.6 

K. Changes to Appendix B to 40 CFR Part 

136—Definition and Procedure for the 

Determination of the Method Detection 

Limit (MDL) 

III. Changes Between the Proposed Rule and 

the Final Rule 

A. Changes to Footnote 30 in Table IA and 

Footnote 27 in Table IH 

B. Changes to Table IB 

C. Changes to Table II 

D. Change to Method Modifications and 

Analytical Requirements in § 136.6, 

Methods Modification Paragraph 

E. Changes to EPA Method 608.3 

F. Change to EPA Method 611 

G. Changes to EPA Method 624.1 

H. Changes to EPA Method 625.1 

I. Changes to Method Detection Limit 

(MDL) Procedure 

J. Changes to WET Errata 

IV. Statutory and Executive Order Reviews 

A. Executive Order 12866: Regulatory 

Planning and Review and Review and 

Executive Order 13563: Improving 

Regulation and Regulatory Review 

B. Paperwork Reduction Act 

C. Regulatory Flexibility Act 

D. Unfunded Mandates Reform Act 

E. Executive Order 13132: Federalism 

F. Executive Order 13175: Consultation 

and Coordination With Indian Tribal 

Governments 

G. Executive Order 13045: Protection of 

Children From Environmental Health 

Risks and Safety Risks 

H. Executive Order 13211: Actions That 

Significantly Affect Energy Supply, 

Distribution, or Use 

I. National Technology Transfer and 

Advancement Act of 1995 

J. Executive Order 12898: Federal Actions 

to Address Environmental Justice in 

Minority Populations and Low-Income 

Populations 

K. Congressional Review Act 

I. Statutory Authority 

EPA is promulgating this rule 

pursuant to the authority of sections 

301(a), 304(h), and 501(a) of the Clean 

Water Act (‘‘CWA’’) 33 U.S.C. 1311(a), 

1314(h), and 1361(a). Section 301(a) of 

the CWA prohibits the discharge of any 

pollutant into navigable waters unless 

the discharge complies with, among 

other provisions, a National Pollutant 

Discharge Elimination System (NPDES) 

permit issued under section 402 of the 

CWA. Section 304(h) of the CWA 

requires the Administrator of the EPA to 

‘‘* * * promulgate guidelines 

establishing test procedures for the 

analysis of pollutants that shall include 

the factors which must be provided in 

any certification pursuant to [section 

401 of the CWA] or permit application 

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

Section 501(a) of the CWA authorizes 

the Administrator to ‘‘* * * prescribe 

such regulations as are necessary to 

carry out this function under [the 

CWA].’’ EPA generally has codified its 

test procedure regulations (including 

analysis and sampling requirements) for 

CWA programs at 40 CFR part 136, 

though some requirements are codified 

in other Parts (e.g., 40 CFR chapter I, 

subchapters N and O). 

II. Summary of Final Rule 

The following sections describe the 

changes EPA is making in this final rule. 

In addition, further information 

concerning the rule may be found in a 

document prepared for this rule 

providing EPA’s responses to comments 

it received on the proposed rule. That 

document (‘‘Response to Comments 

Document for the Methods Update Rule 

Proposal (80 CFR 8956, February 19, 

2015’’) is available in the electronic 

docket listed in the ADDRESSES section 

at the beginning of this document. The 

following sections describe changes 

EPA is making in this final rule. 

A. New Versions of Previously Approved 

EPA Methods in 40 CFR 136.3 and 

Appendix A 

This rule approves new versions of 

already approved EPA methods and 

corrects typographical errors in the 

methods. The following briefly 

describes the EPA methods added to 

part 136. 

1. EPA Methods 608.3, 611, 624.1 and 

625.1 

Method 608.3, Organochlorine 

Pesticides and PCBs by GC/HSD. This 

method measures organochorine 

pesticides and polychlorinated 

biphenyls (PCBs) in industrial 

discharges and other environmental 

samples by gas chromatography (GC) 

combined with a halogen-specific 

detector (HSD: e.g., electron capture, 

electrolytic conductivity), as provided 

under 40 CFR 136.1. 

EPA Method 611, Haloethers. This 

method measures the following 

haloethers: Bis(2-chloroethyl) ether, 

bis(2-chloroethoxy) methane, 

2, 2′-oxybis (1-chloropropane), 

4-bromophenyl phenyl ether, and 

4-chlorophenyl phenyl ether in 

municipal and industrial discharges by 

gas chromatography (GC) as provided 

under 40 CFR 136.1. The only change 

EPA has made is correcting a 

typographical error in the list of 

parameters by changing 

‘‘4-Chlorophenyl phenyl either’’ to 

‘‘4-Chlorophenyl phenyl ether’’ and has 

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corrected an analyte name to 

2,2′-oxybis(1-chloropropane), which 

matches the CAS Number 108–60–1. 

EPA Method 624.1, Purgeables by GC/ 

MS. This method measures purgeable 

organic pollutants in industrial 

discharges and other environmental 

samples by gas chromatography (GC) 

combined with mass spectrometry (MS), 

as provided under 40 CFR 136.1. 

EPA Method 625.1, Base/Neutrals and 

Acids by GC/MS. This method measures 

semivolatile organic pollutants in 

industrial discharges and other 

environmental samples by GC/MS, as 

provided under 40 CFR 136.1. 

2. EPA Methods 1600, 1603, 1680, and 

1682 

This rule implements the following 

changes for EPA microbiological 

methods 1600, 1603, 1680, and 1682 

that correct typographical or other errors 

that EPA identified in the methods after 

publication. This rule revises all of 

these methods with new EPA document 

numbers and dates. 

EPA Method 1600 for Enterococci 

using membrane filtration: In Table 3 

Verification controls, EPA changed the 

negative control for brain heart infusion 

broth incubated at 45 °C from 

Escherichia coli to Enterobacter 

aerogenes. E. coli is thermotolerant and 

E. aerogenes is not, so E. coli is not an 

appropriate negative control when 

heated. 

EPA Method 1603 for E. coli using 

membrane filtration: In section 11.5, 

EPA changed the number of colonies on 

a countable plate from 20–60 to 20–80 

colonies. Sixty colonies was a 

typographical error. In addition, the 

following sentence was inadvertently 

omitted and EPA included it: Sample 

volumes of 1–100 mL are normally 

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

10, and 3 mL). 

EPA Method 1680 for fecal coliforms 

using multiple tube fermentation: In 

section 3.1 Definitions, the sentence 

‘‘The predominant fecal coliform is E. 

coli.’’ now reads ‘‘The predominant 

fecal coliform can be E. coli.’’ 

EPA Method 1682 for Salmonella by 

MSRV medium: (1) In section 9.3, Table 

2, the lab-prepared spike acceptance 

criteria now reads: ‘‘Detect–254%’’ and 

‘‘Detect–287%’’ and (2) in section 14.5, 

Table 9, the spiked Salmonella for 

Example 2, Liquid now reads ‘‘3.7 x 108

CFU/mL.’’ 

B. Methods Incorporated by Reference 

Currently, hundreds of methods and 

ATPs are incorporated by reference 

within 40 CFR part 136. In most cases, 

40 CFR part 136 contains multiple 

approved methods for a single pollutant 

and regulated entities often have a 

choice in the selected method. This rule 

incorporates by reference revisions to 

methods from two VCSBs: Standard 

Methods and ASTM. The VCSB 

methods in this rule are in compliance, 

as discussed more fully in Section IV.I 

below, with the National Technology 

Transfer Act which directs EPA to use 

voluntary consensus standards so long 

as they are consistent with applicable 

law and not otherwise impractical. The 

methods are available on their 

respective VCSB Web sites to everyone 

at a cost determined by the VCSB, 

generally from $40 to $80. Both 

organizations also offer memberships or 

subscriptions that allow unlimited 

access to their methods. The cost of 

obtaining these methods is not a 

significant financial burden for a 

discharger or environmental laboratory, 

making the methods reasonably 

available. This rule also includes USGS 

methods and vendor ATPs that are 

incorporated by reference. The ATPs 

and USGS methods are available free of 

charge on the Web site for that 

organization. Therefore, EPA concludes 

that the methods and Alternate Test 

Procedures (ATPs) incorporated by 

reference are reasonably available. The 

individual standards are discussed in 

greater detail below. 

C. New Standard Methods and New 

Versions of Approved Standard 

Methods in 40 CFR 136.3 

This rule approves new versions of 

currently approved Standard Methods. 

The new versions of currently approved 

Standard Methods clarify or improve 

the instructions in the method, improve 

the QC requirements, or make editorial 

corrections. Consistent with the 

previous method update rule (77 FR 

29758, May 18, 2012), EPA generally 

approves and includes in 40 CFR part 

136 only the most recent version of a 

method published by the Standard 

Methods Committee by listing only one 

version of the method with the year of 

publication designated by the last four 

digits in the method number (e.g., SM 

3111 B–2011). The date indicates the 

latest revision date of the method. This 

allows use of a specific method in any 

edition that includes a method with the 

same method number and year of 

publication. 

Most of the revisions included to 

Standard Methods in this rule do not 

contain any substantive changes. Each 

Standard Method entry contains the 

Standard Methods number and date, the 

parameter, and a brief description of the 

analytical technique. The methods 

listed below are organized according to 

the table at 40 CFR part 136 in which 

they appear. 

The following identifies new versions 

of previously approved Standard 

Methods that EPA is including in Table 

IB at 40 CFR part 136. Where there are 

substantive changes to the method, 

these are noted: 

1. SM 2120 B–2011, color, platinum 

cobalt visual comparison method. 

2. SM 2120 F–2011, color, ADMI 

weighted-ordinate spectrophotometer 

method. EPA previously approved this 

method as SM 2120 E–1993. It is also 

similar to the currently approved 

National Council for Air and Stream 

Improvement, Inc. method that uses 

American Dye Manufacturers Institute 

weighted-ordinate.spectrophotometric 

parameters. A footnote on the method 

specifies that the pH should be 7.6 and 

not 7.0 when used for NPDES 

monitoring purposes, since the original 

method was approved with a reference 

pH of 7.6. Additionally, the currently 

approved methods for the Color 

parameter are assigned more specific 

parameter names. 

3. SM 2130 B–2011, turbidity, 

nephelometric method. 

4. SM 2310 B–2011, acidity, titration 

using electrometric endpoint or 

phenolphthalein endpoint. 

5. SM 2320 B–2011, alkalinity, 

electrometric or colorimetric titration to 

pH 4.5. 

6. SM 2340 B–2011 and SM 2340 C– 

2011, hardness, by the calculation 

method or EDTA titration. 

7. SM 2510 B–2011, conductivity, 

Wheatstone bridge method. 

8. SM 2540 B–2011, SM 2540 C–2011, 

SM 2540 D–2011, SM 2540 E–2011, and 

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

(solids, listed in the same order as the 

method numbers), all by gravimetric 

methodologies. 

9. SM 2550 B–2010, temperature, 

thermometric. 

10. SM 3111 B–2011, SM 3111 C– 

2011, SM 3111 D–2011, and SM 3111 E– 

2011, metals, direct aspiration atomic 

absorption (AA) methods with different 

gas mixtures. Each method has a 

different list of metals; these lists were 

not changed. 

11. SM 3112 B–2011, metals, 

applicable to mercury, cold-vapor 

atomic absorption spectrometric 

method. 

12. SM 3113 B–2010, metals, 

electrothermic atomic absorption 

spectrometric method. The only 

substantive change is a reduction in the 

required replicate analyses of each 

calibration standard from three to two. 

Similar EPA methods do not require 

replicates of each calibration standard. 

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13. SM 3114 B–2011 and SM 3114 C– 

2011, total arsenic and total selenium, 

hydride generation/atomic absorption 

spectrometric methods. Both analyze 

total arsenic and total selenium. 

14. SM 3120 B–2011, metals, 

inductively coupled plasma (ICP) 

method; no changes were made to the 

approved list of metals. 

15. SM 3125 B–2011, metals, 

inductively coupled plasma/mass 

spectrometry (ICP/MS) method; no 

changes were made to the approved list 

of metals. 

16. SM 3500-Al B–2011, aluminum, 

colorimetric method. 

17. SM 3500-As B–2011, arsenic, 

colorimetric method silver 

diethyldithiocarbamate (SDDC) method. 

18. SM 3500-Ca B–2011, calcium, 

titrimetric method (EDTA). 

19. SM 3500-Cr B–2011 and SM 3500- 

Cr C–2011, chromium. The ‘‘B’’ method 

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

dissolved chromium. The ‘‘C’’ method 

uses ion chromatography and is only 

approved for dissolved chromium. 

20. SM 3500-Cu B–2011 and SM 

3500-Cu C–2011, copper. Both method 

sections use colorimetric methods. The 

‘‘B’’ method uses a neocuproine reagent, 

and the ‘‘C’’ method uses a 

bathocuproine reagent. 

21. SM 3500-Fe B–2011, iron, 

colorimetric method (phenanthroline). 

22. SM 3500-K B–2011 and SM 3500- 

K C–2011, potassium. The ‘‘B’’ method 

is a flame photometric method, and the 

‘‘C’’ method is an electrode method. 

23. SM 3500-Mn B–2011, manganese, 

colorimetric method (persulfate). 

24. SM 3500-Na B–2011, sodium, 

flame photometric method. 

25. SM 3500-Pb B–2011, lead, 

colorimetric method (dithizone). 

26. SM 3500-V B–2011, vanadium, 

colorimetric method (gallic acid). 

27. SM 3500-Zn B–2011, zinc, 

colorimetric method (zincon). 

28. SM 4110 (B–D)–2011, anions, ion 

chromatography; no changes were made 

to the approved analyte list. 

29. SM 4140 B–2011, inorganic 

anions, capillary ion electrophoresis 

with indirect ultraviolet (UV) detection: 

No changes were made to the approved 

analyte list. 

30. SM 4500-B B–2011, boron, 

spectrophotometer or filter photometer 

(curcumin) 

31. SM 4500-Cl¥ (B–E)–2011, 

chloride, titrimetric: (Silver nitrate), 

(mercuric nitrate), automated 

(ferricyanide), potentiometric titration. 

32. SM 4500-Cl (B–G)–2011, chlorine 

(residual), amperometric direct, 

amperometric direct (low level), 

iodometric direct, back titration ether 

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

ammonium sulfate (DPD-FAS), 

spectrophotometric (DPD). 

33. SM 4500-CN¥ (B–G)–2011, 

cyanide, manual distillation with MgCl2

followed by: Titrimetric, 

spectrophotometric, manual, ion 

selective electrode, cyanide amenable to 

chlorination (CATC); manual 

distillation with MgCl2, followed by: 

Titrimetric or spectrophotometric. 

34. SM 4500-F¥ (B–E)–2011, fluoride, 

manual distillation, followed by any of 

the following: Electrode, manual, 

colorimetric, fluoride dye reagent 

(SPADNS is the common name for the 

fluoride dye reagent which is a mixture 

of chemicals), automated complexone. 

35. SM 4500-H+ B–2011, hydrogen 

ion (pH), electrometric measurement. 

36. SM 4500-NH3 (B–H)–2011, 

ammonia (as nitrogen), manual 

distillation or gas diffusion (pH > 11), 

followed by any of the following: 

Titration, electrode, manual phenate, 

salicylate, or other substituted phenols 

in Berthelot reaction based methods; 

automated phenate, salicylate, or other 

substituted phenols in Berthelot 

reaction based methods. 

37. SM 4500-NO2

¥ B–2011, nitrite (as 

nitrogen), spectrophotometric: Manual. 

38. SM 4500-NO3

¥ D–2011, nitrate (as 

nitrogen), ion selective electrode. 

39. SM 4500-NO3

¥ (E, F, H)–2011, 

nitrate-nitrite (as nitrogen), colorimetric: 

Cadmium reduction-manual and 

automated, and colorimetric: Automated 

hydrazine. 

40. SM 4500-NO3

¥ (E, F)–2011, nitrite 

(as nitrogen), colorimetric: Cadmium 

reduction-manual and automated. 

41. SM 4500-Norg (B–D)–2011, total 

Kjeldahl nitrogen (as nitrogen, organic), 

semi-automated block digester 

colorimetric (distillation not required). 

42. SM 4500-O (B–G)–2011, oxygen 

(dissolved), Winkler (azide 

modification), electrode. 

43. SM 4500-P (B(5), E–H)–2011, 

phosphorus and ortho-phosphate, 

persulfate digestion, digestion, followed 

by any of the following: Manual or 

automated ascorbic acid reduction. The 

‘‘B Part 5’’ method is the persulfate 

digestion procedure and is required 

prior to measurement of total 

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

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

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

approved for total phosphorous. 

44. SM 4500-S2¥ (B–D, F, G)–2011, 

sulfide, sample pretreatment, titrimetric 

(iodine) analysis, colorimetric 

(methylene blue), ion selective 

electrode. 

45. SM 4500-SiO2 (C, E, F)–2011, 

silica, 0.45-micron filtration followed by 

any of the following: Colorimetric, 

manual or automated (molybdosilicate). 

46. SM 4500-SO3

2¥ B–2011, sulfite, 

titrimetric (iodine-iodate). 

47. SM 4500-SO4

2¥ (C–G)–2011, 

sulfate, automated colorimetric, 

gravimetric, and turbidimetric. 

48. SM 5210 B–2011, biochemical 

oxygen demand (BOD5), dissolved 

oxygen depletion. 

49. SM 5220 (B–D)–2011, chemical 

oxygen demand (COD), titrimetric; 

spectrophotometric, manual or 

automatic. 

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

carbon (TOC), combustion, heated 

persulfate or UV persulfate oxidation. 

51. SM 5520 (B, F)–2011, oil and 

grease, hexane extractable material 

(HEM): n-hexane extraction and 

gravimetry, silica gel treated HEM 

(SGT–HEM): Silica gel treatment and 

gravimetry. 

52. SM 5530 (B, D)–2010, phenols, 

manual distillation, followed by 

colorimetric 4-aminoantipyrine (4AAP) 

manual. 

53. SM 5540 C–2011, surfactants, 

colorimetric (methylene blue). 

The following identifies new versions 

of previously approved Standard 

Methods that EPA is including in Table 

IC at 40 CFR part 136: 

1. SM 6200 (B, C)–2011, volatile 

organic compounds, purge and trap 

capillary-column gas chromatographic/

mass spectrometric (GC/MS), purge and 

trap capillary-column gas 

chromatographic (GC) 

2. SM 6440 B–2005, polynuclear 

aromatic hydrocarbons (PAHs), high 

performance liquid chromatography 

(HPLC) 

The following identifies new versions 

of previously approved methods that 

EPA is including in Table ID at 40 CFR 

part 136: 

1. SM 6630 (B, C)–2007, 

organochlorine pesticides, gas 

chromatography (GC) 

2. SM 6640 B–2006, acidic herbicide 

compounds, gas chromatography (GC) 

EPA also revised the approval of 

certain Standard Methods previously 

approved in part 136 for which 

Standard Methods adopted updates that 

contain substantive changes. The 

following summarizes these changes for 

each method, organized by the table at 

40 CFR part 136 in which they appear. 

The following identifies previously 

approved Standard Methods in Table IA 

and/or Table IH at 40 CFR part 136 

Table IB at 40 CFR part 136 where there 

are substantive changes to the method: 

1. EPA replaced the membrane 

filtration method SM 9222 B–1997 with 

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SM 9222 B–2006. This method analyzes 

Coliform (total) in the presence of 

chlorine. The newer method includes a 

number of technology updates that do 

not significantly change the procedure. 

In addition, the method: 

a. Modified the procedure to allow for 

the use of a humidified incubator if 

loose-lidded plates are used during 

incubation. 

b. Added a note that five typical and 

five atypical colonies per membrane 

need to be identified during coliform 

verification. 

c. Moved the definition of ‘‘Coliform’’ 

that was Section 4 of SM 9222, and 

renumbered the rest of the document, 

such that the ‘‘Procedure’’ is now 

Section 4, instead of Section 5. This is 

not a substantive change except that in 

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

in presence of chlorine, number per 100 

mL’’ the citation for ‘‘MF with 

enrichment’’ will be changed from 

‘‘9222 (B+B.5c)–1997’’ to ‘‘9222 

(B+B.4c)–2006.’’ 

2. This rule replaces the membrane 

filtration method SM 9222 D–1997 with 

SM 9222 D–2006. This method analyzes 

Coliform (fecal) and Coliform (fecal) in 

the presence of chlorine. The new 

method allows use of a dry recirculating 

incubator as specified in the culture 

dishes section. In addition, this rule 

adds the following footnote to Tables IA 

and IH regarding SM 9222 D–2006 for 

fecal coliform verification frequency: 

‘‘The verification frequency is at least 

five typical and five atypical colonies 

per sampling site on the day of sample 

collection & analysis.’’ SM 9222 D–2006 

specifies that the fecal coliform colonies 

should be verified ‘‘at a frequency 

established by the laboratory,’’ which 

can be as low as zero. Colonies need to 

be verified to prevent misidentification 

of results as false positive or false 

negative. 

3. This rule replaces the membrane 

filtration method SM 9222 G–1997 with 

SM 9222 G–2006 in Table IH. These 

methods analyze for E. coli and Fecal 

Coliforms. The newer method includes 

a number of technology updates that do 

not significantly change the procedure. 

In addition, the method now has a 

modified composition of EC broth to 

include different quantities of KH2PO4

and 4-methylumbelliferyl-b-Dglucuronide. 

D. New Versions of Approved ASTM 

Methods in 40 CFR 136.3 

This rule approves new versions of 

currently approved ASTM methods, for 

the same reasons outlined in the first 

paragraph of Section II.B above. Many of 

the new versions of ASTM Methods 

approved in 40 CFR part 136 do not 

contain any substantive changes. Each 

entry contains (in the following order): 

Approved ASTM method number and 

date, the parameter, a brief description 

of the analytical technique. Where there 

were substantive changes, they are 

identified. The methods listed below are 

organized according to the table at 40 

CFR part 136 in which they appear. 

The following identifies new versions 

of currently approved ASTM methods 

that are included in Table IB at 40 CFR 

part 136: 

1. ASTM D 511–09 (A, B), calcium 

and magnesium, titrimetric 

ethylenediamine tetraacetic acid 

(EDTA), AA direct aspiration. 

2. ASTM D 516–11, sulfate ion, 

turbidimetric. 

3. ASTM D 858–12 (A–C), manganese, 

atomic absorption (AA) direct 

aspiration, AA furnace. 

4. ASTM D 859–10, silica, 

colorimetric, manual. 

5. ASTM D 1067–11, acidity or 

alkalinity, electrometric endpoint or 

phenolphthalein endpoint; 

electrometric or colorimetric titration to 

pH 4.5, manual. 

6. ASTM D 1068–10 (A–C), iron, AA 

direct aspiration; AA furnace; 

colorimetric (phenanthroline). 

7. ASTM D 1126–12, hardness, 

titrimetric (EDTA). 

8. ASTM D 1179–10 (A, B), fluoride 

ion, electrode, manual; colorimetric, 

(SPADNS). 

9. ASTM D 1246–10, bromide ion, 

electrode. 

10. ASTM D 1687–12 (A–C), 

chromium (total) and dissolved 

hexavalent chromium, colorimetric 

(diphenyl–carbazide); AA direct 

aspiration; AA furnace. 

11. ASTM D 1688–12 (A–C), copper, 

AA direct aspiration, AA furnace. 

12. ASTM D 1691–12 (A, B), zinc, AA 

direct aspiration. 

13. ASTM D 1976–12, dissolved, 

total-recoverable, or total elements, 

inductively coupled plasma/atomic 

emission spectroscopy (ICP/AES). 

14. ASTM D 3223–12, total mercury, 

cold vapor, manual. 

15. ASTM D 3373–12, vanadium, AA 

furnace. 

16. ASTM D 3557–12 (A–D), 

cadmium, AA direct aspiration, AA 

furnace, voltammetry. 

17. ASTM D 3590–11 (A, B), total 

Kjeldahl nitrogen, manual digestion and 

distillation or gas diffusion; semiautomated block digester colorimetric 

(distillation not required). 

18. ASTM D 4382–12, barium, AA 

furnace. 

19. ASTM D 4658–09, sulfide ion, ion 

selective electrode. 

20. ASTM D 5257–11, dissolved 

hexavalent chromium, ion 

chromatography. 

21. ASTM D 5673–10, dissolved 

elements and total-recoverable 

elements, ICP/MS. 

22. ASTM D 5907–13, filterable 

matter (total dissolved solids) and 

nonfilterable matter (total suspended 

solids), gravimetric, 180 °C gravimetric, 

103–105 °C post washing of residue. 

23. ASTM D 6508–10, inorganic 

anions (fluoride, bromide, chloride, 

nitrite, nitrate, orthophosphate, and 

sulfate), capillary ion electrophoresis 

with indirect UV detection. 

24. ASTM D 7284–13, total cyanide, 

manual distillation with MgCl2 followed 

by flow injection, gas diffusion 

amperometry. 

25. ASTM D 7511–12, total cyanide, 

segmented flow injection, in-line 

ultraviolet digestion, followed by gas 

diffusion amperometry. 

EPA has changed Table IC at 40 CFR 

part 136 as follows: 

1. ASTM D 7065–11, nonylphenol, 

bisphenol A, p-tert-octylphenol, 

nonylphenol monoethoxylate, 

nonylphenol diethoxylate, gas 

chromatography/mass spectrometry 

(GC/MS). 

E. New United States Geological Survey 

(USGS) Methods in 40 CFR 136.3 

1. This rule adds USGS Methods 

I–2547–11 and I–2548–11 titled 

‘‘Colorimetric Determination of Nitrate 

Plus Nitrite in Water by Enzymatic 

Reduction, Automated Discrete 

Analyzer Methods,’’ to Table IB for the 

analytes nitrate, nitrite, and combined 

nitrate-nitrite. Method I–2548–11 is a 

low level (analytical range) version of 

Method I–2547–11. Both methods are 

included in the same method title. The 

method can be found in USGS Survey 

Techniques and Methods, Book 5, 

Chapter B8. The method is available at 

no cost from the USGS Web site. This 

method follows the same procedure as 

in ATP Case No. N07–0003—Nitrate 

Elimination Company Inc.’s (NECi) 

Method N07–0003, Revision 9.0, March 

2014, ‘‘Method for Nitrate Reductase 

Nitrate-Nitrogen Analysis,’’ which EPA 

approved in this rule. 

F. New ATPs in 40 CFR 136.3 

This rule approves six methods 

submitted to EPA for review through the 

alternate test procedures (ATP) program 

and deemed acceptable based on the 

evaluation of documented method 

performance. 

The following ATP has nationwide 

approval for wastewater and is 

incorporated into Table IA: 

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1. IDEXX Laboratories, Inc., Colilert®- 

18, ‘‘Coliform/

Test for Fecal Coliforms in Wastewater’’ 

(ATP Case No. N09–0004). The method 

is similar to the already approved E. coli 

Colilert®-18 method, with the addition 

of an increased incubation temperature 

for fecal coliforms, which requires the 

use of a waterbath incubator. The 

Colilert®-18 Coliform/

Substrate Test can be obtained from 

IDEXX Laboratories Inc., One IDEXX 

Drive, Westbrook, ME 04092. 

Telephone: 800–321–0207. 

The following four ATPs have 

nationwide approval for all matrix types 

and are incorporated into Table IB: 

1. The Nitrate Elimination Company 

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

Reductase Nitrate-Nitrogen Analysis,’’ 

Revision 9.0, dated March 2014 (The 

Nitrate Elimination Company, Inc., 

2014a). The analysis measures nitrate, 

nitrite, and combined nitrate-nitrite. 

NECi Method N07–0003 is a ‘‘green’’ 

alternative to the other approved 

methods which use cadmium, a known 

carcinogen for the reduction of nitrate to 

nitrite prior to analyses. NECi Method 

N07–0003 can be obtained from The 

Nitrate Elimination Company, 334 Hecla 

Street, Lake Linden, Michigan, 49945. 

Telephone: 888–NITRATE. 

2. Timberline Instruments, LLC 

Method Ammonia-001, ‘‘Determination 

of Inorganic Ammonia by Continuous 

Flow Gas Diffusion and Conductivity 

Cell Analysis,’’ dated June 24, 2011 

(Timberline Instruments, LLC 2011a). 

Timberline Instruments, LLC Method 

Ammonia-001 can be obtained from 

Timberline Instruments, LLC, 1880 

South Flatiron Court, Boulder, Colorado 

80301. Telephone: 303–440–8779. 

3. Hach Company Method 10242, 

‘‘Simplified Spectrophotometric 

Measurement of Total Kjeldahl Nitrogen 

in Water and Wastewater,’’ Revision 1.1, 

dated January 10, 2013 (Hach Company 

2013a). Hach Company Method 10242 is 

a simplified green chemistry alternative 

to the other approved methods for 

measuring TKN. The method uses less 

toxic reagents (e.g., eliminating the use 

of mercuric sulfate). Hach Company 

Method 10242 can be obtained from 

Hach Company, 5600 Lindbergh Drive, 

Loveland, CO 80539. Telephone: 970– 

669–3050. 

4. Hach Company Method 10206, 

‘‘Spectrophotometric Measurement of 

Nitrate in Water and Wastewater,’’ 

Revision 2.1, dated January 10, 2013 

(Hach Company 2013b). Hach Company 

Method 10206 is a ‘‘green’’ alternative to 

the other approved methods which use 

cadmium, a known carcinogen for the 

reduction of nitrate to nitrite prior to 

analyses. Hach Company Method 10206 

can be obtained from Hach Company, 

5600 Lindbergh Drive, Loveland, CO 

80539. Telephone: 970–669–3050. 

The following ATP has nationwide 

approval for only pulp, paper and 

paperboard mill biologically treated 

effluent and is incorporated into Table 

IB: 

1. National Council for Air and 

Stream Improvement, Inc. (NCASI) 

Method TNTP–W10900, ‘‘Total 

(Kjeldahl) Nitrogen (TKN) and Total 

Phosphorus in Pulp and Paper 

Biologically Treated Effluent by 

Alkaline Persulfate Digestion,’’ dated 

June 2011 (National Council for Air and 

Stream Improvement, Inc. 2011a). 

NCASI Method TNTP–W10900 can be 

obtained from The National Council for 

Air and Stream Improvement, Inc., 

Publications Coordinator, P.O. Box 

13318, Research Triangle Park, NC 

27709–3318, Telephone: 919–941–6400. 

G. Changes to 40 CFR Part 136 To Align 

With 40 CFR Part 122 

This rule amends 40 CFR 136.1 to 

substitute the term ‘‘Director’’ for the 

terms ‘‘Administrator’’ and ‘‘State 

having an authorized program.’’ In 

addition, the rule amends 40 CFR 

136.2(d) to state that the term ‘‘Director’’ 

by cross-reference to the definition of 

‘‘Director’’ in the NPDES regulations at 

40 CFR 122.2. 

EPA eliminated the words ‘‘be 

sufficiently sensitive and’’ from 40 CFR 

136.6(b)(2) to eliminate unnecessary 

confusion with the term ‘‘sufficiently 

sensitive,’’ as used in 40 CFR 122. 

Deleting this term did not change the 

requirements of 40 CFR 136.6(b)(2). 

H. Corrections to 40 CFR Part 136 

This rule corrected typographical 

errors, updated methods from VCSBs 

that went unnoticed during the last 

update to 40 CFR part 136, and added 

technology updates to toxicity methods. 

1. This rule makes multiple 

clarifications and corrections to the 

Whole Effluent Toxicity acute and 

chronic methods manuals (Methods for 

Measuring the Acute Toxicity of 

Effluents and Receiving Waters to 

Freshwater and Marine Organisms, 

EPA–821–R–02–012, October 2002; 

Short-term Methods for Estimating the 

Chronic Toxicity of Effluents and 

Receiving Waters to Freshwater 

Organisms, EPA/821/R–02/013, October 

2002; and Methods for Measuring the 

Chronic Toxicity of Effluents and 

Receiving Waters to Marine and 

Estuarine Organisms, EPA/821/R–02/

014, October 2002) listed in Table IA. 

Clarifications included definition of 

terms (e.g., the acronym YCT—yeast, 

cereal leaves, and trout chow, was not 

defined), consistency corrections among 

the three manuals, notation that Cusum 

figure axes should be log scale, pH and 

temperature measurements should be 

done at the beginning of the test (rather 

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

Corrections also included deletion of 

unavailable products, typographical 

errors, etc. Among the corrections that 

EPA proposed was a change to the 

language for Fathead Minnows, 

Daphnids, and Green Alga in the 

document Short-term Methods for 

Estimating the Chronic Toxicity of 

Effluents and Receiving Waters to 

Freshwater Organisms, Fourth Edition, 

U.S. Environmental Protection Agency, 

Office of Water, Washington, DC EPA/ 

821/R–02/013, October 2002. For 

Fathead Minnows and Daphnids, EPA 

proposed to change ‘‘Conductivity, 

alkalinity, and hardness are measured in 

each new sample (100% effluent or 

receiving water) and in the control’’ to 

read ‘‘Conductivity, alkalinity, and 

hardness are measured at the beginning 

of the test for all test concentrations in 

each new sample and in the control 

before they are dispersed to the test 

chambers.’’ EPA received a number of 

comments stating that this change 

would constitute a change to the test 

rather than a correction or clarification. 

EPA is in agreement with these 

comments, and for that reason, will not 

add the inserted language ‘‘at the 

beginning of the test for all test 

concentrations.’’ EPA is retaining its 

deletion of ‘‘(100% effluent or receiving 

water)’’ and the insertion of ‘‘before they 

are dispensed to the test chamber’’ to 

the end of the sentence. Thus, the 

sentence will now read ‘‘Conductivity, 

alkalinity, and hardness are measured in 

each new sample and in the control 

before they are dispensed to the test 

chamber.’’ For Green Alga, the proposed 

change has been eliminated from the 

errata because only the increased testing 

was proposed. 

2. This rule changes the Standard 

Method listed for E. coli most probable 

number (MPN) in Tables IA and IH. 

During a previous revision, Standard 

Methods added sampling as section 

9221 B.1. As a result, section 9221 B.1 

in previously approved versions has 

become section 9221 B.2. EPA changed 

SM 9221 B.1 to 9221 B.2 in Tables IA 

and IH for E. coli MPN. The related 

footnotes in Tables IA and IH (12, 14 

and 11, 13, respectively) are accurate 

and EPA did not propose to change 

them. 

3. This rule adds a line for 

Enterococci that was erroneously 

deleted in the 2012 Methods Update 

Rule. The line states ‘‘MPN, multiple 

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tube’’ with Standard Method 9230B– 

2007. 

4. This rule revises a hardness entry 

in Table IB to state ‘‘Ca plus Mg as their 

carbonates, by any approved method for 

Ca and Mg (See Parameters 13 and 33), 

provided that the sum of the lowest 

point of quantitation for Ca and Mg is 

below the NPDES permit requirement 

for Hardness.’’ Previously, this was only 

allowed for inductively coupled plasma 

or AA direct aspiration Ca and Mg 

methods. The rationale behind this 

change is that if one calcium and 

magnesium method approved by EPA 

can be used to calculate hardness, then 

other EPA approved methods should 

also be permitted to do so. 

5. This rule deletes ‘‘p 14’’ from 

footnote 24 of Table IB because the 

method is not on that page. 

6. This rule deletes Method 200.5, in 

Table IB from the cobalt, molybdenum 

and thallium entries. These analytes 

have not undergone formal testing by 

this method, and this method should 

not have been approved for these 

analytes. 

7. This rule removes the reference to 

costs in 40 CFR 136.3(b) because costs 

are not included in the referenced 

documents. 

8. This rule removes the first instance 

of ‘‘are’’ in 40 CFR 136.3(e) because it 

is a typographical error. 

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

to Required Containers, Preservation 

Techniques, and Holding Times 

This rule revises Table II at 40 CFR 

136.3(e) as follows. 

1. The rule adds rows to Table II that 

specify holding times for total/fecal 

coliforms, and fecal streptococci in 

Table IH. Previously the holding times 

for these bacterial tests were 

unspecified. Now these methods have 

the same holding time requirements as 

the other bacterial tests. 

2. This rule changes the sodium 

thiosulfate concentrations in Table II for 

bacterial tests from 0.0008% sodium 

thiosulfate to 0.008%. EPA proposed 

this change in its last update to 40 CFR 

part 136 (75 FR 58066–58067), but 

inadvertently omitted it in the 

publication of the final rule. 

3. The rule re-inserts language that 

was accidentally deleted from footnote 

5 of Table II during the previous update 

to 40 CFR part 136. Footnote 5 now 

reads ‘‘ASTM D7365–09a specifies 

treatment options for samples 

containing oxidants (e.g., chlorine) for 

cyanide analysis. Also, Section 9060A 

of Standard Methods for the 

Examination of Water and Wastewater 

(20th and 21st editions) addresses 

dechlorination procedures for 

microbiological analyses.’’ Previously, 

the words: ‘‘for microbiological 

analyses,’’ were not present, so the 

footnote did not specify that treatment 

options for samples containing oxidants 

is specifically for cyanide analysis, and 

that the dechlorination procedures are 

specifically for microbiological 

analyses. 

4. EPA requested public comment on 

how to approve variances to sample 

preservation, containers or holding 

times listed in Table II for specific 

dischargers. Currently, 40 CFR 136.3(e) 

grants authority to either the permitting 

authority in the Region or the Regional 

ATP Program Coordinator to grant 

exceptions to Table II for a specific 

discharger. 

Of the eight comments received, four 

commenters thought that the permitting 

authority should have the sole authority 

to approve these variance requests. 

Three commenters thought that the 

Regional ATP Program Coordinators 

should have sole authority to approve 

variance requests, and one commenter 

thought that the best approach was for 

the permitting authority and the 

Regional ATP Program Coordinator to 

approve Table II variances for specific 

dischargers collaboratively. Each of 

these commenters provided sound 

reasoning for their suggested approach 

to the review and approval of these 

types of requests. 

EPA has chosen to defer any decision 

on revising the current language and to 

leave 40 CFR 136.3(e) unchanged in this 

final rule. 

J. Clarifications/Corrections to ATP 

Procedures in 40 CFR 136.4, 136.5 and 

Allowed Modifications in 136.6 

40 CFR 136.4 and 136.5 describe EPA 

procedures for obtaining approval to use 

an alternate test procedure either on a 

national basis, or for limited use by 

dischargers or facilities specified in the 

approval. In the 2012 Method Update 

Rule, EPA made several clarifying 

changes to the language of these 

sections. At the same time, however, in 

many places in 40 CFR 136.4 and 136.5 

where the phrase ‘‘Regional Alternate 

Test Procedures Coordinator’’ or 

‘‘Regional ATP Coordinator’’ appears, 

EPA inadvertently also inserted the 

phrase ‘‘or permitting authority’’ 

following the phrase. This error resulted 

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

function on the computer. The effect of 

the change was to inadvertently 

authorize State permitting authorities to 

approve ATPs for limited use within the 

State. EPA never intended this result, as 

is demonstrated by two facts. First, in its 

proposal for the 2012 Update (75 FR 

58024, September 23, 2010), EPA did 

not propose to authorize State NPDES 

permitting authorities to approve 

limited use ATPs. Second, the rule 

states that the approval may be 

restricted to specific dischargers or 

facilities, or to all dischargers or 

facilities ‘‘specified in the approval for 

the Region.’’ (emphasis added). This 

language evidenced EPA’s intent that 

only the Region—not the State—would 

be authorized to issue any such limited 

use ATP approval. Finally, as further 

evidence of EPA’s intent, in several 

places, the text of the rule only makes 

sense if read to authorize only the 

Regional ATP Coordinator, not the State 

permitting authority, to approve limited 

use ATPs. For example, 40 CFR 

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

of the application by the Alternate Test 

Procedure Regional ATP Coordinator or 

permitting authority, the Regional ATP 

Coordinator or permitting authority 

notifies the applicant and the 

appropriate State agency of approval or 

rejection of the use of the alternate test 

procedure. As previously written, if the 

State is acting on a request for approval, 

the regulation would require the State to 

inform itself of its own action in 

approving or rejecting the ATP, a 

superfluous requirement. 

This rule deletes all instances of ‘‘or 

permitting authority’’ from 40 CFR 

136.4 and 136.5 to correct this error and 

revise the rule text to its original intent. 

Based on this revision, EPA and EPA 

alone has the authority to approve 

limited use ATPs. 

This rule also changes 40 CFR 136.4 

and 136.5 to clarify the process for 

nationwide ATP approvals and the 

Regional ATP Coordinator’s role in 

limited use ATP approvals. These 

changes do not significantly change the 

process; the intent is to make the text 

simpler and clearer. 

Finally, this rule adds language to 40 

CFR 136.6(b)(1) to clarify that if a 

method user is uncertain whether or not 

a modification is allowed under 40 CFR 

136.6, the user should contact either 

their Director or EPA Regional ATP 

Coordinator. 

K. Changes to Appendix B to 40 CFR 

Part 136—Definition and Procedure for 

the Determination of the Method 

Detection Limit (MDL) 

EPA is revising the procedure for 

determination of the MDL primarily to 

address laboratory blank contamination 

and to better account for intra-laboratory 

variability. The MDL procedure has not 

been revised since it was originally 

promulgated in 1983. The suggestion for 

these revisions came first from The 

National Environmental Laboratory 

Accreditation Conference (NELAC) 

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Institute. EPA proposed to adopt these 

revisions. Following proposal, EPA 

further evaluated the proposed revision 

in conjunction with input from the 

states and commercial laboratories. EPA 

received extensive comments on the 

proposed revisions. 

The revisions address the following 

issues and add new requirements in the 

following areas. 

Background contamination. Under 

the revisions to appendix B, laboratories 

are required to evaluate the MDL to 

account for background levels of 

contamination. As laboratory methods 

become more and more sensitive, 

background levels of contamination are 

more likely to contribute to the result. 

These revisions will reduce false 

positive detects. 

MDLs that represent multiple 

instruments. Under the revisions, if a 

laboratory uses MDL values that 

represent multiple instruments, then the 

laboratory is required to calculate the 

MDL by analyzing MDL samples and 

method blanks on all of these 

instruments. (Note: MDL samples are a 

reference matrix, such as reagent water, 

spiked with a known and consistent 

quantity of the analyte.) Previously, 

laboratories were known to run all of 

their prepared MDL samples on the 

most sensitive instrument, and then use 

that MDL for other instruments. This 

modification makes the MDL more 

representative of the laboratory’s actual 

analytical capability. Deriving an MDL 

that is representative of multiple 

instruments is an option, not a 

requirement; laboratories can determine 

individual MDL values for individual 

instruments if they prefer. 

Under the revisions, laboratories are 

required to run MDL samples and 

method blanks every quarter that 

samples are analyzed using a specific 

method. Previously, laboratories 

redetermined the MDL once a year, 

often under the most ideal 

circumstances (e.g., immediately after 

the instrument has been serviced or 

after an annual maintenance routine). 

Quarterly MDL samples and method 

blanks will determine if the detection 

limit has significantly drifted over time. 

Laboratories will be exempt from 

running the quarterly MDL samples and 

method blanks for a method during 

quarters when no samples are analyzed 

using that method. The ongoing 

quarterly MDL samples and method 

blanks are used to calculate the MDL 

every year, recalculation of the MDL is 

required once every thirteen months. 

Thirteen months was selected to give 

laboratories more flexibility. For 

example, a laboratory can recalculate an 

MDL on January 8th one year and then 

January 17th the next, and still be in 

compliance. 

EPA received comments from 

industries that purchase laboratory 

services that stated the revised MDL 

procedure may increase laboratory 

costs, but not significantly. EPA also 

received comments from some 

laboratories stating the revised MDL 

procedure would impose increased 

costs to laboratories, while other 

laboratories stated the opposite. The 

majority of commenters supported the 

revised MDL procedure. All of the 

laboratory associations, who represent 

the laboratory community, commented 

in favor of the revised MDL procedure. 

Comments not in favor of the MDL 

revision were received from individual 

laboratories, individuals, one utility, 

and two state government departments. 

As a result of the comments, EPA has 

made minor clarifications to the MDL 

procedure. Two options were added to 

the MDL procedure as a result of 

comments received: (1) A streamlined 

approach to determine whether a new 

instrument can be added to a group of 

instruments with an already established 

MDL and (2) laboratories have the 

option to use only the last six months 

of method blank data or the fifty most 

recent method blanks, whichever yields 

the greater number of method blanks to 

calculate the MDL value derived from 

method blanks (MDLb). Both of these 

changes are in line with the goals of the 

revised MDL procedure, and are 

responsive to the comments received. 

Neither of these additions are 

mandatory; however, they provide the 

laboratory with more options for 

calculating the MDL. Commenters also 

noted that the detection limit definition 

in § 136.2(f) should undergo a minor 

revision to match the revisions in the 

MDL procedure (which the definition 

references). The words, ‘‘distinguishable 

from the method blank results’’ has been 

replaced with ‘‘greater than zero’’ in the 

definition. 

III. Changes Between the Proposed Rule 

and the Final Rule 

Except as noted below, the content of 

the final rule is the same as that of the 

proposed rule. 

A. Changes to Footnote 30 in Table IA 

and Footnote 27 in Table IH 

These footnotes regard SM 9222 D– 

2006 for fecal coliform verification 

frequency. EPA proposed a requirement 

of ‘‘at least five typical and five atypical 

colonies per sampling site on the day of 

collection and analysis.’’ A number of 

commenters identified deficiencies with 

the proposed changes. After further 

review, EPA has determined that 

footnote 30 in Table IA and footnote 27 

in Table IH require both modification 

and clarification and is changing both 

footnotes to read ‘‘On a monthly basis, 

at least ten blue colonies from the 

medium must be verified using Lauryl 

Tryptose Broth and EC broth, followed 

by count adjustment based on these 

results; and representative non-blue 

colonies should be verified using Lauryl 

Tryptose Broth. Where possible, 

verifications should be done from 

randomized sample sources.’’ 

B. Changes to Table IB 

As pointed out by multiple 

commenters, and verified by EPA, the 

color parameter in Table IB contains 

methodologies and methods that are 

mislabeled. EPA reorganized the Color 

methodology descriptions and methods 

as follows: (1) The ADMI colorimetric 

procedure SM 2120 F–2011 is now 

listed on a new ‘‘ADMI’’ methodology 

row. (2) Footnote 18 is listed on the 

table row with the methodology 

‘‘spectrophotometric,’’ and footnote 18 

lists both NCASI Technical Bulletin 253 

(1971) and NCASI Technical Bulletin 

803 (2000). NCASI Technical Bulletin 

803 is an update to NCASI Technical 

Bulleting 253 for the measurement of 

color in pulp mill wastewaters. The 

update adds a stabilizing pH buffer and 

turbidity reduction approaches. (3) SM 

2120 B–2011 and USGS Method I– 

1250–85 are on a methodology row 

labeled ‘‘platinum cobalt visual 

comparison’’ methods. 

The Capillary Ion Electrophoresis/

Ultraviolet (CIE/UV) method, D6508, 

Rev. 2 has been moved from the ASTM 

column to the USGS/AOAC/Other 

column because this method is available 

from Waters Corporation (see footnote 

54 in Table IB). This affects the 

following parameters: Bromide, mg/L; 

chloride, mg/L; fluoride—total, mg/L; 

nitrate (as N), mg/L; nitrite (as N), mg/ 

L; orthophosphate (as P), mg/L; and 

sulfate (as SO4) mg/L. 

C. Changes to Table II 

A time clarification of 15 minutes has 

been added to the parameter for 

Temperature. 

The parameter 2-Chloroethylvinyl 

ether has been moved from the first row 

for Table IC organic tests to a separate 

row. Section 9.7 of the revised EPA 

Method 624.1 notes that acidification 

will destroy 2-chlooethylvinyl ether. 

Thus, adding HCl to pH 2 would not be 

acceptable for this parameter. 

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40844 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

D. Change to Method Modifications and 

Analytical Requirements in § 136.6, 

Methods Modification Paragraph 

For clarification purposes, the 

following two lines have been added to 

the methods modification paragraph (b): 

Where the laboratory is using a vendorsupplied method, it is the QC criteria in 

the reference method, not the vendor’s 

method that must be met to show 

equivalency. Where a sample 

preparation step is required (i.e., 

digestion, distillation), QC tests are to be 

run using standards treated in the same 

way as samples. 

Also in this paragraph, the paragraph 

(b)(4)(xvi), ‘‘Changes are allowed in 

purge-and-trap sample volumes or 

operating conditions,’’ was incorrectly 

deleted and is being reinstated. 

Further, paragraph (b)(4)(xvii), 

regarding allowable modifcations to 

Method 625, is being deleted as Method 

625 has been replaced in its entirety 

with an updated version with this 

rulemaking. 

E. Changes to EPA Method 608.3 

EPA received numerous comments on 

Method 608.3, ranging from pointing 

out minor typographical errors to 

questioning substantive technical 

aspects of the proposed method. In 

response, EPA revised the method to 

address many of those comments. See 

the Response to Comments document 

available in the electronic docket listed 

in the ADDRESSES section at the 

beginning of this document for a 

detailed description of the changes. 

Additionally, based on comments 

received in response to the proposal, 

EPA is reverting to the MDL values in 

the earlier version of Method 608 for 

those analytes that were included in 

Table 1 of Method 608.3. The MDLs in 

the proposed version of 608.3 were 

chosen for the proposed revision 

because they were determined with a 

capillary GC column. However, as noted 

by commenters, the values are not 

derived from a multiple laboratory 

validation study. Therefore, EPA has 

restored the original Method 608 MDL 

values. At such time as EPA develops 

new multi-laboratory MDL and ML 

values for the method, they will be 

included in a future revision and 

rulemaking. 

Although EPA received comments 

about updating the QC acceptance 

criteria in Method 608.3, EPA did not 

adopt such changes because EPA lacks 

data from a multi-laboratory validation 

study from which to develop such 

criteria. 

F. Change to EPA Method 611 

In Section 1.1, EPA corrected the last 

parameter in the list of parameters table, 

that read ‘‘4-Chlorophenyl phenyl 

either,’’ a typographical error. The word 

‘‘either’’ should be ‘‘ether.’’ The correct 

parameter name is ‘‘4-Chlorophenyl 

phenyl ether.’’ 

G. Changes to EPA Method 624.1 

EPA received numerous comments on 

Method 624.1, ranging from pointing 

out minor typographical errors to 

questioning substantive technical 

aspects of the proposed method. In 

response, EPA revised the method to 

address many of those comments. See 

the response to comments document 

available in the docket listed in the 

ADDRESSES section at the beginning of 

this document for a detailed description 

of the changes. 

Additionally, section 8.1.2.1.2, 

subsection e, Sample matrices on which 

MS/MSD tests must be performed for 

nationwide use of an allowed 

modification, has been changed to 

update the web link for the list of 

industrial categories with existing 

effluent guidelines to https://

www.epa.gov/cwa-methods/alternatetest-procedure-documents. 

Although EPA received comments 

about updating the QC acceptance 

criteria in Method 624.1, EPA did not 

adopt such changes because EPA lacks 

data from a multi-laboratory validation 

study from which to develop such 

criteria. 

H. Changes to EPA Method 625.1 

EPA received numerous comments on 

Method 625.1, ranging from pointing 

out minor typographical errors to 

questioning substantive technical 

aspects of the proposed method. In 

response, EPA revised the method to 

address many of those comments. See 

the response to comments document 

available in the electronic docket listed 

in the ADDRESSES section at the 

beginning of this document for a 

detailed description of the changes. 

Additionally, as was the case with 

EPA Method 624.1, section 8.1.2.1.2, 

subsection e, Sample matrices on which 

MS/MSD tests must be performed for 

nationwide use of an allowed 

modification, has been changed to 

update the web link for the list of 

industrial categories with existing 

effluent guidelines to https://

www.epa.gov/cwa-methods/alternatetest-procedure-documents. 

Although EPA received comments 

about updating the QC acceptance 

criteria in Method 625.1, EPA did not 

implement such changes because EPA 

lacks data from a multi-laboratory 

validation study from which to develop 

such criteria. 

I. Changes to Method Detection Limit 

(MDL) Procedure, Apppendix B 

No significant revisions were made to 

the proposed MDL procedure. Some 

flexibility was added to the procedure, 

as is discussed in Section II.K above. 

J. Changes to WET Errata 

Among the corrections that EPA 

proposed was a change to the language 

for Fathead minnows, Daphnids, and 

Green Alga in the document Short-term 

Methods for Estimating the Chronic 

Toxicity of Effluents and Receiving 

Waters to Freshwater Organisms, Fourth 

Edition, U.S. Environmental Protection 

Agency, Office of Water, Washington, 

DC EPA/821/R–02/013, October 2002. 

For Fathead Minnows and Daphnids, 

EPA proposed to change ‘‘Conductivity, 

alkalinity, and hardness are measured in 

each new sample (100% effluent or 

receiving water) and in the control’’ to 

read ‘‘Conductivity, alkalinity, and 

hardness are measured at the beginning 

of the test for all test concentrations in 

each new sample and in the control 

before they are dispersed to the test 

chambers.’’ EPA agrees with 

commenters that this change would 

constitute a change to the test rather 

than a correction or clarification. For 

that reason, EPA will not add the 

inserted language ‘‘at the beginning of 

the test for all test concentrations.’’ EPA 

is retaining its deletion of ‘‘(100% 

effluent or receiving water)’’ and the 

insertion of ‘‘before they are dispensed 

to the test chamber’’ to the end of the 

sentence. Thus, the sentence will now 

read ‘‘Conductivity, alkalinity, and 

hardness are measured in each new 

sample and in the control before they 

are dispensed to the test chamber.’’ For 

Green Alga, the proposed change has 

been eliminated from the errata because 

only the increased testing was proposed. 

IV. Statutory and Executive Order 

Reviews 

A. Executive Order 12866: Regulatory 

Planning and Review and Executive 

Order 13563: Improving Regulation and 

Regulatory Review 

This rule is not a ‘‘significant 

regulatory action’’ under the terms of 

Executive Order (EO) 12866 (58 FR 

51735, October 4, 1993) and is therefore 

not subject to review under EO 12866 

and EO 13563. 

B. Paperwork Reduction Act 

This action does not impose an 

information collection burden under the 

provisions of the Paperwork Reduction 

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Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40845 

Act, 44 U.S.C. 3501 et seq. Burden is 

defined at 5 CFR 1320.3(b). This rule 

does not impose any information 

collection, reporting, or recordkeeping 

requirements. This rule merely adds 

new and revised versions of testing 

procedures, and sample preservation 

requirements. 

C. Regulatory Flexibility Act 

The Regulatory Flexibility Act (RFA) 

generally requires an agency to prepare 

a regulatory flexibility analysis of any 

rule subject to notice and comment 

rulemaking requirements under the 

Administrative Procedure Act or any 

other statute unless the agency certifies 

that the rule will not have a significant 

economic impact on a substantial 

number of small entities. Small entities 

include small businesses, small 

organizations, and small governmental 

jurisdictions. 

For purposes of assessing the impacts 

of this rule on small entities for methods 

under the Clean Water Act, small entity 

is defined as: (1) A small business that 

meets RFA default definitions (based on 

SBA size standards) found in 13 CFR 

121.201; (2) a small governmental 

jurisdiction that is a government of a 

city, county, town, school district or 

special district with a population less 

than 50,000; and (3) a small 

organization that is any not-for-profit 

enterprise which is independently 

owned and operated and is not 

dominant in its field. 

After considering the economic 

impacts of this final rule on small 

entities, I certify that this action will not 

have a significant economic impact on 

a substantial number of small entities. 

This action approves new and revised 

versions of testing procedures. 

Generally, these changes will have a 

positive impact on small entities by 

increasing method flexibility, thereby 

allowing entities to reduce costs by 

choosing more cost-effective methods. 

D. Unfunded Mandates Reform Act 

This action contains no Federal 

mandates under the provisions of Title 

II of the Unfunded Mandates Reform 

Act of 1995 (UMRA), 2 U.S.C. 1531– 

1538 for State, local, or tribal 

governments, or the private sector. 

EPA has determined that this final 

rule contains no regulatory 

requirements that might significantly or 

uniquely affect small governments. 

Generally, this action will have a 

positive impact by increasing method 

flexibility, thereby allowing method 

users to reduce costs by choosing more 

cost effective methods. In some cases, 

analytical costs may increase slightly 

due to changes in methods, but these 

increases are neither significant, nor 

unique to small governments. This rule 

merely approves new and revised 

versions of testing procedures, and new 

sample collection, preservation, and 

holding time requirements. 

Thus, this rule is not subject to the 

requirements of Section 203 of UMRA. 

E. Executive Order 13132: Federalism 

This final rule does not have 

federalism implications. It will not have 

substantial direct effects on the States, 

on the relationship between the national 

government and the States, or on the 

distribution of power and 

responsibilities among the various 

levels of government, as specified in 

Executive Order 13132 (64 FR 43255, 

Aug. 10, 1999). This rule merely 

approves new and revised versions of 

testing procedures, and new sample 

collection, preservation, and holding 

time requirements. The costs to State 

and local governments will be minimal. 

In fact, governments may see a cost 

savings because the rule adds flexibility 

for laboratories and permittees to choose 

between additional approved test 

methods and it also provides additional 

flexibility to modify existing test 

methods. Thus, laboratories and 

permittees will not make as many 

requests for approval of alternative test 

methods or method modifications, and 

the rule does not preempt State law. 

Thus, Executive Order 13132 does not 

apply to this rule. 

In the spirit of Executive Order 13132, 

and consistent with EPA policy to 

promote communications between EPA 

and State and local governments, EPA 

specifically solicited comment on the 

proposed rule from State and local 

officials. 

F. Executive Order 13175: Consultation 

and Coordination With Indian Tribal 

Governments 

This final rule does not have tribal 

implications, as specified in Executive 

Order 13175, (65 FR 67249, Nov. 9, 

2000). It will not have substantial direct 

effects on Tribal governments, on the 

relationship between the federal 

government and Indian tribes, or on the 

distribution of power and 

responsibilities between the federal 

government and Indian tribes. This rule 

merely approves new and revised 

versions of testing procedures, and new 

sample collection, preservation, and 

holding time requirements. The costs to 

tribal governments will be minimal. In 

fact, tribal governments may see a cost 

savings because the rule adds flexibility 

for laboratories and permittees to choose 

between additional approved test 

methods and it also provides additional 

flexibility to modify existing test 

methods. Thus, laboratories and 

permittees will not make as many 

requests for approval of alternative test 

methods or method modifications. 

Thus, Executive Order 13175 does not 

apply to this rule. 

In the spirit of Executive Order 13175, 

and consistent with EPA policy to 

promote communications between EPA 

and Indian tribes, EPA specifically 

solicited comment on the proposed rule 

from tribal officials. EPA did not receive 

any comments from Indian tribes. 

G. Executive Order 13045: Protection of 

Children From Environmental Health 

Risks and Safety Risks 

EPA interprets E.O. 13045 (62 FR 

19885, April 23, 1997) as applying only 

to those regulatory actions that concern 

health or safety risks, such that the 

analysis required under section 5–501 of 

the E.O. has the potential to influence 

the regulation. This action is not subject 

to E.O. 13045 because it does not 

establish an environmental standard 

intended to mitigate health or safety 

risks. This rule approves new and 

revised versions of testing procedures, 

and new sample collection, 

preservation, and holding time 

requirements. 

H. Executive Order 13211: Actions That 

Significantly Affect Energy Supply, 

Distribution, or Use 

This action is not subject to Executive 

Order 13211, ‘‘Actions Concerning 

Regulations That Significantly Affect 

Energy Supply, Distribution, or Use’’ (66 

FR 28355 (May 22, 2001)) because it is 

not a significant regulatory action under 

Executive Order 12866. 

I. National Technology Transfer and 

Advancement Act of 1995 

Section 12(d) of the National 

Technology Transfer and Advancement 

Act of 1995, (NTTAA), Public Law 104– 

113, section 12(d) (15 U.S.C. 272 note), 

directs EPA to use voluntary consensus 

standards in its regulatory activities 

unless to do so would be inconsistent 

with applicable law or otherwise 

impractical. Voluntary consensus 

standards are technical standards (e.g., 

material specifications, test methods, 

sampling procedures, and business 

practices) that are developed or adopted 

by voluntary consensus standard bodies. 

The NTTAA directs EPA to provide 

Congress, through the OMB, 

explanations when the Agency decides 

not to use available and applicable 

voluntary consensus standards. 

This final rule approves the use of 

technical standards developed by the 

Standard Methods Committee, and 

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40846 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

ASTM International for use in 

compliance monitoring where the 

Agency has determined that those 

standards meet the needs of Clean Water 

Act programs. EPA did not propose to 

add one Standard Method because that 

method had not undergone full interlaboratory validation as recommended 

in current Agency guidance (see Section 

IV.C of the proposal for this rule (80 FR 

8956, February 19, 2015)). All proposed 

voluntary consensus standards are 

approved in this rule. 

J. Executive Order 12898: Federal 

Actions To Address Environmental 

Justice in Minority Populations and 

Low-Income Populations 

Executive Order (E.O.) 12898 (59 FR 

7629 (Feb. 16, 1994)) establishes federal 

executive policy on environmental 

justice. Its main provision directs 

federal agencies, to the greatest extent 

practicable and permitted by law, to 

make environmental justice part of their 

mission by identifying and addressing, 

as appropriate, disproportionately high 

and adverse human health or 

environmental effects of their programs, 

policies, and activities on minority 

populations and low-income 

populations in the United States. 

This final rule provides additional 

compliance methods for use by any 

facility or laboratory with no 

disproportionate impact on minority or 

low-income populations because it 

merely approves new and revised 

versions of testing procedures to 

measure pollutants in water. 

K. Congressional Review Act 

The Congressional Review Act, 5 

U.S.C. 801 et seq., as added by the Small 

Business Regulatory Enforcement 

Fairness Act of 1996, generally provides 

that before a rule may take effect, the 

agency promulgating the rule must 

submit a rule report, which includes a 

copy of the rule, to each House of the 

Congress and to the Comptroller General 

of the United States. EPA will submit a 

report containing this rule and other 

required information to the U.S. Senate, 

the U.S. House of Representatives, and 

the Comptroller General of the United 

States prior to publication of the rule in 

the Federal Register. This action is not 

a ‘‘major rule’’ as defined by 5 U.S.C. 

804(2). This rule will be effective 

September 27, 2017. 

List of Subjects in 40 CFR Part 136 

Environmental protection, 

Incorporation by reference, Reporting 

and recordkeeping requirements, Test 

procedures, Water pollution control. 

Dated: August 7, 2017. 

E. Scott Pruitt, 

Administrator. 

For the reasons set out in the 

preamble, title 40, chapter I of the Code 

of Federal Regulations is amended as 

follows: 

PART 136—GUIDELINES 

ESTABLISHING TEST PROCEDURES 

FOR THE ANALYSIS OF POLLUTANTS 

■ 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 

through 125 of this chapter; and 

(2) Reports required to be submitted 

by dischargers under the NPDES 

established by parts 124 and 125 of this 

chapter; and 

(3) Certifications issued by States 

pursuant to section 401 of the Clean 

Water Act (CWA), as amended. 

* * * * * 

■ 3. Section 136.2 is amended by 

revising paragraphs (d) and (f) to read as 

follows: 

§ 136.2 Definitions. 

* * * * * 

(d) Director means the director as 

defined in 40 CFR 122.2. 

* * * * * 

(f) Detection limit means the 

minimum concentration of an analyte 

(substance) that can be measured and 

reported with a 99% confidence that the 

analyte concentration is distinguishable 

from the method blank results as 

determined by the procedure set forth at 

appendix B of this part. 

■ 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) through (lviii), 

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

(b)(15)(v), (b)(15)(viii) through (x), 

(b)(15)(xii), (b)(15)(xiii), (b)(15)(xv) 

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

(xxiv), (b)(15)(xxx), (b)(15)(xxxv), 

(b)(15)(xxxvii), (b)(15)(xxxix), 

(b)(15)(xlii), (b)(15)(l), (b)(15)(lii), 

(b)(15)(lv), (b)(15)(lviii), (b)(15)(lix), 

(b)(15)(lxi), (b)(15)(lxiv), (b)(15)(lxvi), 

and (b)(15)(lxviii). 

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

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

(x), respectively. 

■ d. Add new 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)(i). 

■ h. Add paragraphs (b)(25)(ii) and (iii). 

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

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

respectively, and redesignate paragraphs 

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

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

■ j. Add new paragraphs (b)(26) and 

(34). 

■ k. Revise newly redesignated 

paragraph (b)(35). 

■ l. Revise paragraph (c) and Table II 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 texts of the 

referenced test procedures are 

incorporated by reference into Tables 

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

after the method number indicates the 

latest editorial change of the method. 

The discharge parameter values for 

which reports are required must be 

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Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40847 

determined by one of the standard 

analytical test procedures incorporated 

by reference and described in Tables IA, 

IB, IC, ID, IE, IF, IG, and IH or by any 

alternate test procedure which has been 

approved by the Administrator under 

the provisions of paragraph (d) of this 

section and §§ 136.4 and 136.5. Under 

certain circumstances (paragraph (c) of 

this section, in § 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. 132,3 1680,11 15

1681 11 20.

9221 C E–2006.

Multiple tube/multiple 

well, or.

................................... ................................... ................................... Colilert-18®13 8 21 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. 

Colilert-18® 13 17 18

MF 2678 single step 1603 22 ...................... ................................... ................................... mColiBlue-24®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.

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.

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40848 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

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 

Fathead minnow, 

Pimephales 

promelas, embryolarval 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. U.S. EPA. 

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

Biological and Microbiological Samples. 1989. USGS. 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. 11Approved 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. 21Approved for enumeration of target organism in wastewater effluent. 22 Method 1603: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar (modified mTEC), EPA– 

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

U.S. EPA. 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. 29To use Colilert-18® to assay for fecal coliforms, the incubation temperature is 44.5 ± 0.2 °C, and a water bath incubator is used. 

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30On a monthly basis, at least ten blue colonies from the medium must be verified using Lauryl Tryptose Broth and EC broth, followed by count adjustment based 

on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications should be done from randomized 

sample sources. 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES

Parameter Methodology 58 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–2011 .................. 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 ....................... 993.14,3 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 Ammonia001.74

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).

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 .. Digestion,4 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 ....................... 993.14,3 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

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

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, 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: 

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

2011.

D3557–12 (A or B) ......... 974.27,3 p. 37,9 I–3135– 

852 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, 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 endpoint 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.

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 ....................... 993.23.3

Colorimetric (diphenylcarbazide).......................................... 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

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

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 (diphenylcarbazide).......................................... 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 78.

Platinum cobalt visual 

comparison.

......................................... 2120 B–2011 .................. ......................................... I–1250–85.2

Spectrophotometric ........ ......................................... ......................................... ......................................... See footnote.18

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– 

852 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

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–X,56 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).

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40852 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

Automated complexone .. ......................................... 4500–F¥ E–2011.

Ion Chromatography ....... 300.0, Rev 2.1 (1993) 

and 300.1, 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 ....................... 973.52B,3 I–1338–85.2

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 B–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 gas diffusion, 

followed by conductivity cell analysis.

......................................... ......................................... ......................................... Timberline Ammonia001.74

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

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

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

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 10242.76

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

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, 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 419D1, 7 p. 28.9

Spectrophotometric (2,6- 

dimethylphenol).

......................................... ......................................... ......................................... Hach 10206.75

Nitrate-nitrite N minus Nitrite N (See parameters 39 and 40).

39. Nitrate-nitrite (as N), 

mg/L.

Cadmium reduction, 

Manual.

......................................... 4500–NO3

¥ E–2011 ...... D3867–04 (B).

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

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, 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

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, 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

Automated (*bypass Enzymatic reduction).......................................... ......................................... ......................................... I–2547–11,72 I–2548– 

11,72 N07–0003.73

41. Oil and grease—Total 

recoverable, mg/L.

Hexane extractable material (HEM): n-Hexane 

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-201138.

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, 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

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) ................... 973.45B,3 I–1575–78.8

Electrode ........................ ......................................... 4500–O G–2011 ............. D888–09 (B) ................... I–1576–78.8

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).

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

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.

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–SiO2 C–2011 ........ D859–10 ......................... I–1700–85.2

Automated 

(Molybdosilicate).

......................................... 4500–SiO2 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 Digestion,4 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

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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

65. Sulfate (as SO4), mg/

L.

Automated colorimetric ... 375.2, Rev. 2.0 (1993) ... 4500–SO4

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, 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–S2¥ B, C–2011.

Titrimetric (iodine) ........... ......................................... 4500–S2¥ F–2011 .......... ......................................... I–3840–85.2

Colorimetric (methylene 

blue).

......................................... 4500–S2¥ D–2011.

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

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. 

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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 5-day BOD.’’ The addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit requires reporting the traditional BOD5 may not use a nitrification inhibitor in the procedure for reporting the results. Only when a discharger’s permit specifically states CBOD5 is required can 

the permittee report data using a nitrification inhibitor. 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 253 (1971) and Technical Bulletin 803, May 2000. 19 Method 8506, Bicinchoninate 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 Na2S2O3and 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. 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, 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. 

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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. 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, ’’Nitrate Reductase Nitrate-Nitrogen Analysis,’’ Revision 9.0, March 2014, The Nitrate Elimination Co., Inc. 74Timberline Instruments, LLC Method Ammonia-001, ‘‘Determination of Inorganic Ammonia by Continuous Flow Gas Diffusion and Conductivity Cell Analysis,’’ 

June 2011, Timberline Instruments, LLC. 75 Hach Company Method 10206, ‘‘Spectrophotometric Measurement of Nitrate in Water and Wastewater,’’ Revision 2.1, January 2013, Hach Company. 76 Hach Company Method 10242, ‘‘Simplified Spectrophotometric Measurement of Total Kjeldahl Nitrogen in Water and Wastewater,’’ Revision 1.1, January 2013, 

Hach Company. 77 National Council for Air and Stream Improvement (NCASI) Method TNTP–W10900, ‘‘Total (Kjeldahl) Nitrogen and Total Phosphorus in Pulp and Paper Biologically Treated Effluent by Alkaline Persulfate Digestion,’’ June 2011, National Council for Air and Stream Improvement, Inc. 78The pH adjusted sample is to be adjusted to 7.6 for NPDES reporting purposes. 

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

Parameter 1 Method 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 ....................... 6440 B–2005 ........ D4657–92 (98) .....................

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

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

7. Benzidine ................................... Spectro-photometric ... ............................... ............................... .............................................. See footnote,3 p.1. 

GC/MS ........................ 625.15, 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 ........................ 624.1, 1625B ........ 6200 B–2011 ........ .............................................. See footnote,9 p. 27. 

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

GC/MS ........................ 624.1, 1625B ........ 6200 B–2011 ........ .............................................. See footnote,9 p. 27. 

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

GC/MS ........................ 624.1, 1625B ........ 6200 B–2011 ........ .............................................. See footnote,9 p. 27. 

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

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

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

GC/MS ........................ ............................... 6200 C–2011 ........ ..............................................

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

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

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

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

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

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

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

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

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

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

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

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

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

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

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

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

53. 2, 4-Dinitrophenol .................... GC .............................. 604 ....................... 6420 B–2000 ........ .............................................. See footnote,9 p. 27. 

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

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

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

GC/MS ........................ 625.1, 1625B ........ 6410 B–2000 ........ .............................................. See footnote,9 p. 27. 

56. Epichlorohydrin ........................ GC .............................. ............................... ............................... .............................................. See footnote,3 p. 130. 

GC/MS ........................ ............................... ............................... .............................................. See footnote,6 p. S102. 

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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 

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-Heptachlorodibenzofuran.GC/MS ........................ 1613B ................... ............................... ..............................................

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

62. 1,2,3,4,6,7,8- Heptachlorodibenzo-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-Hexachlorodibenzofuran.GC/MS ........................ 1613B ................... ............................... ..............................................

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

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

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

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

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

72. 1,2,3,7,8,9-Hexachlorodibenzo-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. 

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 ........................ 1613B10 ............... ............................... ..............................................

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

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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 .................... 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-Pentachlorodibenzofuran.GC/MS ........................ 1613B ................... ............................... ..............................................

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

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

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-Tetrachlorodibenzofuran.GC/MS ........................ 1613B10 ............... ............................... ..............................................

103. 2,3,7,8-Tetrachloro-dibenzo-pdioxin.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: 

1 All parameters are expressed in micrograms per liter (μg/L) except for Method 1613B, in which the parameters are expressed in picograms per liter (pg/L). 2 The full text of Methods 601–613, 1613B, 1624B, and 1625B are provided at appendix A, Test Procedures for Analysis of Organic Pollutants. The standardized 

test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at appendix B of this part, Definition and Procedure for the 

Determination of the Method Detection Limit. These methods are available at: https://www.epa.gov/cwa-methods as individual PDF files. 3 Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA. 4 Method 624.1 may be used for quantitative determination of acrolein and acrylonitrile, provided that the laboratory has documentation to substantiate the ability to 

detect and quantify these analytes at levels necessary to comply with any associated regulations. In addition, the use of sample introduction techniques other than 

simple purge-and-trap may be required. QC acceptance criteria from Method 603 should be used when analyzing samples for acrolein and acrylonitrile in the absence 

of such criteria in Method 624.1. 5 Method 625.1 may be extended to include benzidine, hexachlorocyclopentadiene, N-nitrosodimethylamine, N-nitrosodi-n-propylamine, and Nnitrosodiphenylamine. However, when they are known to be present, Methods 605, 607, and 612, or Method 1625B, are preferred methods for these compounds. 5a Method 625.1 screening only. 6 Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency, Supplement to the 15th Edition of Standard Methods for 

the Examination of Water and Wastewater. 1981. American Public Health Association (APHA). 7 Each analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601–603, 1624B, and 

1625B in accordance with procedures each in Section 8.2 of each of these Methods. Additionally, each laboratory, on an on-going basis must spike and analyze 10% 

(5% for Methods 624.1 and 625.1 and 100% for methods 1624B and 1625B) of all samples to monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the quality control (QC) acceptance criteria in the pertinent method, analytical 

results for that parameter in the unspiked sample are suspect. The results should be reported but cannot be used to demonstrate regulatory compliance. If the method does not contain QC acceptance criteria, control limits of +/¥ three standard deviations around the mean of a minimum of five replicate measurements must be 

used. These quality control requirements also apply to the Standard Methods, ASTM Methods, and other methods cited. 8 Organochlorine Pesticides and PCBs in Wastewater Using 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. 

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10 Analysts may use Fluid Management Systems, Inc. Power-Prep system in place of manual cleanup provided the analyst meets the requirements of Method 

1613B (as specified in Section 9 of the method) and permitting authorities. Method 1613, Revision B, Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope 

Dilution HRGC/HRMS. Revision B, 1994. U.S. EPA. The full text of this method is provided in appendix A to this part and at https://www.epa.gov/cwa-methods/approved-cwa-methods-organic-compounds. 11 Method 1650, Adsorbable Organic Halides by Adsorption and Coulometric Titration. Revision C, 1997 U.S. EPA. Method 1653, Chlorinated Phenolics in Wastewater by In Situ Acetylation and GCMS. Revision A, 1997 U.S. EPA. The full text for both of these methods is provided at appendix A in part 430 of this chapter, The 

Pulp, Paper, and Paperboard Point Source Category. 12 The compound was formerly inaccurately labeled as 2,2’-oxybis(2-chloropropane) and bis(2-chloroisopropyl) ether. Some versions of Methods 611, and 1625 inaccurately list the analyte as ‘‘bis(2-chloroisopropyl)ether,’’ but use the correct CAS number of 108–60–1. 

TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1

Parameter Method 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. 

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.

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

Parameter Method EPA2 7 10 Standard methods ASTM Other 

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. 

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, 625.15 ...... 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 ............ ........................................ ........................................ ........................................ See footnote,11 O–1126–95. 

44. Malathion .................. GC ................... 614, 1657 ...................... 6630 B–2007 ................. ........................................ See footnote,3 p. 25; See footnote,6

p. S51. 

GC/MS ............ 625.1 .............................. ........................................ ........................................ See footnote,11 O–1126–95. 

45. Methiocarb ................ TLC ................. ........................................ ........................................ ........................................ See footnote,3 p. 94; See footnote,6

p. S60. 

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

HPLC/MS ........ ........................................ ........................................ ........................................ See footnote,12 O–2060–01. 

46. Methoxychlor ............. GC ................... 505, 508, 608.2, 617, 

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 ....... ........................................ ........................................ See footnote,11 O–1126–95. 

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

Parameter Method EPA2 7 10 Standard methods ASTM Other 

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. 

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 of this section, 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 of this part, Definition 

and Procedure for the Determination of the Method Detection Limit. 3 Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater. September 1978. U.S. EPA. This EPA publication includes thin-layer chromatography (TLC) methods. 

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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 https://www.epa.gov/cwa-methods/approved-cwa-test-methods-organic-compounds. 11 Method O–1126–95 is in Open-File Report 95–181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of pesticides in water by C–18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring. 1995. USGS. 12 Method O–2060–01 is in Water-Resources Investigations Report 01–4134, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Pesticides in Water by Graphitized Carbon-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass Spectrometry. 

2001. USGS. 13 Method O–2002–01 is in Water-Resources Investigations Report 01–4098, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of moderate-use pesticides in water by C–18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry. 2001. USGS. 14 Method O–1121–91 is in Open-File Report 91–519, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of 

organonitrogen herbicides in water by solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring. 1992. USGS. 

* * * * * 

TABLE IF—LIST OF APPROVED METHODS FOR PHARMACEUTICAL POLLUTANTS

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 

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 IF note: 

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

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

TABLE IG—TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS

[40 CFR part 455] 

EPA 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. 

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TABLE IG—TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS—Continued 

[40 CFR part 455] 

EPA survey 

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

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-Dichloro-phenoxyacetic 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-Methyl-4- 

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

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 ........................... 314–40–9 507/633/525.1/525.2/1656/608.3/625.1. 

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. 

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-tetrachloro-terephthalate] ...... 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 cyanodithio-imidocarbonate] ...... 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. 

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TABLE IG—TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS—Continued 

[40 CFR part 455] 

EPA survey 

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

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-methyl-dithiocarbamate] ...... 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. 

268 ................. Ziram [Zinc dimethyldithiocarbamate] .......................... 137–30–4 630/630.1. 

Table IG 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. The full 

text of Method 200.7 is provided at appendix C of this part. Methods 608.3 and 625.1 are available at https://www.epa.gov/cwa-methods/approved-cwa-test-methods-organic-compounds. 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 IH—LIST OF APPROVED MICROBIOLOGICAL METHODS FOR AMBIENT WATER

Parameter and units Method 1 EPA Standard methods AOAC, ASTM, 

USGS Other 

Bacteria 

1. Coliform (fecal), number 

per 100 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 Colilert18®.12 15 16

MF,25678 two step, or ......... 1103.1 19 .................... 9222 B–2006/9222 G– 

2006,18 9213 D–2007.

D–5392–93. 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

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TABLE IH—LIST OF APPROVED MICROBIOLOGICAL METHODS FOR AMBIENT WATER—Continued 

Parameter and units Method 1 EPA Standard methods AOAC, ASTM, 

USGS Other 

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 IH 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. U.S. EPA. 

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

Biological and Microbiological Samples. 1989. USGS. 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 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 

byE. 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 andE. 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®, and Quanti-Tray® 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–2006 or other membrane filter procedure to 9222G–2006 using NA–MUG media. 19 Method 1103.1:Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane-ThermotolerantEscherichia coli Agar (mTEC), EPA–821–R–10–002. 

March 2010. U.S. EPA. 20 Method 1603:Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-ThermotolerantEscherichia coli Agar (Modified mTEC), EPA– 

821–R–14–010. September 2014. U.S. 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 andEscherichia coli in Water. Appl. Environ. Microbiol. 59:3534–3544 and in Method 1604: Total Coliforms andEscherichia coli (E. coli) in 

Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI Medium), EPA 821–R–02–024, September 2002, U.S. EPA. 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. 

U.S. 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. U.S. EPA. 25 Method 1622 uses a filtration, concentration, immunomagnetic separation of oocysts from captured material, immunofluorescence assay to determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the detection of Cryptosporidium. Method 1622: Cryptosporidium 

in Water by Filtration/IMS/FA, EPA–821–R–05–001. December 2005. U.S. EPA. 26 Method 1623 uses a filtration, concentration, immunomagnetic separation of oocysts and cysts from captured material, immunofluorescence assay to determine 

concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the simultaneous detection of Cryptosporidium 

and Giardia oocysts and cysts. Method 1623: Cryptosporidium and Giardia in Water by Filtration/IMS/FA. EPA–821–R–05–002. December 2005. U.S. EPA. 27On a monthly basis, at least ten blue colonies from the medium must be verified using Lauryl Tryptose Broth and EC broth, followed by count adjustment based 

on these results; and representative non-blue colonies should be verified using Lauryl Tryptose Broth. Where possible, verifications should be done from randomized 

sample sources. 

(b) Certain material is incorporated by 

reference into this part with the 

approval of the Director of the Federal 

Register under 5 U.S.C. 552(a) and 1 

CFR part 51. All approved material is 

available for inspection at EPA’s Water 

Docket, EPA West, 1301 Constitution 

Avenue NW., Room 3334, Washington, 

DC 20004, Telephone: 202–566–2426, 

and is available from the sources listed 

below. It is also available for inspection 

at the National Archives and Records 

Administration (NARA). For 

information on the availability of this 

material at NARA, call 202–741–6030, 

or go to: https://www.archives.gov/

federal-register/cfr/ibr-locations.html. 

* * * * * 

(8) * * * 

(iv) Method 1600: Enterococci in 

Water by Membrane Filtration Using 

membrane-Enterococcus Indoxyl-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. 

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Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40869 

September 2014. EPA–821–R–14–009. 

Table IA, Note 15. 

* * * * * 

(xv) Method 1682: Salmonella in 

Sewage Sludge (Biosolids) by Modified 

Semisolid Rappaport-Vassiliadis 

(MSRV) Medium. September 2014. EPA 

821–R–14–012. Table IA, Note 23. 

* * * * * 

(10) * * * 

(viii) 2120, Color. 2011. Table IB. 

(ix) 2130, Turbidity. 2011. Table IB. 

(x) 2310, Acidity. 2011. Table IB. 

(xi) 2320, Alkalinity. 2011. Table IB. 

(xii) 2340, Hardness. 2011. Table IB. 

(xiii) 2510, Conductivity. 2011. Table 

IB. 

(xiv) 2540, Solids. 2011. Table IB. 

(xv) 2550, Temperature. 2010. Table 

IB. 

(xvi) 3111, Metals by Flame Atomic 

Absorption Spectrometry. 2011. Table 

IB. 

(xvii) 3112, Metals by Cold-Vapor 

Atomic Absorption Spectrometry. 2011. 

Table IB. 

(xviii) 3113, Metals by Electrothermal 

Atomic Absorption Spectrometry. 2010. 

Table IB. 

(xix) 3114, Arsenic and Selenium by 

Hydride Generation/Atomic Absorption 

Spectrometry. 2011. Table IB. 

(xx) 3120, Metals by Plasma Emission 

Spectroscopy. 2011. Table IB. 

(xxi) 3125, Metals by Inductively 

Coupled Plasma-Mass Spectrometry. 

2011. Table IB. 

(xxii) 3500-Al, Aluminum. 2011. 

Table IB. 

(xxiii) 3500-As, Arsenic. 2011. Table 

IB. 

(xxiv) 3500-Ca, Calcium. 2011. Table 

IB. 

(xxv) 3500-Cr, Chromium. 2011. Table 

IB. 

(xxvi) 3500-Cu, Copper. 2011. Table 

IB. 

(xxvii) 3500-Fe, Iron. 2011. Table IB. 

(xxviii) 3500-Pb, Lead. 2011. Table IB. 

(xxix) 3500-Mn, Manganese. 2011. 

Table IB. 

(xxx) 3500-K, Potassium. 2011. Table 

IB. 

(xxxi) 3500-Na, Sodium. 2011. Table 

IB. 

(xxxii) 3500-V, Vanadium. 2011. 

Table IB. 

(xxxiii) 3500-Zn, Zinc. 2011. Table IB. 

(xxxiv) 4110, Determination of Anions 

by Ion Chromatography. 2011. Table IB. 

(xxxv) 4140, Inorganic Anions by 

Capillary Ion Electrophoresis. 2011. 

Table IB. 

(xxxvi) 4500-B, Boron. 2011. Table IB. 

(xxxvii) 4500-Cl¥, Chloride. 2011. 

Table IB. 

(xxxviii) 4500-Cl, Chlorine (Residual). 

2011. Table IB. 

(xxxix) 4500-CN¥, Cyanide. 2011. 

Table IB. 

(xl) 4500-F¥, Fluoride. 2011. Table 

IB. 

(xli) 4500-H+, pH Value. 2011. Table 

IB. 

(xlii) 4500-NH3, Nitrogen (Ammonia). 

2011. Table IB. 

(xliii) 4500-NO2

¥, Nitrogen (Nitrite). 

2011. Table IB. 

(xliv) 4500–NO3

¥, Nitrogen (Nitrate). 

2011. Table IB. 

(xlv) 4500–Norg, Nitrogen (Organic). 

2011. Table IB. 

(xlvi) 4500–O, Oxygen (Dissolved). 

2011. Table IB. 

(xlvii) 4500–P, Phosphorus. 2011. 

Table IB. 

(xlviii) 4500–SiO2, Silica. 2011. Table 

IB. 

(xlix) 4500–S2¥, Sulfide. 2011. Table 

IB. 

(l) 4500–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 

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40870 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

Inductively Coupled Plasma—Mass 

Spectrometry. September 2010. Table 

IB. 

(lix) ASTM D5(19)907–13, Standard 

Test Method for Filterable Matter (Total 

Dissolved Solids) and Nonfilterable 

Matter (Total Suspended Solids) in 

Water. July 2013. Table IB. 

* * * * * 

(lxi) ASTM. D6508–10, Standard Test 

Method for Determination of Dissolved 

Inorganic Anions in Aqueous Matrices 

Using Capillary Ion Electrophoresis and 

Chromate Electrolyte. October 2010. 

Table IB, Note 54. 

* * * * * 

(lxiv) ASTM. D7065–11, Standard 

Test Method for Determination of 

Nonylphenol, Bisphenol A, p-tertOctylphenol, Nonylphenol 

Monoethoxylate and Nonylphenol 

Diethoxylate in Environmental Waters 

by Gas Chromatography Mass 

Spectrometry. July 2011. Table IB. 

* * * * * 

(lxvi) ASTM. D7284–13, Standard 

Test Method for Total Cyanide in Water 

by Micro Distillation followed by Flow 

Injection Analysis with Gas Diffusion 

Separation and Amperometric 

Detection. July 2013. Table IB. 

* * * * * 

(lxviii) ASTM. D7511–12, Standard 

Test Method for Total Cyanide by 

Segmented Flow Injection Analysis, InLine Ultraviolet Digestion and 

Amperometric Detection. January 2012. 

Table IB. 

* * * * * 

(19) * * * 

(vii) Method 10206, Hach Company 

TNTplus 835/836 Nitrate Method 

10206, Spectrophotometric 

Measurement of Nitrate in Water and 

Wastewater. Revision 2.1, January 10, 

2013. Table IB, Note 75. 

(viii) Method 10242, Hach Company 

TNTplus 880 Total Kjeldahl Nitrogen 

Method 10242, Simplified 

Spectrophotometric Measurement of 

Total Kjeldahl Nitrogen in Water and 

Wastewater. Revision 1.1, January 10, 

2013. Table IB, Note 76. 

* * * * * 

(20) * * * 

(i) Colilert. 2013. Table IA, Notes 17 

and 18; Table IH, Notes 14, 15 and 16. 

(ii) Colilert-18. 2013. Table IA, Notes 

17 and 18; Table IH, Notes 14, 15 and 

16. 

(iii) Enterolert. 2013. Table IA, Note 

24; Table IH, Note 12. 

(iv) Quanti-Tray Insert and Most 

Probable Number (MPN) Table. 2013. 

Table IA, Note 18; Table IH, Notes 14 

and 16. 

* * * * * 

(25) * * * 

(i) NCASI Method TNTP–W10900, 

Total Nitrogen and Total Phophorus in 

Pulp and Paper Biologically Treated 

Effluent by Alkaline Persulfate 

Digestion. June 2011. Table IB, Note 77. 

(ii) NCASI Technical Bulletin No. 

253, An Investigation of Improved 

Procedures for Measurement of Mill 

Effluent and Receiving Water Color. 

December 1971. Table IB, Note 18. 

(iii) NCASI Technical Bulletin No. 

803, An Update of Procedures for the 

Measurement of Color in Pulp Mill 

Wastewaters. May 2000. Table IB, Note 

18. 

(26) The Nitrate Elimination Co., Inc. 

(NECi), 334 Hecla St., Lake Linden NI 

49945. 

(i) NECi Method N07–0003, Method 

for Nitrate Reductase Nitrate-Nitrogen 

Analysis. Revision 9.0. March 2014. 

Table IB, Note 73. 

(ii) [Reserved] 

* * * * * 

(34) Timberline Instruments, LLC, 

1880 South Flatiron Ct., Unit I, Boulder 

CO 80301. 

(i) Timberline Amonia-001, 

Determination of Inorganic Ammonia by 

Continuous Flow Gas Diffusion and 

Conductivity Cell Analysis. June 24, 

2011. Table IB, Note 74. 

(ii) [Reserved] 

(35) U.S. Geological Survey (USGS), 

U.S. Department of the Interior, Reston, 

Virginia. Available from USGS Books 

and Open-File Reports (OFR) Section, 

Federal Center, Box 25425, Denver, CO 

80225. 

(i) Colorimetric determination of 

nitrate plus nitrite in water by 

enzymatic reduction, automated 

discrete analyzer methods. U.S. 

Geological Survey Techniques and 

Methods, Book 5—Laboratory Analysis, 

Section B—Methods of the National 

Water Quality Laboratory, Chapter 8. 

2011. Table IB, Note 72. 

(ii) Methods for Determination of 

Inorganic Substances in Water and 

Fluvial Sediments, editors, Techniques 

of Water-Resources Investigations of the 

U.S. Geological Survey, Book 5, Chapter 

A1. 1979. Table IB, Note 8. 

(iii) Methods for Determination of 

Inorganic Substances in Water and 

Fluvial Sediments, Techniques of 

Water-Resources Investigations of the 

U.S. Geological Survey, Book 5, Chapter 

A1. 1989. Table IB, Note 2. 

(iv) Methods for the Determination of 

Organic Substances in Water and 

Fluvial Sediments. Techniques of 

Water-Resources Investigations of the 

U.S. Geological Survey, Book 5, Chapter 

A3. 1987. Table IB, Note 24; Table ID, 

Note 4. 

(v) OFR 76–177, Selected Methods of 

the U.S. Geological Survey of Analysis 

of Wastewaters. 1976. Table IE, Note 2. 

(vi) OFR 91–519, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Organonitrogen 

Herbicides in Water by Solid-Phase 

Extraction and Capillary-Column Gas 

Chromatography/Mass Spectrometry 

With Selected-Ion Monitoring. 1992. 

Table ID, Note 14. 

(vii) OFR 92–146, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Total Phosphorus by a 

Kjeldahl Digestion Method and an 

Automated Colorimetric Finish That 

Includes Dialysis. 1992. Table IB, Note 

48. 

(viii) OFR 93–125, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Inorganic and Organic 

Constituents in Water and Fluvial 

Sediments. 1993. Table IB, Note 51; 

Table IC, Note 9. 

(ix) OFR 93–449, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Chromium in Water by 

Graphite Furnace Atomic Absorption 

Spectrophotometry. 1993. Table IB, 

Note 46. 

(x) OFR 94–37, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Triazine and Other 

Nitrogen-containing Compounds by Gas 

Chromatography With Nitrogen 

Phosphorus Detectors. 1994. Table ID, 

Note 9. 

(xi) OFR 95–181, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Pesticides in Water by 

C–18 Solid-Phase Extraction and 

Capillary-Column Gas Chromatography/ 

Mass Spectrometry With Selected-Ion 

Monitoring. 1995. Table ID, Note 11. 

(xii) OFR 97–198, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Molybdenum in Water 

by Graphite Furnace Atomic Absorption 

Spectrophotometry. 1997. Table IB, 

Note 47. 

(xiii) OFR 98–165, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Elements in 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— 

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Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40871 

Determination of Arsenic and Selenium 

in Water and Sediment by Graphite 

Furnace—Atomic Absorption 

Spectrometry. 1999. Table IB, Note 49. 

(xv) OFR 00–170, Methods of 

Analysis by the U.S. Geological Survey 

National Water Quality Laboratory— 

Determination of Ammonium Plus 

Organic Nitrogen by a Kjeldahl 

Digestion Method and an Automated 

Photometric Finish that Includes Digest 

Cleanup by Gas Diffusion. 2000. Table 

IB, Note 45. 

(xvi) Techniques and Methods Book 

5–B1, Determination of Elements in 

Natural-Water, Biota, Sediment and Soil 

Samples Using Collision/Reaction Cell 

Inductively Coupled Plasma-Mass 

Spectrometry. Chapter 1, Section B, 

Methods of the National Water Quality 

Laboratory, Book 5, Laboratory 

Analysis. 2006. Table IB, Note 70. 

(xvii) U.S. Geological Survey 

Techniques of Water-Resources 

Investigations, Book 5, Laboratory 

Analysis, Chapter A4, Methods for 

Collection and Analysis of Aquatic 

Biological and Microbiological Samples. 

1989. Table IA, Note 4; Table IH, Note 

4. 

(xviii) Water-Resources Investigation 

Report 01–4098, Methods of Analysis by 

the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Moderate-Use 

Pesticides and Selected Degradates in 

Water by C–18 Solid-Phase Extraction 

and Gas Chromatography/Mass 

Spectrometry. 2001. Table ID, Note 13. 

(xix) Water-Resources Investigations 

Report 01–4132, Methods of Analysis by 

the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Organic Plus Inorganic 

Mercury in Filtered and Unfiltered 

Natural Water With Cold Vapor-Atomic 

Fluorescence Spectrometry. 2001. Table 

IB, Note 71. 

(xx) Water-Resources Investigation 

Report 01–4134, Methods of Analysis by 

the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Pesticides in Water by 

Graphitized Carbon-Based Solid-Phase 

Extraction and High-Performance Liquid 

Chormatography/Mass Spectrometry. 

2001. Table ID, Note 12. 

(xxi) Water Temperature—Influential 

Factors, Field Measurement and Data 

Presentation, Techniques of 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. 

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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

38. Nitrate ...................................... P, FP, G ........................................ Cool, ≤6 °C 18 ............................... 48 hours. 

39. Nitrate-nitrite ............................ P, FP, G ........................................ Cool, ≤6 °C,18H2SO4 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. 

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 within 15 minutes. 

73. Turbidity ................................... P, FP, G ........................................ Cool, ≤6 °C 18 ............................... 48 hours. 

Table IC—Organic Tests 8

13, 18–20, 22, 24, 25, 27,28, 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

HCl to pH 2.

14 days. 

26. 2-Chloroethylvinyl ether ........... 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. 

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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

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. 

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. 

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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. 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 

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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. 

■ 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)(xvii). 

■ c. Redesignate paragraphs (b)(4)(xviii) 

through the first occurrence of (xxii) as 

paragraphs (b)(4)(xvii) through (xxi), 

respectively and retaining the second 

occurrence of paragraph (b)(4)(xxii). 

■ d. Add paragraph (c). 

The revisions 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. Where the 

laboratory is using a vendor-supplied 

method, it is the QC criteria in the 

reference method, not the vendor’s 

method, that must be met to show 

equivalency. Where a sample 

preparation step is required (i.e., 

digestion, distillation), QC tests are to be 

run using standards treated in the same 

way as the samples. The method user’s 

Standard Operating Procedure (SOP) 

must clearly document the 

modifications made to the reference 

method. Examples of allowed method 

modifications are listed in this section. 

If the method user is uncertain whether 

a method modification is allowed, the 

Regional ATP Coordinator or Director 

should be contacted for approval prior 

to implementing the modification. The 

method user should also complete 

necessary performance checks to verify 

that acceptable performance is achieved 

with the method modification prior to 

analyses of compliance samples. 

(2) Requirements. The modified 

method must meet or exceed 

performance of the approved method(s) 

for the analyte(s) of interest, as 

documented by meeting the initial and 

ongoing quality control requirements in 

the method. 

* * * * * 

(c) The permittee must notify their 

permitting authority of the intent to use 

a modified method. Such notification 

should be of the form ‘‘Method xxx has 

been modified within the flexibility 

allowed in 40 CFR 136.6.’’ The 

permittee may indicate the specific 

paragraph of § 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. Remove Method 608; 

■ b. Add Method 608.3; 

■ c. Revise Method 611 section 1.1.; 

■ d. Remove Method 624; 

■ e. Add Method 624.1; 

■ f. Remove Method 625; and 

■ g. Add Method 625.1. 

The additions and revisions read as 

follows: 

Appendix A to Part 136—Methods for 

Organic Chemical Analysis of 

Municipal and Industrial Wastewater 

* * * * * 

Method 608.3—Organochlorine Pesticides 

And PCBs By GC/HSD 

1. Scope and Application 

1.1 This method is for determination of 

organochlorine pesticides and 

polychlorinated biphenyls (PCBs) in 

industrial discharges and other 

environmental samples by gas 

chromatography (GC) combined with a 

halogen-specific detector (HSD; e.g., electron 

capture, electrolytic conductivity), as 

provided under 40 CFR 136.1. This revision 

is based on a previous protocol (Reference 1), 

on the revision promulgated October 26, 

1984, on an inter-laboratory method 

validation study (Reference 2), and on EPA 

Method 1656 (Reference 16). The analytes 

that may be qualitatively and quantitatively 

determined using this method and their CAS 

Registry numbers are listed in Table 1. 

1.2 This method may be extended to 

determine the analytes listed in Table 2. 

However, extraction or gas chromatography 

challenges for some of these analytes may 

make quantitative determination difficult. 

1.3 When this method is used to analyze 

unfamiliar samples for an analyte listed in 

Table 1 or Table 2, analyte identification 

must be supported by at least one additional 

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qualitative technique. This method gives 

analytical conditions for a second GC column 

that can be used to confirm and quantify 

measurements. Additionally, Method 625.1 

provides gas chromatograph/mass 

spectrometer (GC/MS) conditions appropriate 

for the qualitative confirmation of results for 

the analytes listed in Tables 1 and 2 using 

the extract produced by this method, and 

Method 1699 (Reference 18) provides high 

resolution GC/MS conditions for qualitative 

confirmation of results using the original 

sample. When such methods are used to 

confirm the identifications of the target 

analytes, the quantitative results should be 

derived from the procedure with the 

calibration range and sensitivity that are most 

appropriate for the intended application. 

1.4 The large number of analytes in 

Tables 1 and 2 makes testing difficult if all 

analytes are determined simultaneously. 

Therefore, it is necessary to determine and 

perform quality control (QC) tests for the 

‘‘analytes of interest’’ only. The analytes of 

interest are those required to be determined 

by a regulatory/control authority or in a 

permit, or by a client. If a list of analytes is 

not specified, the analytes in Table 1 must be 

determined, at a minimum, and QC testing 

must be performed for these analytes. The 

analytes in Table 1 and some of the analytes 

in Table 2 have been identified as Toxic 

Pollutants (40 CFR 401.15), expanded to a list 

of Priority Pollutants (40 CFR part 423, 

appendix A). 

1.5 In this revision to Method 608, 

Chlordane has been listed as the alpha- and 

gamma- isomers in Table 1. Reporting may be 

by the individual isomers, or as the sum of 

the concentrations of these isomers, as 

requested or required by a regulatory/control 

authority or in a permit. Technical Chlordane 

is listed in Table 2 and may be used in cases 

where historical reporting has only been the 

Technical Chlordane. Toxaphene and the 

PCBs have been moved from Table 1 to Table 

2 (Additional Analytes) to distinguish these 

analytes from the analytes required in quality 

control tests (Table 1). QC acceptance criteria 

for Toxaphene and the PCBs have been 

retained in Table 4 and may continue to be 

applied if desired, or if these analytes are 

requested or required by a regulatory/control 

authority or in a permit. Method 1668C 

(Reference 17) may be useful for 

determination of PCBs as individual 

chlorinated biphenyl congeners, and Method 

1699 (Reference 18) may be useful for 

determination of the pesticides listed in this 

method. However, at the time of writing of 

this revision, Methods 1668C and 1699 had 

not been approved for use at 40 CFR part 136. 

1.6 Method detection limits (MDLs; 

Reference 3) for the analytes in Tables 1 and 

some of the analytes in Table 2 are listed in 

those tables. These MDLs were determined in 

reagent water (Reference 3). Advances in 

analytical technology, particularly the use of 

capillary (open-tubular) columns, allowed 

laboratories to routinely achieve MDLs for 

the analytes in this method that are 2–10 

times lower than those in the version 

promulgated in 1984. The MDL for an analyte 

in a specific wastewater may differ from 

those listed, depending upon the nature of 

interferences in the sample matrix. 

1.6.1 EPA has promulgated this method 

at 40 CFR part 136 for use in wastewater 

compliance monitoring under the National 

Pollutant Discharge Elimination System 

(NPDES). The data reporting practices 

described in section 15.6 are focused on such 

monitoring needs and may not be relevant to 

other uses of the method. 

1.6.2 This method includes ‘‘reporting 

limits’’ based on EPA’s ‘‘minimum level’’ 

(ML) concept (see the glossary in section 23). 

Tables 1 and 2 contain MDL values and ML 

values for many of the analytes. 

1.7 The separatory funnel and continuous 

liquid-liquid sample extraction and 

concentration steps in this method are 

essentially the same as those steps in 

Methods 606, 609, 611, and 612. Thus, a 

single sample may be extracted to measure 

the analytes included in the scope of each of 

these methods. Samples may also be 

extracted using a disk-based solid-phase 

extraction (SPE) procedure developed by the 

3M Corporation and approved by EPA as an 

Alternate Test Procedure (ATP) for 

wastewater analyses in 1995 (Reference 20). 

1.8 This method is performance-based. It 

may be modified to improve performance 

(e.g., to overcome interferences or improve 

the accuracy of results) provided all 

performance requirements are met. 

1.8.1 Examples of allowed method 

modifications are described at 40 CFR 136.6. 

Other examples of allowed modifications 

specific to this method are described in 

section 8.1.2. 

1.8.2 Any modification beyond those 

expressly permitted at 40 CFR 136.6 or in 

section 8.1.2 of this method shall be 

considered a major modification subject to 

application and approval of an alternate test 

procedure under 40 CFR 136.4 and 136.5. 

1.8.3 For regulatory compliance, any 

modification must be demonstrated to 

produce results equivalent or superior to 

results produced by this method when 

applied to relevant wastewaters (section 

8.1.2). 

1.9 This method is restricted to use by or 

under the supervision of analysts 

experienced in the use of GC/HSD. The 

laboratory must demonstrate the ability to 

generate acceptable results with this method 

using the procedure in section 8.2. 

1.10 Terms and units of measure used in 

this method are given in the glossary at the 

end of the method. 

2. Summary of Method 

2.1 A measured volume of sample, the 

amount required to meet an MDL or reporting 

limit (nominally 1–L), is extracted with 

methylene chloride using a separatory 

funnel, a continuous liquid/liquid extractor, 

or disk-based solid-phase extraction 

equipment. The extract is dried and 

concentrated for cleanup, if required. After 

cleanup, or if cleanup is not required, the 

extract is exchanged into an appropriate 

solvent and concentrated to the volume 

necessary to meet the required compliance or 

detection limit, and analyzed by GC/HSD. 

2.2 Qualitative identification of an 

analyte in the extract is performed using the 

retention times on dissimilar GC columns. 

Quantitative analysis is performed using the 

peak areas or peak heights for the analyte on 

the dissimilar columns with either the 

external or internal standard technique. 

2.3 Florisil®, alumina, a C18 solid-phase 

cleanup, and an elemental sulfur cleanup 

procedure are provided to aid in elimination 

of interferences that may be encountered. 

Other cleanup procedures may be used if 

demonstrated to be effective for the analytes 

in a wastewater matrix. 

3. Contamination and Interferences 

3.1 Solvents, reagents, glassware, and 

other sample processing lab ware may yield 

artifacts, elevated baselines, or matrix 

interferences causing misinterpretation of 

chromatograms. All materials used in the 

analysis must be demonstrated free from 

contamination and interferences by running 

blanks initially and with each extraction 

batch (samples started through the extraction 

process in a given 24-hour period, to a 

maximum of 20 samples—see Glossary for 

detailed definition), as described in section 

8.5. Specific selection of reagents and 

purification of solvents by distillation in allglass systems may be required. Where 

possible, labware is cleaned by extraction or 

solvent rinse, or baking in a kiln or oven. 

3.2 Glassware must be scrupulously 

cleaned (Reference 4). Clean all glassware as 

soon as possible after use by rinsing with the 

last solvent used in it. Solvent rinsing should 

be followed by detergent washing with hot 

water, and rinses with tap water and reagent 

water. The glassware should then be drained 

dry, and heated at 400 °C for 15–30 minutes. 

Some thermally stable materials, such as 

PCBs, may require higher temperatures and 

longer baking times for removal. Solvent 

rinses with pesticide quality acetone, hexane, 

or other solvents may be substituted for 

heating. Do not heat volumetric labware 

above 90 °C. After drying and cooling, store 

inverted or capped with solvent-rinsed or 

baked aluminum foil in a clean environment 

to prevent accumulation of dust or other 

contaminants. 

3.3 Interferences by phthalate esters can 

pose a major problem in pesticide analysis 

when using the electron capture detector. 

The phthalate esters generally appear in the 

chromatogram as large late eluting peaks, 

especially in the 15 and 50% fractions from 

Florisil®. 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 solventwetted 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 

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samples high in total organic carbon (TOC) 

may result in elevated baselines, or by 

enhancing or suppressing a signal at or near 

the retention time of an analyte of interest. 

Analyses of the matrix spike and matrix 

spike duplicate (Section 8.3) may be useful 

in identifying matrix interferences, and the 

cleanup procedures in Section 11 may aid in 

eliminating these interferences. EPA has 

provided guidance that may aid in 

overcoming matrix interferences (Reference 

7); however, unique samples may require 

additional cleanup approaches to achieve the 

MDLs listed in Tables 1 and 2. 

4. Safety 

4.1 Hazards associated with each reagent 

used in this method have not been precisely 

defined; however, each chemical compound 

should be treated as a potential health 

hazard. From this viewpoint, exposure to 

these chemicals must be reduced to the 

lowest possible level by whatever means 

available. The laboratory is responsible for 

maintaining a current awareness file of 

OSHA regulations regarding the safe 

handling of the chemicals specified in this 

method. A reference file of safety data sheets 

(SDSs, OSHA, 29 CFR 1910.12009(g)) should 

also be made available to all personnel 

involved in sample handling and chemical 

analysis. Additional references to laboratory 

safety are available and have been identified 

(References 8 and 9) for the information of 

the analyst. 

4.2 The following analytes covered by 

this method have been tentatively classified 

as known or suspected human or mammalian 

carcinogens: 4,4′-DDT, 4,4′-DDD, the BHCs, 

and the PCBs. Primary standards of these 

toxic analytes should be prepared in a 

chemical fume hood, and a NIOSH/MESA 

approved toxic gas respirator should be worn 

when high concentrations are handled. 

4.3 This method allows the use of 

hydrogen as a carrier gas in place of helium 

(section 5.8.2). The laboratory should take 

the necessary precautions in dealing with 

hydrogen, and should limit hydrogen flow at 

the source to prevent buildup of an explosive 

mixture of hydrogen in air. 

5. Apparatus and Materials 

Note: Brand names and suppliers are for 

illustration purposes only. No endorsement 

is implied. Equivalent performance may be 

achieved using equipment and materials 

other than those specified here. 

Demonstrating that the equipment and 

supplies used in the laboratory achieve the 

required performance is the responsibility of 

the laboratory. Suppliers for equipment and 

materials in this method may be found 

through an on-line search. Please do not 

contact EPA for supplier information. 

5.1 Sampling equipment, for discrete or 

composite sampling. 

5.1.1 Grab sample bottle—Amber glass 

bottle large enough to contain the necessary 

sample volume (nominally 1 L), fitted with 

a fluoropolymer-lined screw cap. Foil may be 

substituted for fluoropolymer if the sample is 

not corrosive. If amber bottles are not 

available, protect samples from light. Unless 

pre-cleaned, the bottle and cap liner must be 

washed, rinsed with acetone or methylene 

chloride, and dried before use to minimize 

contamination. 

5.1.2 Automatic sampler (optional)—The 

sampler must use a glass or fluoropolymer 

container and tubing for sample collection. If 

the sampler uses a peristaltic pump, a 

minimum length of compressible silicone 

rubber tubing may be used. Before use, rinse 

the compressible tubing thoroughly with 

methanol, followed by repeated rinsing with 

reagent water to minimize the potential for 

sample contamination. An integrating flow 

meter is required to collect flow proportional 

composites. The sample container must be 

kept refrigerated at ≤6 °C and protected from 

light during compositing. 

5.2. Lab ware. 

5.2.1 Extraction. 

5.2.1.1 pH measurement. 

5.2.1.1.1 pH meter, with combination 

glass electrode. 

5.2.1.1.2 pH paper, wide range (Hydrion 

Papers, or equivalent). 

5.2.1.2 Separatory funnel—Size 

appropriate to hold the sample and 

extraction solvent volumes, equipped with 

fluoropolymer stopcock. 

5.2.1.3 Continuous liquid-liquid 

extractor—Equipped with fluoropolymer or 

glass connecting joints and stopcocks 

requiring no lubrication. (Hershberg-Wolf 

Extractor, Ace Glass Company, Vineland, NJ, 

or equivalent.) 

5.2.1.3.1 Round-bottom flask, 500-mL, 

with heating mantle. 

5.2.1.3.2 Condenser, Graham, to fit 

extractor. 

5.2.1.4 Solid-phase extractor—90-mm 

filter apparatus (Figure 2) or multi-position 

manifold. 

Note: The approved ATP for solid-phase 

extraction is limited to disk-based extraction 

media and associated peripheral equipment. 

5.2.1.4.1 Vacuum system—Capable of 

achieving 0.1 bar (25 inch) Hg (house 

vacuum, vacuum pump, or water aspirator), 

equipped with shutoff valve and vacuum 

gauge. 

5.2.1.4.2 Vacuum trap—Made from 500- 

mL sidearm flask fitted with single-hole 

rubber stopper and glass tubing. 

5.2.2 Filtration. 

5.2.2.1 Glass powder funnel, 125- to 250- 

mL. 

5.2.2.2 Filter paper for above, Whatman 

41, or equivalent. 

5.2.2.3 Prefiltering aids—90-mm 1-mm 

glass fiber filter or Empore® Filter Aid 400. 

5.2.3 Drying column. 

5.2.3.1 Chromatographic column— 

Approximately 400 mm long x 15 mm ID, 

with fluoropolymer stopcock and coarse frit 

filter disc (Kontes or equivalent). 

5.2.3.2 Glass wool—Pyrex, extracted with 

methylene chloride or baked at 450 °C for 1 

hour minimum. 

5.2.4 Column for Florisil® or alumina 

cleanup—Approximately 300 mm long x 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, KudernaDanish—10-mL, graduated (Kontes or 

equivalent). Calibration must be checked at 

the volumes employed for extract volume 

measurement. A ground-glass stopper is used 

to prevent evaporation of extracts. 

5.2.5.1.2 Evaporative flask, 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. 

5.2.5.3.1 A recirculating water pump and 

chiller are recommended, as use of tap water 

for cooling the evaporator wastes large 

volumes of water and can lead to 

inconsistent performance as water 

temperatures and pressures vary. 

5.2.5.3.2 Round-bottom flask—100-mL 

and 500-mL or larger, with ground-glass 

fitting compatible with the rotary evaporator 

Note: This equipment is used to prepare 

copper foil or copper powder for removing 

sulfur from sample extracts (see Section 

6.7.4). 

5.2.5.4 Automated concentrator— 

Equipped with glassware sufficient to 

concentrate 3–400 mL extract to a final 

volume of 1–10 mL under controlled 

conditions of temperature and nitrogen flow 

(Turbovap, or equivalent). Follow 

manufacturer’s directions and requirements. 

5.2.5.5 Boiling chips—Glass, silicon 

carbide, or equivalent, approximately 10/40 

mesh. Heat at 400 °C for 30 minutes, or 

solvent rinse or Soxhlet extract with 

methylene chloride. 

5.2.6 Solid-phase extraction disks—90- 

mm extraction disks containing 2 g of 8-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. 

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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 single-hole rubber 

stopper and glass tubing. 

5.5.3.4 Rack for holding 50-mL 

volumetric flasks in the manifold. 

5.5.3.5 Cartridge—Mega Bond Elute, Nonpolar, C18 Octadecyl, 10 g/60 mL 

(Analytichem International or equivalent), 

used for solid-phase cleanup of sample 

extracts (see Section 11.2). 

5.5.4 Sulfur removal tube—40- to 50-mL 

bottle, test tube, or Erlenmeyer flask with 

fluoropolymer-lined screw cap. 

5.6 Centrifuge apparatus. 

5.6.1 Centrifuge—Capable of rotating 500- 

mL centrifuge bottles or 15-mL centrifuge 

tubes at 5,000 rpm minimum. 

5.6.2 Centrifuge bottle—500-mL, with 

screw cap, to fit centrifuge. 

5.6.3 Centrifuge tube—15-mL, with screw 

cap, to fit centrifuge. 

5.7 Miscellaneous lab ware—Graduated 

cylinders, pipettes, beakers, volumetric 

flasks, vials, syringes, and other lab ware 

necessary to support the operations in this 

method. 

5.8 Gas chromatograph—Dual-column 

with simultaneous split/splitless, 

temperature programmable split/splitless 

(PTV), or on-column injection; temperature 

program with isothermal holds, and all 

required accessories including syringes, 

analytical columns, gases, and detectors. An 

autosampler is highly recommended because 

it injects volumes more reproducibly than 

manual injection techniques. Alternatively, 

two separate single-column gas 

chromatographic systems may be employed. 

5.8.1 Example columns and operating 

conditions. 

5.8.1.1 DB–608 (or equivalent), 30-m long 

x 0.53-mm ID fused-silica capillary, 0.83-mm 

film thickness. 

5.8.1.2 DB–1701 (or equivalent), 30-m 

long x 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: 

(a) Carrier gas flow rate: Approximately 7 

mL/min, 

(b) Initial temperature: 150 °C for 0.5 

minute, 

(c) Temperature program: 150–270 °C at 5 

°C/min, and 

(d) 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, 

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 allglass 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 foil-covered glass container and allow to 

cool. Alternatively, 500 mg cartridges (J.T. 

Baker, or equivalent) may be used. 

6.7.1.1 Cartridge certification—Each 

cartridge lot must be certified to ensure 

recovery of the analytes of interest and 

removal of 2,4,6-trichlorophenol. To make 

the test mixture, add the trichlorophenol 

solution (section 6.7.1.3) to the same 

standard used to prepare the Quality Control 

Check Sample (section 6.8.3). Transfer the 

mixture to the column and dry the column. 

Pre-elute with three 10-mL portions of 

elution solvent, drying the column between 

elutions. Elute the cartridge with 10 mL each 

of methanol and water, as in section 11.2.3.3. 

6.7.1.2 Concentrate the eluant to per 

section 10.3.3, exchange to isooctane or 

hexane per section 10.3.3, and inject 1.0 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), the recovery of trichlorophenol 

shall be less than 5%, and no peaks 

interfering with the target analytes shall be 

detected. Otherwise the Florisil cartridge is 

not performing properly and the cartridge lot 

shall be rejected. 

6.7.1.3 Florisil cartridge calibration 

solution—2,4,6-Trichlorophenol, 0.1 mg/mL 

in acetone. 

6.7.2 SPE elution solvent—Methylene 

chloride:acetonitrile:hexane (50:3:47). 

6.7.3 Alumina, neutral, Brockman 

Activity I, 80–200 mesh (Fisher Scientific 

certified, or equivalent). Heat in a glass bottle 

for 16 hours at 400 to 450 °C. Seal and cool 

to room temperature. Add 7% (w/w) reagent 

water and mix for 10 to 12 hours. Keep bottle 

tightly sealed. 

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6.7.4 Sulfur removal. 

6.7.4.1 Copper foil or powder—Fisher, 

Alfa Aesar, or equivalent. Cut copper foil into 

approximately 1-cm squares. Copper must be 

activated before it may be used, as described 

below. 

6.7.4.1.1 Place the quantity of copper 

needed for sulfur removal (section 11.5.1.3) 

in a ground-glass-stoppered Erlenmeyer flask 

or bottle. Cover the foil or powder with 

methanol. 

6.7.4.1.2 Add HCl dropwise (0.5–1.0 mL) 

while swirling, until the copper brightens. 

6.7.4.1.3 Pour off the methanol/HCl and 

rinse 3 times with reagent water to remove 

all traces of acid, then 3 times with acetone, 

then 3 times with hexane. 

6.7.4.1.4 For copper foil, cover with 

hexane after the final rinse. Store in a 

stoppered flask under nitrogen until used. 

For the powder, dry on a rotary evaporator. 

Store in a stoppered flask under nitrogen 

until used. Inspect the copper foil or powder 

before each use. It must have a bright, nonoxidized appearance to be effective. Copper 

foil or powder that has oxidized may be 

reactivated using the procedure described 

above. 

6.7.4.2 Tetrabutylammonium sulfite (TBA 

sulfite)—Prepare as described below. 

6.7.4.2.1 Tetrabutylammonium hydrogen 

sulfate, [CH3(CH2)3]4NHSO4.

6.7.4.2.2 Sodium sulfite, Na2SO3.

6.7.4.2.3 Dissolve approximately 3 g 

tetrabutylammonium hydrogen sulfate in 100 

mL of reagent water in an amber bottle with 

fluoropolymer-lined screw cap. Extract with 

three 20-mL portions of hexane and discard 

the hexane extracts. 

6.7.4.2.4 Add 25 g sodium sulfite to 

produce a saturated solution. Store at room 

temperature. Replace after 1 month. 

6.7.5 Sodium chloride—Reagent grade, 

prepare at 5% (w/v) solution in reagent 

water. 

6.8 Stock standard solutions—Stock 

standard solutions may be prepared from 

pure materials, or purchased as certified 

solutions. Traceability must be to the 

National Institute of Standards and 

Technology (NIST) or other national or 

international standard, when available. Stock 

solution concentrations alternative to those 

below may be used. Because of the toxicity 

of some of the compounds, primary dilutions 

should be prepared in a hood, and a NIOSH/ 

MESA approved toxic gas respirator should 

be worn when high concentrations of neat 

materials are handled. The following 

procedure may be used to prepare standards 

from neat materials. 

6.8.1 Accurately weigh about 0.0100 g of 

pure material in a 10-mL volumetric flask. 

Dilute to volume in pesticide quality hexane, 

isooctane, or other suitable solvent. Larger 

volumes may be used at the convenience of 

the laboratory. When compound purity is 

assayed to be 96% or greater, the weight may 

be used without correction to calculate the 

concentration of the stock standard. 

Commercially prepared stock standards may 

be used at any concentration if they are 

certified by the manufacturer or by an 

independent source. 

6.8.1.1 Unless stated otherwise in this 

method, store non-aqueous standards in 

fluoropolymer-lined screw-cap, or heatsealed, glass containers, in the dark at ¥20 

to ¥10 °C. Store aqueous standards; e.g., the 

aqueous LCS (section 8.4), in the dark at 

≤6 °C, but do not freeze. 

6.8.1.2 Standards prepared by the 

laboratory may be stored for up to one year, 

except when comparison with QC check 

standards indicates that a standard has 

degraded or become more concentrated due 

to evaporation, or unless the laboratory has 

data on file to prove stability for a longer 

period. Commercially prepared standards 

may be stored until the expiration date 

provided by the vendor, except when 

comparison with QC check standards 

indicates that a standard has degraded or 

become more concentrated due to 

evaporation, or unless the laboratory has data 

from the vendor on file to prove stability for 

a longer period. 

6.8.2 Calibration solutions—It is 

necessary to prepare calibration solutions for 

the analytes of interest (section 1.4) only 

using an appropriate solvent (isooctane or 

hexane may be used). Whatever solvent is 

used, both the calibration standards and the 

final sample extracts must use the same 

solvent. Other analytes may be included as 

desired. 

6.8.2.1 Prepare calibration standards for 

the single-component analytes of interest and 

surrogates at a minimum of three 

concentration levels (five are suggested) by 

adding appropriate volumes of one or more 

stock standards to volumetric flasks. One of 

the calibration standards should be at a 

concentration at or below the ML specified 

in Table 1, or 2, or as specified by a 

regulatory/control authority or in a permit. 

The ML value may be rounded to a whole 

number that is more convenient for preparing 

the standard, but must not exceed the ML 

value listed in Tables 1 or 2 for those 

analytes which list ML values. Alternatively, 

the laboratory may establish an ML for each 

analyte based on the concentration of the 

lowest calibration standard in a series of 

standards produced by the laboratory or 

obtained from a commercial vendor, again, 

provided that the ML does not exceed the ML 

in Table 1 and 2, and provided that the 

resulting calibration meets the acceptance 

criteria in section 7.5.2 based on the RSD, 

RSE, or R2. 

(a) The other concentrations should 

correspond to the expected range of 

concentrations found in real samples or 

should define the working range of the GC 

system. A minimum of six concentration 

levels is required for a second order, nonlinear (e.g., quadratic; ax2 + bx + c = 0) 

calibration (section 7.5.2 or 7.6.2). 

Calibrations higher than second order are not 

allowed. A separate standard near the MDL 

may be analyzed as a check on sensitivity, 

but should not be included in the linearity 

assessment. The solvent for the standards 

must match the final solvent for the sample 

extracts (e.g., isooctane or hexane). 

Note: The option for non-linear calibration 

may be necessary to address specific 

instrumental techniques. However, it is not 

EPA’s intent to allow non-linear calibration 

to be used to compensate for detector 

saturation or to avoid proper instrument 

maintenance. 

(b) Given the number of analytes included 

in this method, it is highly likely that some 

will coelute on one or both of the GC 

columns used for the analysis. Divide the 

analytes into two or more groups and prepare 

separate calibration standards for each group, 

at multiple concentrations (e.g., a five-point 

calibration will require ten solutions to cover 

two groups of analytes). Table 7 provides 

information on dividing the target analytes 

into separate calibration mixtures that should 

minimize or eliminate co-elutions. This table 

is provided solely as guidance, based on the 

GC columns suggested in this method. If an 

analyte listed in Table 7 is not an analyte of 

interest in a given laboratory setting, then it 

need not be included in a calibration 

mixture. 

Note: Many commercially available 

standards are divided into separate mixtures 

to address this issue. 

(c) If co-elutions occur in analysis of a 

sample, a co-elution on one column is 

acceptable so long as effective separation of 

the co-eluting compounds can be achieved 

on the second column. 

6.8.2.2 Multi-component analytes (e.g., 

PCBs as Aroclors, and Toxaphene). 

6.8.2.2.1 A standard containing a mixture 

of Aroclor 1016 and Aroclor 1260 will 

include many of the peaks represented in the 

other Aroclor mixtures. As a result, a multipoint 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 

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real samples and should bracket the linear 

range of the detector. 

6.8.3 Quality Control (QC) Check Sample 

Concentrate—Prepare one or more mid-level 

standard mixtures (concentrates) in acetone 

(or other water miscible solvent). The 

concentrate is used as the spiking solution 

with which to prepare the Demonstration of 

Capabilities (DOC) samples, the Laboratory 

Control Sample (LCS), and Matrix Spike (MS) 

and Matrix Spike Duplicate (MSD) samples 

described in section 8. If prepared by the 

laboratory (as opposed the purchasing it from 

a commercial supplier), the concentrate must 

be prepared independently from the 

standards used for calibration, but may be 

prepared from the same source as the secondsource standard used for calibration 

verification (section 7.7). Regardless of the 

source, the concentrate must be in a watermiscible solvent, as noted above. The 

concentrate is used to prepare the DOC and 

LCS (sections 8.2.1 and 8.4) and MS/MSD 

samples (section 8.3). Depending on the 

analytes of interest for a given sample (see 

Section 1.4), multiple solutions and multiple 

LCS or MS/MSD samples may be required to 

account for co-eluting analytes. However, a 

co-elution on one column is acceptable so 

long as effective separation of the co-eluting 

compounds can be achieved on the second 

column. In addition, the concentrations of 

the MS/MSD samples should reflect any 

relevant compliance limits for the analytes of 

interest, as described in section 8.3.1. If a 

custom spiking solution is required for a 

specific discharge (section 8.3.1), prepare it 

separately from the DOC and LCS solution. 

Note: Some commercially available 

standards are divided into separate mixtures 

to address the co-elution issue. 

6.8.4 Calibration Verification Standards— 

In order to verify the results of the initial 

calibration standards, prepare one or more 

mid-level standard mixtures in isooctane or 

hexane, using standards obtained from a 

second source (different manufacturer or 

different certified lot from the calibration 

standards). These standards will be analyzed 

to verify the accuracy of the calibration 

(sections 7.7 and 13.6.2). As with the QC 

sample concentrate in section 6.8.3, multiple 

solutions may be required to address coelutions among all of the analytes. 

6.8.5 Internal standard solution—If the 

internal standard calibration technique is to 

be used, prepare pentachloronitrobenzene 

(PCNB) at a concentration of 10 mg/mL in 

ethyl acetate. Alternative and multiple 

internal standards; e.g., tetrachloro-m-xylene, 

4,4′-dibromobiphenyl, and/or 

decachlorobiphenyl may be used provided 

that the laboratory performs all QC tests and 

meets all QC acceptance criteria with the 

alternative or additional internal standard(s) 

as an integral part of this method. 

6.8.6 Surrogate solution—Prepare a 

solution containing one or more surrogates at 

a concentration of 2 mg/mL in acetone. 

Potential surrogates include: dibutyl 

chlorendate (DBC), tetrachloro-m-xylene 

(TCMX), 4,4′-dibromobiphenyl, or 

decachlorobiphenyl. Alternative surrogates 

and concentrations may be used, provided 

the laboratory performs all QC tests and 

meets all QC acceptance criteria with the 

alternative surrogate(s) as an integral part of 

this method. If the internal standard 

calibration technique is used, do not use the 

internal standard as a surrogate. 

6.8.7 DDT and endrin decomposition 

(breakdown) solution—Prepare a solution 

containing endrin at a concentration of 50 

ng/mL and 4,4’-DDT at a concentration of 100 

ng/mL, in isooctane or hexane. A 1-mL 

injection of this standard will contain 50 

picograms (pg) of endrin and 100 pg of DDT. 

The concentration of the solution may be 

adjusted by the laboratory to accommodate 

other injection volumes such that the same 

masses of the two analytes are introduced 

into the instrument. 

7. Calibration 

7.1 Establish gas chromatographic 

operating conditions equivalent to those in 

Section 5.8.1 and Footnote 2 to Table 3. 

Alternative temperature program and flow 

rate conditions may be used. The system may 

be calibrated using the external standard 

technique (section 7.5) or the internal 

standard technique (section 7.6). It is 

necessary to calibrate the system for the 

analytes of interest (section 1.4) only. 

7.2 Separately inject the mid-level 

calibration standard for each calibration 

mixture. Store the retention time on each GC 

column. 

7.3 Injection of calibration solutions— 

Inject a constant volume in the range of 0.5 

to 2.0 mL of each calibration solution into the 

GC column/detector pairs. An alternative 

volume (see Section 12.3) may be used 

provided all requirements in this method are 

met. Beginning with the lowest level mixture 

and proceeding to the highest level mixture 

may limit the risk of carryover from one 

standard to the next, but other sequences 

may be used. An instrument blank should be 

analyzed after the highest standard to 

demonstrate that there is no carry-over 

within the system for this calibration range. 

7.4 For each analyte, compute, record, 

and store, as a function of the concentration 

injected, the retention time and peak area on 

each column/detector system. If multicomponent 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, As, vs. concentration Cs. If used, 

the regression must be weighted inversely 

proportional to concentration. The coefficient 

of determination (R2) of the weighted 

regression must be greater than 0.920. 

Alternatively, the relative standard error 

(Reference 10) may be used as an acceptance 

criterion. As with the RSD, the RSE must be 

less than 20%. If an RSE less than 20% 

cannot be achieved for a quadratic regression, 

system performance is unacceptable and the 

system must be adjusted and re-calibrated. 

Note: Regression calculations are not 

included in this method because the 

calculations are cumbersome and because 

many GC/ECD data systems allow selection 

of weighted regression for calibration and 

calculation of analyte concentrations. 

7.6 Internal standard calibration. 

7.6.1 From the calibration data (Section 

7.4), calculate the response factor (RF) for 

each analyte at each concentration according 

to the following equation: 

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 nonlinear (e.g., quadratic) regression. If used, the 

regression must be weighted inversely 

proportional to concentration, and the 

coefficient of determination of the weighted 

regression must be greater than 0.920. 

Alternatively, the relative standard error 

(Reference 10) may be used as an acceptance 

criterion. As with the RSD, the RSE must be 

less than 15%. If an RSE less than 15% 

cannot be achieved for a quadratic regression, 

system performance is unacceptable and the 

system must be adjusted and re-calibrated. 

7.7 The working calibration curve, CF, or 

RF must be verified immediately after 

calibration and at the beginning and end of 

each 24-hour shift by the analysis of a midlevel calibration standard. The calibration 

verification standard(s) must be obtained 

from a second manufacturer or a 

manufacturer’s batch prepared 


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independently from the batch used for 

calibration (Section 6.8.4). Requirements for 

calibration verification are given in Section 

13.6 and Table 4. Alternatively, calibration 

verification may be performed after a set 

number of injections (e.g., every 20 

injections), to include injection of extracts of 

field samples, QC samples, instrument 

blanks, etc. (i.e., it is based on the number 

of injections performed, not sample extracts). 

The time for the injections may not exceed 

24 hours. 

Note: The 24-hour shift begins after 

analysis of the combined QC standard 

(calibration verification) and ends 24 hours 

later. The ending calibration verification 

standard is run immediately after the last 

sample run during the 24-hour shift, so the 

beginning and ending calibration 

verifications are outside of the 24-hour shift. 

If calibration verification is based on the 

number of injections instead of time, then the 

ending verification standard for one group of 

injections may be used as the beginning 

verification for the next group of injections. 

7.8 Florisil® 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 must repeat 

demonstration of capability (DOC) at least 

annually. 

8.1.2 In recognition of advances that are 

occurring in analytical technology, and to 

overcome matrix interferences, the laboratory 

is permitted certain options (section 1.8 and 

40 CFR 136.6(b) [Reference 12]) to improve 

separations or lower the costs of 

measurements. These options may include 

alternative extraction (e.g., other solid-phase 

extraction materials and formats), 

concentration, and cleanup procedures, and 

changes in GC columns (Reference 12). 

Alternative determinative techniques, such 

as the substitution of spectroscopic or 

immunoassay techniques, and changes that 

degrade method performance, are not 

allowed. If an analytical technique other than 

the techniques specified in this method is 

used, that technique must have a specificity 

equal to or greater than the specificity of the 

techniques in this method for the analytes of 

interest. The laboratory is also encouraged to 

participate in performance evaluation studies 

(see section 8.8). 

8.1.2.1 Each time a modification listed 

above is made to this method, the laboratory 

is required to repeat the procedure in section 

8.2. If the detection limit of the method will 

be affected by the change, the laboratory is 

required to demonstrate that the MDLs (40 

CFR part 136, appendix B) are lower than 

one-third the regulatory compliance limit or 

as low as the MDLs in this method, 

whichever are greater. If calibration will be 

affected by the change, the instrument must 

be recalibrated per section 7. Once the 

modification is demonstrated to produce 

results equivalent or superior to results 

produced by this method as written, that 

modification may be used routinely 

thereafter, so long as the other requirements 

in this method are met (e.g., matrix spike/

matrix spike duplicate recovery and relative 

percent difference). 

8.1.2.1.1 If an allowed method 

modification, is to be applied to a specific 

discharge, the laboratory must prepare and 

analyze matrix spike/matrix spike duplicate 

(MS/MSD) samples (section 8.3) and LCS 

samples (section 8.4). The laboratory must 

include surrogates (Section 8.7) in each of the 

samples. The MS/MSD and LCS samples 

must be fortified with the analytes of interest 

(section 1.4). If the modification is for 

nationwide use, MS/MSD samples must be 

prepared from a minimum of nine different 

discharges (See section 8.1.2.1.2), and all QC 

acceptance criteria in this method must be 

met. This evaluation only needs to be 

performed once other than for the routine QC 

required by this method (for example it could 

be performed by the vendor of an alternative 

material) but any laboratory using that 

specific material must have the results of the 

study available. This includes a full data 

package with the raw data that will allow an 

independent reviewer to verify each 

determination and calculation performed by 

the laboratory (see section 8.1.2.2.5, items 

(a)–(q)). 

8.1.2.1.2 Sample matrices on which MS/ 

MSD tests must be performed for nationwide 

use of an allowed modification: 

(a) Effluent from a publicly owned 

treatment works (POTW). 

(b) ASTM D5905 Standard Specification 

for Substitute Wastewater. 

(c) Sewage sludge, if sewage sludge will be 

in the permit. 

(d) ASTM D1141 Standard Specification 

for Substitute Ocean Water, if ocean water 

will be in the permit. 

(e) Untreated and treated wastewaters up to 

a total of nine matrix types (see https://

www.epa.gov/eg/industrial-effluentguidelines for a list of industrial categories 

with existing effluent guidelines). 

(i) At least one of the above wastewater 

matrix types must have at least one of the 

following characteristics: 

(A) Total suspended solids greater than 40 

mg/L. 

(B) Total dissolved solids greater than 100 

mg/L. 

(C) Oil and grease greater than 20 mg/L. 

(D) NaCl greater than 120 mg/L. 

(E) CaCO3 greater than 140 mg/L. 

(ii) The interim acceptance criteria for MS, 

MSD recoveries that do not have recovery 

limits in Table 4 or developed in section 

8.3.3, and for surrogates that do not have 

recovery limits developed in section 8.6, 

must be no wider than 60–140%, and the 

relative percent difference (RPD) of the 

concentrations in the MS and MSD that do 

not have RPD limits in Table 4 or developed 

in section 8.3.3, must be less than 30%. 

Alternatively, the laboratory may use the 

laboratory’s in-house limits if they are 

tighter. 

(f) A proficiency testing (PT) sample from 

a recognized provider, in addition to tests of 

the nine matrices (section 8.1.2.1.1). 

8.1.2.2 The laboratory must maintain 

records of modifications made to this 

method. These records include the following, 

at a minimum: 

8.1.2.2.1 The names, titles, and business 

street addresses, telephone numbers, and 

email addresses, of the analyst(s) that 

performed the analyses and modification, 

and of the quality control officer that 

witnessed and will verify the analyses and 

modifications. 

8.1.2.2.2 A list of analytes, by name and 

CAS Registry number. 

8.1.2.2.3 A narrative stating reason(s) for 

the modifications. 

8.1.2.2.4 Results from all quality control 

(QC) tests comparing the modified method to 

this method, including: 

(a) Calibration (section 7). 

(b) Calibration verification (section 13.6). 

(c) Initial demonstration of capability 

(section 8.2). 

(d) Analysis of blanks (section 8.5). 

(e) Matrix spike/matrix spike duplicate 

analysis (section 8.3). 

(f) Laboratory control sample analysis 

(section 8.4). 

8.1.2.2.5 Data that will allow an 

independent reviewer to validate each 

determination by tracing the instrument 

output (peak height, area, or other signal) to 

the final result. These data are to include: 

(a) Sample numbers and other identifiers. 

(b) Extraction dates. 

(c) Analysis dates and times. 

(d) Analysis sequence/run chronology. 

(e) Sample weight or volume (section 10). 

(f) Extract volume prior to each cleanup 

step (sections 10 and 11). 

(g) Extract volume after each cleanup step 

(section 11). 

(h) Final extract volume prior to injection 

(sections 10 and 12). 

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(i) Injection volume (sections 12.3 and 

13.2). 

(j) Sample or extract dilution (section 15.4). 

(k) Instrument and operating conditions. 

(l) Column (dimensions, material, etc.). 

(m) Operating conditions (temperatures, 

flow rates, etc.). 

(n) Detector (type, operating conditions, 

etc.). 

(o) Chromatograms and other recordings of 

raw data. 

(p) Quantitation reports, data system 

outputs, and other data to link the raw data 

to the results reported. 

(q) A written Standard Operating 

Procedure (SOP). 

8.1.2.2.6 Each individual laboratory 

wishing to use a given modification must 

perform the start-up tests in section 8.1.2 

(e.g., DOC, MDL), with the modification as an 

integral part of this method prior to applying 

the modification to specific discharges. 

Results of the DOC must meet the QC 

acceptance criteria in Table 5 for the analytes 

of interest (section 1.4), and the MDLs must 

be equal to or lower than the MDLs in Tables 

1 and 2 for the analytes of interest. 

8.1.3 Before analyzing samples, the 

laboratory must analyze a blank to 

demonstrate that interferences from the 

analytical system, lab ware, and reagents, are 

under control. Each time a batch of samples 

is extracted or reagents are changed, a blank 

must be extracted and analyzed as a 

safeguard against laboratory contamination. 

Requirements for the blank are given in 

section 8.5. 

8.1.4 The laboratory must, on an ongoing 

basis, spike and analyze samples to monitor 

and evaluate method and laboratory 

performance on the sample matrix. The 

procedure for spiking and analysis is given 

in section 8.3. 

8.1.5 The laboratory must, on an ongoing 

basis, demonstrate through analysis of a 

quality control check sample (laboratory 

control sample, LCS; on-going precision and 

recovery sample, OPR) that the measurement 

system is in control. This procedure is 

described in Section 8.4. 

8.1.6 The laboratory should maintain 

performance records to document the quality 

of data that is generated. This procedure is 

given in section 8.7. 

8.1.7 The large number of analytes tested 

in performance tests in this method present 

a substantial probability that one or more 

will fail acceptance criteria when all analytes 

are tested simultaneously, and a re-test 

(reanalysis) is allowed if this situation should 

occur. If, however, continued re-testing 

results in further repeated failures, the 

laboratory should document the failures and 

either avoid reporting results for the analytes 

that failed or report the problem and failures 

with the data. A QC failure does not relieve 

a discharger or permittee of reporting timely 

results. 

8.2 Demonstration of capability (DOC)— 

To establish the ability to generate acceptable 

recovery and precision, the laboratory must 

perform the DOC in sections 8.2.1 through 

8.2.6 for the analytes of interest initially and 

in an on-going manner at least annually. The 

laboratory must also establish MDLs for the 

analytes of interest using the MDL procedure 

at 40 CFR part 136, appendix B. The 

laboratory’s MDLs must be equal to or lower 

than those listed in Tables 1 or 2, or lower 

than one-third the regulatory compliance 

limit, whichever is greater. For MDLs not 

listed in Tables 1 or 2, the laboratory must 

determine the MDLs using the MDL 

procedure at 40 CFR part 136, appendix B 

under the same conditions used to determine 

the MDLs for the analytes listed in Tables 1 

and 2. When analyzing the PCBs as Aroclors, 

it is only necessary to establish an MDL for 

one of the multi-component analytes (e.g., 

PCB 1254), or the mixture of Aroclors 1016 

and 1260 may be used to establish MDLs for 

all of the Aroclors. Similarly, MDLs for other 

multi-component analytes (e.g., Chlordanes) 

may be determined using only one of the 

major components. All procedures used in 

the analysis, including cleanup procedures, 

must be included in the DOC. 

8.2.1 For the DOC, a QC check sample 

concentrate containing each analyte of 

interest (section 1.4) is prepared in a watermiscible solvent using the solution in section 

6.8.3. 

Note: QC check sample concentrates are no 

longer available from EPA. 

8.2.2 Using a pipet or syringe, prepare 

four QC check samples by adding an 

appropriate volume of the concentrate and of 

the surrogate(s) to each of four 1–L aliquots 

of reagent water. Swirl or stir to mix. 

8.2.3 Extract and analyze the well-mixed 

QC check samples according to the method 

beginning in section 10. 

8.2.4 Calculate the average percent 

recovery (X) and the standard deviation (s) of 

the percent recovery for each analyte using 

the four results. 

8.2.5 For each analyte, compare s and X 

with the corresponding acceptance criteria 

for precision and recovery in Table 4. For 

analytes in Table 2 that are not listed in 

Table 4, QC acceptance criteria must be 

developed by the laboratory. EPA has 

provided guidance for development of QC 

acceptance criteria (References 12 and 13). If 

s and X for all analytes of interest meet the 

acceptance criteria, system performance is 

acceptable and analysis of blanks and 

samples can begin. If any individual s 

exceeds the precision limit or any individual 

X falls outside the range for recovery, system 

performance is unacceptable for that analyte. 

Note: The large number of analytes in 

Tables 1 and 2 present a substantial 

probability that one or more will fail at least 

one of the acceptance criteria when many or 

all analytes are determined simultaneously. 

8.2.6 When one or more of the analytes 

tested fail at least one of the acceptance 

criteria, repeat the test for only the analytes 

that failed. If results for these analytes pass, 

system performance is acceptable and 

analysis of samples and blanks may proceed. 

If one or more of the analytes again fail, 

system performance is unacceptable for the 

analytes that failed the acceptance criteria. 

Correct the problem and repeat the test 

(section 8.2). See section 8.1.7 for disposition 

of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between this pair 

of tests. 

8.3 Matrix spike and matrix spike 

duplicate (MS/MSD)—The purpose of the 

MS/MSD requirement is to provide data that 

demonstrate the effectiveness of the method 

as applied to the samples in question by a 

given laboratory, and both the data user 

(discharger, permittee, regulated entity, 

regulatory/control authority, customer, other) 

and the laboratory share responsibility for 

provision of such data. The data user should 

identify the sample and the analytes of 

interest (section 1.4) to be spiked and provide 

sufficient sample volume to perform MS/

MSD analyses. The laboratory must, on an 

ongoing basis, spike at least 5% of the 

samples in duplicate from each discharge 

being monitored to assess accuracy (recovery 

and precision). If direction cannot be 

obtained from the data user, the laboratory 

must spike at least one sample in duplicate 

per extraction batch of up to 20 samples with 

the analytes in Table 1. Spiked sample 

results should be reported only to the data 

user whose sample was spiked, or as 

requested or required by a regulatory/control 

authority, or in a permit. 

8.3.1. If, as in compliance monitoring, the 

concentration of a specific analyte will be 

checked against a regulatory concentration 

limit, the concentration of the spike should 

be at that limit; otherwise, the concentration 

of the spike should be one to five times 

higher than the background concentration 

determined in section 8.3.2, at or near the 

midpoint of the calibration range, or at the 

concentration in the LCS (section 8.4) 

whichever concentration would be larger. 

When no information is available, the midpoint of the calibration may be used. 

8.3.2 Analyze one sample aliquot to 

determine the background concentration (B) 

of the each analyte of interest. If necessary to 

meet the requirement in section 8.3.1, 

prepare a new check sample concentrate 

(section 8.2.1) appropriate for the background 

concentration. Spike and analyze two 

additional sample aliquots of the same 

volume as the original sample, and determine 

the concentrations after spiking (A1 and A2) 

of each analyte. Calculate the percent 

recoveries (P1 and P2) as: 

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. 

(a) If any individual P falls outside the 

designated range for recovery in either 

aliquot, or the RPD limit is exceeded, the 

result for the analyte in the unspiked sample 

is suspect and may not be reported or used 


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for permitting or regulatory compliance. See 

section 8.1.7 for disposition of failures. 

(b) For analytes in Table 2 not listed in 

Table 4, QC acceptance criteria must be 

developed by the laboratory. EPA has 

provided guidance for development of QC 

acceptance criteria (References 12 and 13). 

8.3.4 After analysis of a minimum of 20 

MS/MSD samples for each target analyte and 

surrogate, and if the laboratory chooses to 

develop and apply optional in-house QC 

limits, the laboratory should calculate and 

apply the optional in-house QC limits for 

recovery and RPD of future MS/MSD samples 

(Section 8.3). The optional in-house QC 

limits for recovery are calculated as the mean 

observed recovery ±3 standard deviations, 

and the upper QC limit for RPD is calculated 

as the mean RPD plus 3 standard deviations 

of the RPDs. The in-house QC limits must be 

updated at least every two years and reestablished after any major change in the 

analytical instrumentation or process. At 

least 80% of the analytes tested in the MS/ 

MSD must have in-house QC acceptance 

criteria that are tighter than those in Table 4 

and the remaining analytes (those not 

included in the 80%) must meet the 

acceptance criteria in Table 4. If an in-house 

QC limit for the RPD is greater than the limit 

in Table 4, then the limit in Table 4 must be 

used. Similarly, if an in-house lower limit for 

recovery is below the lower limit in Table 4, 

then the lower limit in Table 4 must be used, 

and if an in-house upper limit for recovery 

is above the upper limit in Table 4, then the 

upper limit in Table 4 must be used. The 

laboratory must evaluate surrogate recovery 

data in each sample against its in-house 

surrogate recovery limits. The laboratory may 

use 60 -140% as interim acceptance criteria 

for surrogate recoveries until in-house limits 

are developed. Alternatively, surrogate 

recovery limits may be developed from 

laboratory control charts. In-house QC 

acceptance criteria must be updated at least 

every two years. 

8.4 Laboratory control sample (LCS)—A 

QC check sample (laboratory control sample, 

LCS; on-going precision and recovery 

sample, OPR) containing each singlecomponent analyte of interest (section 1.4) 

must be extracted, concentrated, and 

analyzed with each extraction batch of up to 

20 samples (section 3.1) to demonstrate 

acceptable recovery of the analytes of interest 

from a clean sample matrix. If multi-peak 

analytes are required, extract and prepare at 

least one as an LCS for each batch. 

Alternatively, the laboratory may set up a 

program where multi-peak LCS is rotated 

with a single-peak LCS. 

8.4.1 Prepare the LCS by adding QC 

check sample concentrate (sections 6.8.3 and 

8.2.1) to reagent water. Include all analytes 

of interest (section 1.4) in the LCS. The 

volume of reagent water must be the same as 

the nominal volume used for the sample, the 

DOC (Section 8.2), the blank (section 8.5), 

and the MS/MSD (section 8.3). Also add a 

volume of the surrogate solution (section 

6.8.6). 

8.4.2 Analyze the LCS prior to analysis of 

samples in the extraction batch (Section 3.1). 

Determine the concentration (A) of each 

analyte. Calculate the percent recovery as: 

where T is the true value of the concentration 

in the LCS. 

8.4.3 For each analyte, compare the 

percent recovery (P) with its corresponding 

QC acceptance criterion in Table 4. For 

analytes of interest in Table 2 not listed in 

Table 4, use the QC acceptance criteria 

developed for the MS/MSD (section 8.3.3.2), 

or limits based on laboratory control charts. 

If the recoveries for all analytes of interest 

fall within the designated ranges, analysis of 

blanks and field samples may proceed. If any 

individual recovery falls outside the range, 

proceed according to section 8.4.4. 

Note: The large number of analytes in 

Tables 1 and 2 present a substantial 

probability that one or more will fail the 

acceptance criteria when all analytes are 

tested simultaneously. Because a re-test is 

allowed in event of failure (sections 8.1.7 and 

8.4.4), it may be prudent to extract and 

analyze two LCSs together and evaluate 

results of the second analysis against the QC 

acceptance criteria only if an analyte fails the 

first test. 

8.4.4 Repeat the test only for those 

analytes that failed to meet the acceptance 

criteria (P). If these analytes now pass, 

system performance is acceptable and 

analysis of blanks and samples may proceed. 

Repeated failure, however, will confirm a 

general problem with the measurement 

system. If this occurs, repeat the test using a 

fresh LCS (section 8.2.1) or an LCS prepared 

with a fresh QC check sample concentrate 

(section 8.2.1), or perform and document 

system repair. Subsequent to analysis of the 

LCS prepared with a fresh sample 

concentrate, or to system repair, repeat the 

LCS test (Section 8.4). If failure of the LCS 

indicates a systemic problem with samples in 

the batch, re-extract and re-analyze the 

samples in the batch. See Section 8.1.7 for 

disposition of repeated failures. 

8.4.5 After analysis of 20 LCS samples, 

and if the laboratory chooses to develop and 

apply optional in-house QC limits, the 

laboratory should calculate and apply the 

optional in-house QC limits for recovery of 

future LCS samples (section 8.4). Limits for 

recovery in the LCS should be calculated as 

the mean recovery ±3 standard deviations. A 

minimum of 80% of the analytes tested for 

in the LCS must have QC acceptance criteria 

tighter than those in Table 4, and the 

remaining analytes (those not included in the 

80%) must meet the acceptance criteria in 

Table 4. If an in-house lower limit for 

recovery is lower than the lower limit in 

Table 4, the lower limit in Table 4 must be 

used, and if an in-house upper limit for 

recovery is higher than the upper limit in 

Table 4, the upper limit in Table 4 must be 

used. Many of the analytes and surrogates do 

not contain acceptance criteria. The 

laboratory should use 60–140% as interim 

acceptance criteria for recoveries of spiked 

analytes and surrogates that do not have 

recovery limits specified in Table 4, and at 

least 80% of the surrogates must meet the 

60–140% interim criteria until in-house LCS 

and surrogate limits are developed. 

Alternatively, acceptance criteria for analytes 

that do not have recovery limits in Table 4 

may be based on laboratory control charts. Inhouse QC acceptance criteria must be 

updated at least every two years. 

8.5 Blank—Extract and analyze a blank 

with each extraction batch (section 3.1) to 

demonstrate that the reagents and equipment 

used for preparation and analysis are free 

from contamination. 

8.5.1 Prepare the blank from reagent 

water and spike it with the surrogates. The 

volume of reagent water must be the same as 

the volume used for samples, the DOC 

(section 8.2), the LCS (section 8.4), and the 

MS/MSD (section 8.3). Extract, concentrate, 

and analyze the blank using the same 

procedures and reagents used for the 

samples, LCS, and MS/MSD in the batch. 

Analyze the blank immediately after analysis 

of the LCS (section 8.4) and prior to analysis 

of the MS/MSD and samples to demonstrate 

freedom from contamination. 

8.5.2 If any analyte of interest is found in 

the blank at a concentration greater than the 

MDL for the analyte, at a concentration 

greater than one-third the regulatory 

compliance limit, or at a concentration 

greater than one-tenth the concentration in a 

sample in the batch (section 3.1), whichever 

is greatest, analysis of samples must be 

halted and samples in the batch must be 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 re-testing of blanks results in 

repeated failures, the laboratory should 

document the failures and report the problem 

and failures with the data. 

8.6 Surrogate recovery—The laboratory 

must spike all samples with the surrogate 

standard spiking solution (section 6.8.6) per 

section 10.2.2 or 10.4.2, analyze the samples, 

and calculate the percent recovery of each 

surrogate. QC acceptance criteria for 

surrogates must be developed by the 

laboratory (section 8.4). If any recovery fails 

its criterion, attempt to find and correct the 

cause of the failure, and if sufficient volume 

is available, re-extract another aliquot of the 

affected sample; otherwise, see section 8.1.7 

for disposition of repeated failures. 

8.7 As part of the QC program for the 

laboratory, it is suggested but not required 

that method accuracy for wastewater samples 

be assessed and records maintained. After 

analysis of five or more spiked wastewater 

samples as in Section 8.3, calculate the 

average percent recovery (X) and the 

standard deviation of the percent recovery 

(sp). Express the accuracy assessment as a 

percent interval from X¥2sp to X+2sp. For 

example, if X = 90% and sp = 10%, the 

accuracy interval is expressed as 70–110%. 

Update the accuracy assessment for each 

analyte on a regular basis to ensure process 

control (e.g., after each 5–10 new accuracy 

measurements). If desired, statements of 

accuracy for laboratory performance, 

independent of performance on samples, may 

be developed using LCSs. 

8.8 It is recommended that the laboratory 

adopt additional quality assurance practices 

for use with this method. The specific 

practices that are most productive depend 


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upon the needs of the laboratory and the 

nature of the samples. Field duplicates may 

be analyzed to assess the precision of 

environmental measurements. When doubt 

exists over the identification of a peak on the 

chromatogram, confirmatory techniques such 

as gas chromatography with another 

dissimilar column, specific element detector, 

or mass spectrometer must be used. 

Whenever possible, the laboratory should 

analyze standard reference materials and 

participate in relevant performance 

evaluation studies. 

9. Sample Collection, Preservation, and 

Handling 

9.1 Collect samples as grab samples in 

glass bottles, or in refrigerated bottles using 

automatic sampling equipment. Collect 1-L of 

ambient waters, effluents, and other aqueous 

samples. If high concentrations of the 

analytes of interest are expected (e.g., for 

untreated effluents or in-process waters), 

collect a smaller volume (e.g., 250 mL), but 

not less than 100 mL, in addition to the 1- 

L sample. Follow conventional sampling 

practices, except do not pre-rinse the bottle 

with sample before collection. Automatic 

sampling equipment must be as free as 

possible of polyvinyl chloride or other tubing 

or other potential sources of contamination. 

If needed, collect additional sample(s) for the 

MS/MSD (section 8.3). 

9.2 Ice or refrigerate the sample at ≤6 °C 

from the time of collection until extraction, 

but do not freeze. If aldrin is to be 

determined and residual chlorine is present, 

add 80 mg/L of sodium thiosulfate but do not 

add excess. Any method suitable for field use 

may be employed to test for residual chlorine 

(Reference 14). If sodium thiosulfate 

interferes in the determination of the 

analytes, an alternative preservative (e.g., 

ascorbic acid or sodium sulfite) may be used. 

9.3 Extract all samples within seven days 

of collection and completely analyze within 

40 days of extraction (Reference 1). If the 

sample will not be extracted within 72 hours 

of collection, adjust the sample pH to a range 

of 5.0–9.0 with sodium hydroxide solution or 

sulfuric acid. Record the volume of acid or 

base used. 

10. Sample Extraction 

10.1 This section contains procedures for 

separatory funnel liquid-liquid extraction 

(SFLLE, section 10.2), continuous liquidliquid extraction (CLLE, section 10.4), and 

disk-based solid-phase extraction (SPE, 

section 10.5). SFLLE is faster, but may not be 

as effective as CLLE for extracting polar 

analytes. SFLLE is labor intensive and may 

result in formation of emulsions that are 

difficult to break. CLLE is less labor 

intensive, avoids emulsion formation, but 

requires more time (18–24 hours), more hood 

space, and may require more solvent. SPE 

can be faster, unless the particulate load in 

an aqueous sample is so high that it slows 

the filtration process. If an alternative 

extraction scheme to those detailed in this 

method is used, all QC tests must be 

performed and all QC acceptance criteria 

must be met with that extraction scheme as 

an integral part of this method. 

10.2 Separatory funnel liquid-liquid 

extraction (SFLLE). 

10.2.1 The SFLLE procedure below 

assumes a sample volume of 1 L. When a 

different sample volume is extracted, adjust 

the volume of methylene chloride 

accordingly. 

10.2.2 Mark the water meniscus on the 

side of the sample bottle for later 

determination of sample volume. Pour the 

entire sample into the separatory funnel. 

Pipet the surrogate standard spiking solution 

(section 6.8.6) into the separatory funnel. If 

the sample will be used for the LCS or MS 

or MSD, pipet the appropriate QC check 

sample concentrate (section 8.3 or 8.4) into 

the separatory funnel. Mix well. If the sample 

arrives in a larger sample bottle, 1 L may be 

measured in a graduated cylinder, then 

added to the separatory funnel. 

Note: Instances in which the sample is 

collected in an oversized bottle should be 

reported by the laboratory to the data user. 

Of particular concern is that fact that this 

practice precludes rinsing the empty bottle 

with solvent as described below, which 

could leave hydrophobic pesticides on the 

wall of the bottle, and underestimate the 

actual sample concentrations. 

10.2.3 Add 60 mL of methylene chloride 

to the sample bottle, seal, and shake for 30 

seconds to rinse the inner surface. Transfer 

the solvent to the separatory funnel and 

extract the sample by shaking the funnel for 

two minutes with periodic venting to release 

excess pressure. Allow the organic layer to 

separate from the water phase for a minimum 

of 10 minutes. If an emulsion forms and the 

emulsion interface between the layers is 

more than one-third the volume of the 

solvent layer, employ mechanical techniques 

to complete the phase separation. The 

optimum technique depends upon the 

sample, but may include stirring, filtration of 

the emulsion through glass wool, use of 

phase-separation paper, centrifugation, 

salting, freezing, or other physical methods. 

Collect the methylene chloride extract in a 

flask. If the emulsion cannot be broken 

(recovery of less than 80% of the methylene 

chloride, corrected for the water solubility of 

methylene chloride), transfer the sample, 

solvent, and emulsion into the extraction 

chamber of a continuous extractor and 

proceed as described in section 10.4. 

10.2.4 Add a second 60-mL volume of 

methylene chloride to the sample bottle and 

repeat the extraction procedure a second 

time, combining the extracts in the flask. 

Perform a third extraction in the same 

manner. Proceed to macro-concentration 

(section 10.3.1). 

10.2.5 Determine the original sample 

volume by refilling the sample bottle to the 

mark and transferring the liquid to an 

appropriately sized graduated cylinder. 

Record the sample volume to the nearest 5 

mL. Sample volumes may also be determined 

by weighing the container before and after 

extraction or filling to the mark with water. 

10.3 Concentration. 

10.3.1 Macro concentration. 

10.3.1.1 Assemble a Kuderna-Danish (K– 

D) concentrator by attaching a 10-mL 

concentrator tube to a 500-mL evaporative 

flask. Other concentration devices or 

techniques may be used in place of the K– 

D concentrator so long as the requirements of 

section 8.2 are met. 

10.3.1.2 Pour the extract through a 

solvent-rinsed drying column containing 

about 10 cm of anhydrous sodium sulfate, 

and collect the extract in the K–D 

concentrator. Rinse the flask and column 

with 20–30 mL of methylene chloride to 

complete the quantitative transfer. 

10.3.1.3 If no cleanup is to be performed 

on the sample, add 500 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 sulfur removal or acid back extraction, 

remove the Snyder column and rinse the 

flask and its lower joint into the concentrator 

tube with 1 to 2 mL of methylene chloride. 

A 5-mL syringe is recommended for this 

operation. Adjust the final volume to 10 mL 

in methylene chloride and proceed to sulfur 

removal (section 11.5) or acid back extraction 

(section 11.6). If the extract is to cleaned up 

using one of the other cleanup procedures or 

is to be injected into the GC, proceed to 

Kuderna-Danish micro-concentration (section 

10.3.2) or nitrogen evaporation and solvent 

exchange (section 10.3.3). 

10.3.2 Kuderna-Danish micro 

concentration—Add another one or two clean 

boiling chips to the concentrator tube and 

attach a two-ball micro-Snyder column. Prewet 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 solidphase cleanup (SPE) are exchanged into 1.0 

mL of the SPE elution solvent (section 

6.7.2.2). Extracts to be subjected to Florisil®

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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 fluoropolymer-lined cap. Seal 

the vial and label with the sample number. 

Store in the dark at room temperature until 

ready for GC analysis. If GC analysis will not 

be performed on the same day, store the vial 

in the dark at ≤6 °C. Analyze the extract by 

GC per the procedure in section 12. 

10.4 Continuous liquid/liquid extraction 

(CLLE). 

10.4.1 Use CLLE when experience with a 

sample from a given source indicates an 

emulsion problem, or when an emulsion is 

encountered using SFLLE. CLLE may be used 

for all samples, if desired. 

10.4.2 Mark the water meniscus on the 

side of the sample bottle for later 

determination of sample volume. Transfer 

the sample to the continuous extractor and, 

using a pipet, add surrogate standard spiking 

solution. If the sample will be used for the 

LCS, MS, or MSD, pipet the appropriate 

check sample concentrate (section 8.2.1 or 

8.3.2) into the separatory funnel. Mix well. 

Add 60 mL of methylene chloride to the 

sample bottle, seal, and shake for 30 seconds 

to rinse the inner surface. Transfer the 

solvent to the extractor. 

10.4.3 Repeat the sample bottle rinse with 

two additional 50–100 mL portions of 

methylene chloride and add the rinses to the 

extractor. 

10.4.4 Add a suitable volume of 

methylene chloride to the distilling flask 

(generally 200–500 mL) and sufficient 

reagent water to ensure proper operation of 

the extractor, and extract the sample for 18– 

24 hours. A shorter or longer extraction time 

may be used if all QC acceptance criteria are 

met. Test and, if necessary, adjust the pH of 

the water to a range of 5.0–9.0 during the 

second or third hour of the extraction. After 

extraction, allow the apparatus to cool, then 

detach the distilling flask. Dry, concentrate, 

solvent exchange, and transfer the extract to 

a vial with fluoropolymer-lined cap, per 

Section 10.3. 

10.4.5 Determine the original sample 

volume by refilling the sample bottle to the 

mark and transferring the liquid to an 

appropriately sized graduated cylinder. 

Record the sample volume to the nearest 5 

mL. Sample volumes may also be determined 

by weighing the container before and after 

extraction or filling to the mark with water. 

10.5 Solid-phase extraction of aqueous 

samples. The steps in this section address the 

extraction of aqueous field samples using 

disk-based solid-phase extraction (SPE) 

media, based on an ATP approved by EPA in 

1995 (Reference 20). This application of SPE 

is distinct from that used in this method for 

the cleanup of sample extracts in section 

11.2. Analysts must be careful not to confuse 

the equipment, supplies, or the procedural 

steps from these two different uses of SPE. 

Note: Changes to the extraction conditions 

described below may be made by the 

laboratory under the allowance for method 

flexibility described in section 8.1, provided 

that the performance requirements in section 

8.2 are met. However, changes in SPE 

materials, formats, and solvents must meet 

the requirements in section 8.1.2 and its 

subsections. 

10.5.1 Mark the water meniscus on the 

side of the sample bottle for later 

determination of sample volume. If the 

sample contains particulates, let stand to 

settle out the particulates before extraction. 

10.5.2 Extract the sample as follows: 

10.5.2.1 Place a 90-mm standard filter 

apparatus on a vacuum filtration flask or 

manifold and attach to a vacuum source. The 

vacuum gauge must read at least 25 in. of 

mercury when all valves are closed. Position 

a 90-mm C18 extraction disk onto the filter 

screen. Wet the entire disk with methanol. To 

aid in filtering samples with particulates, a 

1-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 

relatively clean samples (e.g., treated 

effluents, groundwater, drinking water). If 

particular circumstances require the use of a 

cleanup procedure, the laboratory may use 

any or all of the procedures below or any 

other appropriate procedure (e.g., gel 

permeation chromatography). However, the 

laboratory must first repeat the tests in 

sections 8.2, 8.3, and 8.4 to demonstrate that 

the requirements of those sections can be met 

using the cleanup procedure(s) as an integral 

part of this method. This is particularly 

important when the target analytes for the 

analysis include any of the single component 

pesticides in Table 2, because some cleanups 

have not been optimized for all of those 

analytes. 

11.1.1 The solid-phase cartridge (section 

11.2) removes polar organic compounds such 

as phenols. 

11.1.2 The Florisil® 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, 

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may be removed using activated copper, or 

TBA sulfite. Sulfur removal (section 11.5) is 

required when sulfur is known or suspected 

to be present. Some chlorinated pesticides 

which also contain sulfur may be removed by 

this cleanup. 

11.1.5 Acid back extraction (section 11.6) 

may be useful for cleanup of PCBs and other 

compounds not adversely affected by sulfuric 

acid. 

11.2 Solid-phase extraction (SPE) as a 

cleanup. In order to use the C18 SPE 

cartridge in section 5.5.3.5 as a cleanup 

procedure, the sample extract must be 

exchanged from methylene chloride to 

methylene chloride:acetonitrile:hexane 

(50:3:47). Follow the solvent exchange steps 

in section 10.3.3.2 prior to attempting solidphase cleanup. 

Note: This application of SPE is distinct 

from that used in this method for the 

extraction of aqueous samples in section 

10.5. Analysts must be careful not to confuse 

the equipment, supplies, or procedural steps 

from these two different uses of SPE. 

11.2.1 Setup. 

11.2.1.1 Attach the VacElute Manifold 

(section 5.5.3.2) to a water aspirator or 

vacuum pump with the trap and gauge 

installed between the manifold and vacuum 

source. 

11.2.1.2 Place the SPE cartridges in the 

manifold, turn on the vacuum source, and 

adjust the vacuum to 5 to 10 psi. 

11.2.2 Cartridge washing—Pre-elute each 

cartridge prior to use sequentially with 10- 

mL portions each of hexane, methanol, and 

water using vacuum for 30 seconds after each 

eluting solvent. Follow this pre-elution with 

1 mL methylene chloride and three 10-mL 

portions of the elution solvent (section 

6.7.2.2) using vacuum for 5 minutes after 

each eluting solvent. Tap the cartridge lightly 

while under vacuum to dry between solvent 

rinses. The three portions of elution solvent 

may be collected and used as a cartridge 

blank, if desired. Finally, elute the cartridge 

with 10 mL each of methanol and water, 

using the vacuum for 30 seconds after each 

eluant. 

11.2.3 Extract cleanup. 

11.2.3.1 After cartridge washing (section 

11.2.2), release the vacuum and place the 

rack containing the 50-mL volumetric flasks 

(section 5.5.3.4) in the vacuum manifold. Reestablish 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 pre-cleaned 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 7.8 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 pre-cleaned glass wool in the 

chromatographic column (section 5.2.4) to 

retain the alumina. Add 10 g of alumina 

(section 6.7.3) on top of the plug. Tap the 

column to settle the alumina. Place 1–2 g of 

anhydrous sodium sulfate on top of the 

alumina. 

11.4.2 Close the stopcock and fill the 

column to just above the sodium sulfate with 

hexane. Add 25 mL of hexane. Open the 

stopcock and adjust the flow rate of hexane 

to approximately 2 mL/min. Do not allow the 

column to go dry throughout the elutions. 

11.4.3 When the level of the hexane is at 

the top of the column, quantitatively transfer 

the extract to the column. When the level of 

the extract is at the top of the column, slowly 

add 25 mL of hexane and elute the column 

to the level of the sodium sulfate. Discard the 

hexane. 

11.4.4 Place a K–D flask (section 

5.2.5.1.2) under the column and elute the 

pesticides with approximately 150 mL of 

hexane:ethyl ether (80:20 v/v). It may be 

necessary to adjust the volume of elution 

solvent for slightly different alumina 

activities. 

11.4.5 Concentrate the extract per section 

10.3. 

11.5 Sulfur removal—Elemental sulfur 

will usually elute in Fraction 1 of the 

Florisil® 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 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 fluoropolymerlined 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 

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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 nitrogenevaporation vial or tube and proceed to 

section 10.3.3 for micro-concentration and 

solvent exchange. 

11.6 Acid back extraction (section 6.1.2). 

11.6.1 Quantitatively transfer the extract 

(section 10.3.1.5) to a 250-mL separatory 

funnel. 

11.6.2 Partition the extract against 50 mL 

of sulfuric acid solution (section 6.1.2). 

Discard the aqueous layer. Repeat the acid 

washing until no color is visible in the 

aqueous layer, to a maximum of four 

washings. 

11.6.3 Partition the extract against 50 mL 

of sodium chloride solution (section 6.7.5). 

Discard the aqueous layer. 

11.6.4 Proceed to section 10.3.3 for 

micro-concentration and solvent exchange. 

12. Gas Chromatography 

12.1 Establish the same operating 

conditions used in section 7.1 for instrument 

calibration. 

12.2 If the internal standard calibration 

procedure is used, add the internal standard 

solution (section 6.9.3) to the extract as close 

as possible to the time of injection to 

minimize the possibility of loss by 

evaporation, adsorption, or reaction. For 

example, add 1 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 oncolumn injection. Alternatively, if using a 

single-column GC configuration, inject an 

appropriate volume of the sample extract or 

standard solution onto each GC column 

independently. If the sample is injected 

manually, the solvent-flush technique should 

be used. The injection volume depends upon 

the technique used and the sensitivity 

needed to meet MDLs or reporting limits for 

regulatory compliance. Injection volumes 

must be the same for all extracts. Record the 

volume injected to the nearest 0.05 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 unpierced fluoropolymer-lined septa. 

13. System and Laboratory Performance 

13.1 At the beginning of each shift during 

which standards or extracts are analyzed, GC 

system performance and calibration must be 

verified for all analytes and surrogates on 

both column/detector systems. Adjustment 

and/or recalibration (per section 7) are 

performed until all performance criteria are 

met. Only after all performance criteria are 

met may samples, blanks and other QC 

samples, and standards be analyzed. 

13.2 Inject an aliquot of the calibration 

verification standard (section 6.8.4) on both 

columns. Inject an aliquot of each of the 

multi-component standards. 

13.3 Retention times—The absolute 

retention times of the peak maxima shall be 

within ±2 seconds of the retention times in 

the calibration verification (section 7.8). 

13.4 GC resolution—Resolution is 

acceptable if the valley height between two 

peaks (as measured from the baseline) is less 

than 40% of the shorter of the two peaks. 

13.4.1 DB–608 column—DDT and endrin 

aldehyde 

13.4.2 DB–1701 column—alpha and 

gamma chlordane 

Note: If using other GC columns or 

stationary phases, these resolution criteria 

apply to these four target analytes and any 

other closely eluting analytes on those other 

GC columns. 

13.5 Decomposition of DDT and endrin— 

If DDT, endrin, or their breakdown products 

are to be determined, this test must be 

performed prior to calibration verification 

(section 13.6). DDT decomposes to DDE and 

DDD. Endrin decomposes to endrin aldehyde 

and endrin ketone. 

13.5.1 Inject 1 mL of the DDT and endrin 

decomposition solution (section 6.8.7). As 

noted in section 6.8.7, other injection 

volumes may be used as long as the 

concentrations of DDT and endrin in the 

solution are adjusted to introduce the masses 

of the two analytes into the instrument that 

are listed in section 6.8.7. 

13.5.2 Measure the areas of the peaks for 

DDT, DDE, DDD, endrin, endrin aldehyde, 

and endrin ketone in the chromatogram and 

calculate the percent breakdown as shown in 

the equations below: 

13.5.3 Both the % breakdown of DDT and 

of endrin must be less than 20%, otherwise 

the system is not performing acceptably for 

DDT and endrin. In this case, repair the GC 

column system that failed and repeat the 

performance tests (sections 13.2 to 13.6) until 

the specification is met. 

Note: DDT and endrin decomposition are 

usually caused by accumulations of 

particulates in the injector and in the front 

end of the column. Cleaning and silanizing 

the injection port liner, and breaking off a 

short section of the front end of the column 

will usually eliminate the decomposition 

problem. Either of these corrective actions 

may affect retention times, GC resolution, 

and calibration linearity. 

13.6 Calibration verification. 

13.6.1 Compute the percent recovery of 

each analyte and of the coeluting analytes, 

based on the initial calibration data (section 

7.5 or 7.6). 

13.6.2 For each analyte or for coeluting 

analytes, compare the concentration with the 

limits for calibration verification in Table 4. 

For coeluting analytes, use the coeluting 

analyte with the least restrictive specification 

(the widest range). For analytes in Table 2 

not listed in Table 4, QC acceptance criteria 

must be developed by the laboratory. EPA 

has provided guidance for development of 

QC acceptance criteria (References 13 and 

14). If the recoveries for all analytes meet the 

acceptance criteria, system performance is 

acceptable and analysis of blanks and 

samples may continue. If, however, any 

recovery falls outside the calibration 

verification range, system performance is 

unacceptable for that analyte. If this occurs, 

repair the system and repeat the test (section 

13.6), or prepare a fresh calibration standard 

and repeat the test, or recalibrate (section 7). 

See Section 8.1.7 for information on repeated 

test failures. 

13.7 Laboratory control sample. 

13.7.1 Analyze the extract of the LCS 

(section 6.8.3) extracted with each sample 

batch (Section 8.4). See Section 8.4 for 

criteria acceptance of the LCS. 

13.7.2 It is suggested, but not required, 

that the laboratory update statements of data 


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quality. Add results that pass the 

specifications in section 13.7.3 to initial 

(section 8.7) and previous ongoing data. 

Update QC charts to form a graphic 

representation of continued laboratory 

performance. Develop a statement of 

laboratory data quality for each analyte by 

calculating the average percent recovery (R) 

and the standard deviation of percent 

recovery, sr. Express the accuracy as a 

recovery interval from R ¥ 2sr to R + 2sr. For 

example, if R = 95% and sr = 5%, the 

accuracy is 85 to 105%. 

13.8 Internal standard response—If 

internal standard calibration is used, verify 

that detector sensitivity has not changed by 

comparing the response (area or height) of 

each internal standard in the sample, blank, 

LCS, MS, and MSD to the response in 

calibration verification (section 6.8.3). The 

peak area or height of the internal standard 

should be within 50% to 200% (1⁄2 to 2x) of 

its respective peak area or height in the 

verification standard. If the area or height is 

not within this range, compute the 

concentration of the analytes using the 

external standard method (section 7.5). If the 

analytes are affected, re-prepare and 

reanalyze the sample, blank, LCS, MS, or 

MSD, and repeat the pertinent test. 

14. Qualitative Identification 

14.1 Identification is accomplished by 

comparison of data from analysis of a sample, 

blank, or other QC sample with data from 

calibration verification (section 7.7.1 or 13.5), 

and with data stored in the retention-time 

and calibration libraries (section 7.7). The 

retention time window is determined as 

described in section 14.2. Identification is 

confirmed when retention time agrees on 

both GC columns, as described below. 

Alternatively, GC/MS identification may be 

used to provide another means of 

identification. 

14.2 Establishing retention time 

windows. 

14.2.1 Using the data from the 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 singlecomponent analyte on each column/detector 

system and for the three to five exclusive 

(unique large) peaks for each multicomponent analyte. 

14.2.3 Define the width of the retention 

time window as three times that standard 

deviation. Establish the center of the 

retention time window for each analyte by 

using the absolute retention time for each 

analyte from the calibration verification 

standard at the beginning of the analytical 

shift. For samples run during the same shift 

as an initial calibration, use the retention 

time of the mid-point standard of the initial 

calibration. If the calculated RT window is 

less than 0.02 minutes, then use 0.02 minutes 

as the window. 

Note: Procedures for establishing retention 

time windows from other sources may be 

employed provided that they are clearly 

documented and provide acceptable 

performance. Such performance may be 

evaluated using the results for the spiked QC 

samples described in this method, such as 

laboratory control samples and matrix spike 

samples. 

14.2.4 The retention time windows must 

be recentered when a new GC column is 

installed or if a GC column has been 

shortened during maintenance to a degree 

that the retention times of analytes in the 

calibration verification standard have shifted 

close to the lower limits of the established 

retention time windows. 

14.2.5 RT windows should be checked 

periodically by examining the peaks in 

spiked samples such as the LCS or MS/MSD 

to confirm that peaks for known analytes are 

properly identified. 

14.2.6 If the retention time of an analyte 

in the calibration (Section 7.4) varies by more 

than 5 seconds across the calibration range as 

a function of the concentration of the 

standard, using the standard deviation of the 

retention times (section 14.2.3) to set the 

width of the retention time window may not 

adequately serve to identify the analyte in 

question under routine conditions. In such 

cases, data from additional analyses of 

standards may be required to adequately 

model the chromatographic behavior of the 

analyte. 

14.3 Identifying the analyte in a sample. 

14.3.1 In order to identify a singlecomponent analyte from analysis of a sample, 

blank, or other QC sample, the peak 

representing the analyte must fall within its 

respective retention time windows on both 

column/detector systems (as defined in 

section 14.2). That identification is further 

supported by the comparison of the 

numerical results on both columns, as 

described in section 15.7. 

14.3.2 In order to identify a multicomponent analyte, pattern matching 

(fingerprinting) may be used, or the three to 

five exclusive (unique and largest) peaks for 

that analyte must fall within their respective 

retention time windows on both column/

detector systems (as defined in section 14.2). 

That identification is further supported by 

the comparison of the numerical results on 

both columns, as described in section 15.7. 

Alternatively, GC/MS identification may be 

used. Differentiation among some of the 

Aroclors may require evaluation of more than 

five peaks to ensure correct identification. 

14.4 GC/MS confirmation. When the 

concentration of an analyte is sufficient and 

the presence or identity is suspect, its 

presence should be confirmed by GC/MS. In 

order to match the sensitivity of the GC/ECD, 

confirmation would need to be by GC/MS– 

SIM, or the estimated concentration would 

need to be 100 times higher than the GC/ECD 

calibration range. The extract may be 

concentrated by an additional amount to 

allow a further attempt at GC/MS 

confirmation. 

14.5 Additional information that may aid 

the laboratory in the identification of an 

analyte. The occurrence of peaks eluting near 

the retention time of an analyte of interest 

increases the probability of a false positive 

for the analyte. If the concentration is 

insufficient for confirmation by GC/MS, the 

laboratory may use the cleanup procedures in 

this method (section 11) on a new sample 

aliquot to attempt to remove the interferent. 

After attempts at cleanup are exhausted, the 

following steps may be helpful to assure that 

the substance that appears in the RT 

windows on both columns is the analyte of 

interest. 

14.5.1 Determine the consistency of the 

RT data for the analyte on each column. For 

example, if the RT is very stable (i.e., varies 

by no more than a few seconds) for the 

calibration, calibration verification, blank, 

LCS, and MS/MSD, the RT for the analyte of 

interest in the sample should be within this 

variation regardless of the window 

established in Section 14.2. If the analyte is 

not within this variation on both columns, it 

is likely not present. 

14.5.2 The possibility exists that the RT 

for the analyte in a sample could shift if 

extraneous materials are present. This 

possibility may be able to be confirmed or 

refuted by the behavior of the surrogates in 

the sample. If multiple surrogates are used 

that span the length of the chromatographic 

run, the RTs for the surrogates on both 

columns are consistent with their RTs in 

calibration, calibration verification, blank, 

LCS, and MS/MSD, it is unlikely that the RT 

for the analyte of interest has shifted. 

14.5.3 If the RT for the analyte is shifted 

slightly later on one column and earlier on 

the other, and the surrogates have not shifted, 

it is highly unlikely that the analyte is 

present, because shifts nearly always occur in 

the same direction on both columns. 

15. Quantitative Determination 

15.1 External standard quantitation— 

Calculate the concentration of the analyte in 

the extract using the calibration curve or 

average calibration factor determined in 

calibration (section 7.5.2) and the following 

equation: 

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) 


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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 multi-component 

analytes. 

15.5.1 PCBs as Aroclors. Quantify an 

Aroclor by comparing the sample 

chromatogram to that of the most similar 

Aroclor standard as indicated in section 

14.3.2. Compare the responses of 3 to 5 major 

peaks in the calibration standard for that 

Aroclor with the peaks observed in the 

sample extract. The amount of Aroclor is 

calculated using the individual calibration 

factor for each of the 3 to 5 characteristic 

peaks chosen in section 7.5.1. Determine the 

concentration of each of the characteristic 

peaks, using the average calibration factor 

calculated for that peak in section 7.5.2, and 

then those 3 to 5 concentrations are averaged 

to determine the concentration of that 

Aroclor. 

15.5.2 Other multi-component analytes. 

Quantify any other multi-component analytes 

(technical chlordane or toxaphene) using the 

same peaks used to develop the average 

calibration factors in section 7.5.2. Determine 

the concentration of each of the characteristic 

peaks, and then the concentrations 

represented by those characteristic peaks are 

averaged to determine the concentration of 

the analyte. Alternatively, for toxaphene, the 

analyst may determine the calibration factor 

in section 7.5.2 by summing the areas of all 

of the peaks for the analyte and using the 

summed of the peak areas in the sample 

chromatogram to determine the 

concentration. However, the approach used 

for toxaphene must be the same for the 

calibration and the sample analyses. 

15.6 Reporting of results. As noted in 

section 1.6.1, EPA has promulgated this 

method at 40 CFR part 136 for use in 

wastewater compliance monitoring under the 

National Pollutant Discharge Elimination 

System (NPDES). The data reporting 

practices described here are focused on such 

monitoring needs and may not be relevant to 

other uses of the method. 

15.6.1 Report results for wastewater 

samples in 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 specified 

otherwise by a regulatory authority or in a 

discharge permit, results for analytes that 

meet the identification criteria are reported 

down to the concentration of the ML 

established by the laboratory through 

calibration of the instrument (see section 7.5 

or 7.6 and the glossary for the derivation of 

the ML). EPA considers the terms ‘‘reporting 

limit,’’ ‘‘quantitation limit,’’ and ‘‘minimum 

level’’ to be synonymous. 

15.6.2.1 Report the lower result from the 

two columns (see section 15.7 below) for 

each analyte in each sample or QC standard 

at or above the ML to 3 significant figures. 

Report a result for each analyte in each 

sample or QC standard below the ML as 

‘‘<ML,’’ where ‘‘ML’’ is the concentration of 

the analyte at the ML (e.g., if the ML is 10 

mg/L, then report the result as <10 mg/L), or 

as required by the regulatory authority or 

permit. Report a result for each analyte in a 

blank at or above the MDL to 2 significant 

figures. Report a result for each analyte found 

in a blank below the MDL as ‘‘<MDL,’’ where 

MDL is the concentration of the analyte at the 

MDL, or as required by the regulatory/control 

authority or permit. 

15.6.2.2 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 require reporting results for some 

analytes from different analyses. Results for 

each analyte in 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, 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. See 

section 8.1.7 for dispositions of failures. If 

the holding time would be exceeded for a reanalysis 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 coeluted 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 coeluting 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. See section 8.1.7 for 

disposition of problem results. 

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. 


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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 limits developed in 

Section 8.6, re-extract and reanalyze the 

sample if there is sufficient sample and if it 

is within the 7-day extraction holding time. 

If 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. See Section 

8.1.7 for dispositions of failures. 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 single-component 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. 

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), available from the American 

Chemical Society’s Department of 

Governmental Relations and Science Policy, 

1155 16th Street NW., Washington DC 20036, 

202–872–4477. 

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 handled and 

disposed of as hazardous waste, or 

neutralized and disposed of in accordance 

with all federal, state, and local regulations. 

It is the laboratory’s responsibility to comply 

with all federal, state, and local regulations 

governing waste management, particularly 

the hazardous waste identification rules and 

land disposal restrictions. The laboratory 

using this method has the responsibility to 

protect the air, water, and land by 

minimizing and controlling all releases from 

fume hoods and bench operations. 

Compliance is also required with any sewage 

discharge permits and regulations. For 

further information on waste management, 

see ‘‘The Waste Management Manual for 

Laboratory Personnel,’’ also available from 

the American Chemical Society at the 

address in section 18.3. 

19.3 Many analytes in this method 

decompose above 500 °C. Low-level waste 

such as absorbent paper, tissues, animal 

remains, and plastic gloves may be burned in 

an appropriate incinerator. Gross quantities 

of neat or highly concentrated solutions of 

toxic or hazardous chemicals should be 

packaged securely and disposed of through 

commercial or governmental channels that 

are capable of handling toxic wastes. 

19.4 For further information on waste 

management, consult The Waste 

Management Manual for Laboratory 

Personnel and Less is Better-Laboratory 

Chemical Management for Waste Reduction, 

available from the American Chemical 

Society’s Department of Government 

Relations and Science Policy, 1155 16th 

Street NW., Washington, DC 20036, 202– 

872–4477. 

20. References 

1. ‘‘Determination of Pesticides and PCBs in 

Industrial and Municipal Wastewaters,’’ 

EPA 600/4–82–023, National Technical 

Information Service, PB82–214222, 

Springfield, Virginia 22161, April 1982. 

2. ‘‘EPA Method Study 18 Method 608- 

Organochlorine Pesticides and PCBs,’’ 

EPA 600/4–84–061, National Technical 

Information Service, PB84–211358, 

Springfield, Virginia 22161, June 1984. 

3. ‘‘Method Detection Limit and Analytical 

Curve Studies, EPA Methods 606, 607, 

and 608,’’ Special letter report for EPA 

Contract 68–03–2606, U.S. 

Environmental Protection Agency, 

Environmental Monitoring and Support 

Laboratory, Cincinnati, Ohio 45268, June 

1980. 

4. ASTM Annual Book of Standards, Part 31, 

D3694–78. ‘‘Standard Practice for 

Preparation of Sample Containers and for 

Preservation of Organic Constituents,’’ 

American Society for Testing and 

Materials, Philadelphia. 

5. Giam, C.S., Chan, H.S., and Nef, G.S. 

‘‘Sensitive Method for Determination of 

Phthalate Ester Plasticizers in OpenOcean Biota Samples,’’ Analytical 

Chemistry, 47:2225 (1975). 

6. Giam, C.S. and Chan, H.S. ‘‘Control of 

Blanks in the Analysis of Phthalates in 

Air and Ocean Biota Samples,’’ U.S. 

National Bureau of Standards, Special 

Publication 442, pp. 701–708, 1976. 

7. Solutions to Analytical Chemistry 

Problems with Clean Water Act Methods, 

EPA 821–R–07–002, March 2007. 

8. ‘‘Carcinogens-Working With Carcinogens,’’ 

Department of Health, Education, and 

Welfare, Public Health Service, Center 

for Disease Control, National Institute for 

Occupational Safety and Health, 

Publication No. 77–206, August 1977. 

9. ‘‘Occupational Exposure to Hazardous 

Chemicals in Laboratories,’’ (29 CFR 

1910.1450), Occupational Safety and 

Health Administration, OSHA. 

10. 40 CFR 136.6(b)(4)(j). 

11. Mills, P.A. ‘‘Variation of Florisil Activity: 

Simple Method for Measuring Absorbent 

Capacity and Its Use in Standardizing 

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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-is-better.pdf. 

20. EPA Method 608 ATP 3M0222, An 

alternative test procedure for the 

measurement of organochlorine 

pesticides and polychlorinated 

biphenyls in waste water. Federal 

Register, Vol. 60, No. 148 August 2, 

1995. 

21. Tables 

TABLE 1—PESTICIDES 1

Analyte CAS No. MDL 2

(ng/L) 

ML 3

(ng/L) 

Aldrin ............................................................................................................................................ 309–00–2 4 12 

alpha-BHC ................................................................................................................................... 319–84–6 3 9 

beta-BHC ..................................................................................................................................... 319–85–7 6 18 

delta-BHC .................................................................................................................................... 319–86–8 9 27 

gamma-BHC (Lindane) ................................................................................................................ 58–89–9 4 12 

alpha-Chlordane 4 .................................................................................................................. 5103–71–9 14 42 

gamma-Chlordane 4 ............................................................................................................... 5103–74–2 14 42 

4,4′-DDD ...................................................................................................................................... 72–54–8 11 33 

4,4′-DDE ...................................................................................................................................... 72–55–9 4 12 

4,4′-DDT ....................................................................................................................................... 50–29–3 12 36 

Dieldrin ......................................................................................................................................... 60–57–1 2 6 

Endosulfan I ................................................................................................................................. 959–98–8 14 42 

Endosulfan II ................................................................................................................................ 33213–65–9 4 12 

Endosulfan sulfate ....................................................................................................................... 1031–07–8 66 198 

Endrin ........................................................................................................................................... 72–20–8 6 18 

Endrin aldehyde ........................................................................................................................... 7421–93–4 23 70 

Heptachlor .................................................................................................................................... 76–44–8 3 9 

Heptachlor epoxide ...................................................................................................................... 1024–57–3 83 249 

1All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A). 

2 40 CFR part 136, appendix B, June 30, 1986. 

3 ML = Minimum Level—see Glossary for definition and derivation, calculated as 3 times the MDL. 

4 MDL based on the MDL for Chlordane. 

TABLE 2—ADDITIONAL ANALYTES

Analyte CAS No. MDL 3

(ng/L) 

ML 4

(ng/L) 

Acephate ...................................................................................................................................... 30560–19–1 ........................ ........................

Alachlor ........................................................................................................................................ 15972–60–8 ........................ ........................

Atrazine ........................................................................................................................................ 1912–24–9 ........................ ........................

Benfluralin (Benefin) .................................................................................................................... 1861–40–1 ........................ ........................

Bromacil ....................................................................................................................................... 314–40–9 ........................ ........................

Bromoxynil octanoate .................................................................................................................. 1689–99–2 ........................ ........................

Butachlor ...................................................................................................................................... 23184–66–9 ........................ ........................

Captafol ........................................................................................................................................ 2425–06–1 ........................ ........................

Captan ......................................................................................................................................... 133–06–2 ........................ ........................

Carbophenothion (Trithion) .......................................................................................................... 786–19–6 ........................ ........................

Chlorobenzilate ............................................................................................................................ 510–15–6 ........................ ........................

Chloroneb (Terraneb) .................................................................................................................. 2675–77–6 ........................ ........................

Chloropropylate (Acaralate) ......................................................................................................... 5836–10–2 ........................ ........................

Chlorothalonil ............................................................................................................................... 1897–45–6 ........................ ........................

Cyanazine .................................................................................................................................... 21725–46–2 ........................ ........................

DCPA (Dacthal) ........................................................................................................................... 1861–32–1 ........................ ........................

2,4′-DDD ...................................................................................................................................... 53–19–0 ........................ ........................

2,4′-DDE ...................................................................................................................................... 3424–82–6 ........................ ........................

2,4′-DDT ....................................................................................................................................... 789–02–6 ........................ ........................

Diallate (Avadex) ......................................................................................................................... 2303–16–4 ........................ ........................

1,2-Dibromo-3-chloropropane (DBCP) ........................................................................................ 96–12–8 ........................ ........................

Dichlone ....................................................................................................................................... 117–80–6 ........................ ........................

Dichloran ...................................................................................................................................... 99–30–9 ........................ ........................

Dicofol .......................................................................................................................................... 115–32–2 ........................ ........................

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TABLE 2—ADDITIONAL ANALYTES—Continued 

Analyte CAS No. MDL 3

(ng/L) 

ML 4

(ng/L) 

Endrin ketone ............................................................................................................................... 53494–70–5 ........................ ........................

Ethalfluralin (Sonalan) ................................................................................................................. 55283–68–6 ........................ ........................

Etridiazole .................................................................................................................................... 2593–15–9 ........................ ........................

Fenarimol (Rubigan) .................................................................................................................... 60168–88–9 ........................ ........................

Hexachlorobenzene 1 ................................................................................................................... 118–74–1 ........................ ........................

Hexachlorocyclopentadiene 1 ....................................................................................................... 77–47–4 ........................ ........................

Isodrin .......................................................................................................................................... 465–73–6 ........................ ........................

Isopropalin (Paarlan) ................................................................................................................... 33820–53–0 ........................ ........................

Kepone ......................................................................................................................................... 143–50–0 ........................ ........................

Methoxychlor ................................................................................................................................ 72–43–5 ........................ ........................

Metolachlor .................................................................................................................................. 51218–45–2 ........................ ........................

Metribuzin .................................................................................................................................... 21087–64–9 ........................ ........................

Mirex ............................................................................................................................................ 2385–85–5 ........................ ........................

Nitrofen (TOK) ............................................................................................................................. 1836–75–5 ........................ ........................

cis-Nonachlor ............................................................................................................................... 5103–73–1 ........................ ........................

trans-Nonachlor ........................................................................................................................... 39765–80–5 ........................ ........................

Norfluorazon ................................................................................................................................ 27314–13–2 ........................ ........................

Octachlorostyrene ........................................................................................................................ 29082–74–4 ........................ ........................

Oxychlordane ............................................................................................................................... 27304–13–8 ........................ ........................

PCNB (Pentachloronitrobenzene) ............................................................................................... 82–68–8 ........................ ........................

Pendamethalin (Prowl) ................................................................................................................ 40487–42–1 ........................ ........................

cis-Permethrin .............................................................................................................................. 61949–76–6 ........................ ........................

trans-Permethrin .......................................................................................................................... 61949–77–7 ........................ ........................

Perthane (Ethylan) ....................................................................................................................... 72–56–0 ........................ ........................

Propachlor .................................................................................................................................... 1918–16–7 ........................ ........................

Propanil ........................................................................................................................................ 709–98–8 ........................ ........................

Propazine ..................................................................................................................................... 139–40–2 ........................ ........................

Quintozene ................................................................................................................................... 82–68–8 ........................ ........................

Simazine ...................................................................................................................................... 122–34–9 ........................ ........................

Strobane ...................................................................................................................................... 8001–50–1 ........................ ........................

Technazene ................................................................................................................................. 117–18–0 ........................ ........................

Technical Chlordane 2 .................................................................................................................. ........................ ........................ ........................

Terbacil ........................................................................................................................................ 5902–51–2 ........................ ........................

Terbuthylazine ............................................................................................................................. 5915–41–3 ........................ ........................

Toxaphene 1 ................................................................................................................................. 8001–35–2 240 720 

Trifluralin ...................................................................................................................................... 1582–09–8 ........................ ........................

PCB–1016 1 ................................................................................................................................. 12674–11–2 ........................ ........................

PCB–1221 1 ................................................................................................................................. 11104–28–2 ........................ ........................

PCB–1232 1 ................................................................................................................................. 11141–16–5 ........................ ........................

PCB–1242 1 ................................................................................................................................. 53469–21–9 65 95 

PCB–1248 1 ................................................................................................................................. 12672–29–6 ........................ ........................

PCB–1254 1 ................................................................................................................................. 11097–69–1 ........................ ........................

PCB–1260 1 ................................................................................................................................. 11096–82–5 ........................ ........................

PCB–1268 .................................................................................................................................... 11100–14–4 ........................ ........................

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, June 30, 1986. 

4 ML = Minimum Level—see Glossary for definition and derivation, calculated as 3 times the MDL. 

TABLE 3—EXAMPLE RETENTION TIMES 1

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 

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TABLE 3—EXAMPLE RETENTION TIMES 1—Continued 

Analyte 

Retention time 

(min) 2

DB–608 DB–1701 

Dichlone ................................................................................................................................................................... 10.80 (4) 

Terbacil .................................................................................................................................................................... 11.11 12.63 

delta-BHC ................................................................................................................................................................ 11.20 12.98 

Alachlor .................................................................................................................................................................... 11.57 11.06 

Propanil .................................................................................................................................................................... 11.60 14.10 

Aldrin ........................................................................................................................................................................ 11.84 11.46 

DCPA ....................................................................................................................................................................... 12.18 12.09 

Metribuzin ................................................................................................................................................................ 12.80 11.68 

Triadimefon .............................................................................................................................................................. 12.99 13.57 

Isopropalin ............................................................................................................................................................... 13.06 13.37 

Isodrin ...................................................................................................................................................................... 13.47 11.12 

Heptachlor epoxide .................................................................................................................................................. 13.97 12.56 

Pendamethalin ......................................................................................................................................................... 14.21 13.46 

Bromacil ................................................................................................................................................................... 14.39 (3) 

alpha-Chlordane ...................................................................................................................................................... 14.63 14.20 

Butachlor .................................................................................................................................................................. 15.03 15.69 

gamma-Chlordane ................................................................................................................................................... 15.24 14.36 

Endosulfan I ............................................................................................................................................................. 15.25 13.87 

4,4′-DDE .................................................................................................................................................................. 16.34 14.84 

Dieldrin ..................................................................................................................................................................... 16.41 15.25 

Captan ..................................................................................................................................................................... 16.83 15.43 

Chlorobenzilate ........................................................................................................................................................ 17.58 17.28 

Endrin ....................................................................................................................................................................... 17.80 15.86 

Nitrofen (TOK) ......................................................................................................................................................... 17.86 17.47 

Kepone ..................................................................................................................................................................... 17.92 (3 5) 

4,4′-DDD .................................................................................................................................................................. 18.43 17.77 

Endosulfan II ............................................................................................................................................................ 18.45 18.57 

Bromoxynil octanoate .............................................................................................................................................. 18.85 18.57 

4,4′-DDT .................................................................................................................................................................. 19.48 18.32 

Carbophenothion ..................................................................................................................................................... 19.65 18.21 

Endrin aldehyde ....................................................................................................................................................... 19.72 19.18 

Endosulfan sulfate ................................................................................................................................................... 20.21 20.37 

Captafol .................................................................................................................................................................... 22.51 21.22 

Norfluorazon ............................................................................................................................................................ 20.68 22.01 

Mirex ........................................................................................................................................................................ 22.75 19.79 

Methoxychlor ............................................................................................................................................................ 22.80 20.68 

Endrin ketone ........................................................................................................................................................... 23.00 21.79 

Fenarimol ................................................................................................................................................................. 24.53 23.79 

cis-Permethrin .......................................................................................................................................................... 25.00 23.59 

trans-Permethrin ...................................................................................................................................................... 25.62 23.92 

PCB–1016 ................................................................................................................................................................ ........................ ........................

PCB–1221 ................................................................................................................................................................ ........................ ........................

PCB–1232 ................................................................................................................................................................ ........................ ........................

PCB–1242 ................................................................................................................................................................ ........................ ........................

PCB–1248 ................................................................................................................................................................ ........................ ........................

PCB–1254 ................................................................................................................................................................ ........................ ........................

PCB–1260 (5 peaks) ............................................................................................................................................... 15.44 14.64 

15.73 15.36 

16.94 16.53 

17.28 18.70 

19.17 19.92 

Toxaphene (5 peaks) ............................................................................................................................................... 16.60 16.60 

17.37 17.52 

18.11 17.92 

19.46 18.73 

19.69 19.00 

1 Data from EPA Method 1656 (Reference 16). 

2 Columns: 30-m long x 0.53-mm ID fused-silica capillary; DB–608, 0.83 μm; and DB–1701, 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 trans-Permethrin elutes. 

Carrier gas flow rates approximately 7 mL/min. 

3 Does not elute from DB–1701 column at level tested. 

4 Not recovered from water at the levels tested. 

5 Dichlone and Kepone do not elute from the DB–1701 column and should be confirmed on DB–5. 

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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 for the DOC (section 8.2.4). 

X = Average of four recovery measurements for the DOC (section 8.2.4). 

P = Recovery for the LCS (section 8.4.3). 

Note: These criteria were developed from data in Table 5 (Reference 2). Where necessary, limits for recovery have been broadened to assure 

applicability to concentrations below those in Table 5. 

TABLE 5—PRECISION AND RECOVERY AS FUNCTIONS OF CONCENTRATION

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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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 ........................

Endosulfan I ................................................................................................................................. 37 64 ........................

Endosulfan II ................................................................................................................................ 0 7 91 

Endosulfan sulfate ....................................................................................................................... 0 0 106 

Endrin ........................................................................................................................................... 4 96 ........................

Endrin aldehyde ........................................................................................................................... 0 68 26 

Heptachlor .................................................................................................................................... 100 ........................ ........................

Heptachlor epoxide ...................................................................................................................... 100 ........................ ........................

Toxaphene ................................................................................................................................... 96 ........................ ........................

PCB–1016 .................................................................................................................................... 97 ........................ ........................

PCB–1221 .................................................................................................................................... 97 ........................ ........................

PCB–1232 .................................................................................................................................... 95 4 ........................

PCB–1242 .................................................................................................................................... 97 ........................ ........................

PCB–1248 .................................................................................................................................... 103 ........................ ........................

PCB–1254 .................................................................................................................................... 90 ........................ ........................

PCB–1260 .................................................................................................................................... ........................ ........................ ........................

1 Eluant composition: 

Fraction 1—6% ethyl ether in hexane. 

Fraction 2—15% ethyl ether in hexane. 

Fraction 3—50% ethyl ether in hexane. 

TABLE 7—SUGGESTED CALIBRATION

GROUPS 1

Analyte 

Calibration Group 1: 

Acephate 

Alachlor 

Atrazine 

beta-BHC 

Bromoxynil octanoate 

Captafol 

Diallate 

Endosulfan sulfate 

Endrin 

Isodrin 

Pendimethalin (Prowl) 

trans-Permethrin 

Calibration Group 2: 

alpha-BHC 

DCPA 

4,4′-DDE 

4,4′-DDT 

Dichlone 

Ethalfluralin 

Fenarimol 

Methoxychlor 

Metribuzin 

Calibration Group 3: 

gamma-BHC (Lindane) 

gamma-Chlordane 

TABLE 7—SUGGESTED CALIBRATION

GROUPS 1—Continued 

Analyte 

Endrin ketone 

Heptachlor epoxide 

Isopropalin 

Nitrofen (TOK) 

PCNB 

cis-Permethrin 

Trifluralin 

Callibration Group 4: 

Benfluralin 

Chlorobenzilate 

Dieldrin 

Endosulfan I 

Mirex 

Terbacil 

Terbuthylazine 

Triadimefon 

Calibration Group 5: 

alpha-Chlordane 

Captan 

Chlorothalonil 

4,4′-DDD 

Norfluorazon 

Simazine 

Calibration Group 6: 

Aldrin 

delta-BHC 

TABLE 7—SUGGESTED CALIBRATION

GROUPS 1—Continued 

Analyte 

Bromacil 

Butachlor 

Endosulfan II 

Heptachlor 

Kepone 

Calibration Group 7: 

Carbophenothion 

Chloroneb 

Chloropropylate 

DBCP 

Dicofol 

Endrin aldehyde 

Etridiazone 

Perthane 

Propachlor 

Propanil 

Propazine 

1The analytes may be organized in other 

calibration groups, provided that there are no 

coelution problems and that all QC requirements are met. 

22. Figures 

BILLING CODE 6560–50–P 

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5 6 1 8 9 '10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 

Figure 1 Example Chromatogram of Selected Organochlorine Pesticides 
Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40897 

BILLING CODE 6560–50–C 

23. Glossary 

These definitions and purposes are specific 

to this method but have been conformed to 

common usage to the extent possible. 

23.1 Units of weight and measure and 

their abbreviations. 

23.1.1 Symbols. 

°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 

hr hour 

ID inside diameter 


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-1000 

-760 

-500 

-250 

90-mm GMF 150 Aller 

1-tlter Suction Flask 

Figure 2 Disk-based solid-phase extraction apparatus 
40898 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

in. inch 

L liter 

M molar solution—one mole or gram 

molecular weight of solute in one liter of 

solution 

mg milligram 

min minute 

mL milliliter 

mm millimeter 

N Normality—one equivalent of solute in 

one liter of solution 

ng nanogram 

psia pounds-per-square inch absolute 

psig pounds-per-square inch gauge 

v/v volume per unit volume 

w/v weight per unit volume 

23.2 Definitions and acronyms (in 

alphabetical order) 

Analyte—A compound or mixture of 

compounds (e.g., PCBs) tested for by this 

method. The analytes are listed in Tables 1 

and 2. 

Analytical batch—The set of samples 

analyzed on a given instrument during a 24- 

hour period that begins and ends with 

calibration verification (sections 7.8 and 13). 

See also ‘‘Extraction batch.’’ 

Blank (method blank; laboratory blank)— 

An aliquot of reagent water that is treated 

exactly as a sample including exposure to all 

glassware, equipment, solvents, reagents, 

internal standards, and surrogates that are 

used with samples. The blank is used to 

determine if analytes or interferences are 

present in the laboratory environment, the 

reagents, or the apparatus. 

Calibration factor (CF)—See section 7.5.1. 

Calibration standard—A solution prepared 

from stock solutions and/or a secondary 

standards and containing the analytes of 

interest, surrogates, and internal standards. 

This standard is used to model the response 

of the GC instrument against analyte 

concentration. 

Calibration verification—The process of 

confirming that the response of the analytical 

system remains within specified limits of the 

calibration. 

Calibration verification standard—The 

standard (section 6.8.4) used to verify 

calibration (sections 7.8 and 13.6). 

Extraction Batch—A set of up to 20 field 

samples (not including QC samples) started 

through the extraction process in a given 24- 

hour shift. Each extraction batch of 20 or 

fewer samples must be accompanied by a 

blank (section 8.5), a laboratory control 

sample (LCS, section 8.4), a matrix spike and 

duplicate (MS/MSD; section 8.3), resulting in 

a minimum of five samples (1 field sample, 

1 blank, 1 LCS, 1 MS, and 1 MSD) and a 

maximum of 24 samples (20 field samples, 1 

blank, 1 LCS, 1 MS, and 1 MSD) for the 

batch. If greater than 20 samples are to be 

extracted in a 24-hour shift, the samples must 

be separated into extraction batches of 20 or 

fewer samples. 

Field Duplicates—Two samples collected 

at the same time and place under identical 

conditions, and treated identically 

throughout field and laboratory procedures. 

Results of analyses the field duplicates 

provide an estimate of the precision 

associated with sample collection, 

preservation, and storage, as well as with 

laboratory procedures. 

Field blank—An aliquot of reagent water or 

other reference matrix that is placed in a 

sample container in the field, and treated as 

a sample in all respects, including exposure 

to sampling site conditions, storage, 

preservation, and all analytical procedures. 

The purpose of the field blank is to 

determine if the field or sample transporting 

procedures and environments have 

contaminated the sample. See also ‘‘Blank.’’ 

GC—Gas chromatograph or gas 

chromatography. 

Gel-permeation chromatography (GPC)—A 

form of liquid chromatography in which the 

analytes are separated based on exclusion 

from the solid phase by size. 

Internal standard—A compound added to 

an extract or standard solution in a known 

amount and used as a reference for 

quantitation of the analytes of interest and 

surrogates. Also see Internal standard 

quantitation. 

Internal standard quantitation—A means of 

determining the concentration of an analyte 

of interest (Tables 1 and 2) by reference to 

a compound not expected to be found in a 

sample. 

IDC—Initial Demonstration of Capability 

(section 8.2); four aliquots of a reference 

matrix spiked with the analytes of interest 

and analyzed to establish the ability of the 

laboratory to generate acceptable precision 

and recovery. An IDC is performed prior to 

the first time this method is used and any 

time the method or instrumentation is 

modified. 

Laboratory Control Sample (LCS; 

laboratory fortified blank; section 8.4)—An 

aliquot of reagent water spiked with known 

quantities of the analytes of interest and 

surrogates. The LCS is analyzed exactly like 

a sample. Its purpose is to assure that the 

results produced by the laboratory remain 

within the limits specified in this method for 

precision and recovery. 

Laboratory Fortified Sample Matrix—See 

Matrix spike. 

Laboratory reagent blank—See blank. 

Matrix spike (MS) and matrix spike 

duplicate (MSD) (laboratory fortified sample 

matrix and duplicate)—Two aliquots of an 

environmental sample to which known 

quantities of the analytes of interest and 

surrogates are added in the laboratory. The 

MS/MSD are prepared and analyzed exactly 

like a field sample. Their purpose is to 

quantify any additional bias and imprecision 

caused by the sample matrix. The 

background concentrations of the analytes in 

the sample matrix must be determined in a 

separate aliquot and the measured values in 

the MS/MSD corrected for background 

concentrations. 

May—This action, activity, or procedural 

step is neither required nor prohibited. 

May not—This action, activity, or 

procedural step is prohibited. 

Method detection limit (MDL)—A 

detection limit determined by the procedure 

at 40 CFR part 136, appendix B. The MDLs 

determined by EPA are listed in Tables 1 and 

2. As noted in section 1.6, use the MDLs in 

Tables 1 and 2 in conjunction with current 

MDL data from the laboratory actually 

analyzing samples to assess the sensitivity of 

this procedure relative to project objectives 

and regulatory requirements (where 

applicable). 

Minimum level (ML)—The term 

‘‘minimum level’’ refers to either the sample 

concentration equivalent to the lowest 

calibration point in a method or a multiple 

of the method detection limit (MDL), 

whichever is higher. Minimum levels may be 

obtained in several ways: They may be 

published in a method; they may be based on 

the lowest acceptable calibration point used 

by a laboratory; or they may be calculated by 

multiplying the MDL in a method, or the 

MDL determined by a laboratory, by a factor 

of 3. For the purposes of NPDES compliance 

monitoring, EPA considers the following 

terms to be synonymous: ‘‘quantitation 

limit,’’ ‘‘reporting limit,’’ and ‘‘minimum 

level.’’ 

MS—Mass spectrometer or mass 

spectrometry. 

Must—This action, activity, or procedural 

step is required. 

Preparation blank—See blank. 

Reagent water—Water demonstrated to be 

free from the analytes of interest and 

potentially interfering substances at the 

MDLs for the analytes in this method. 

Regulatory compliance limit—A limit on 

the concentration or amount of a pollutant or 

contaminant specified in a nationwide 

standard, in a permit, or otherwise 

established by a regulatory/control authority. 

Relative standard deviation (RSD)—The 

standard deviation times 100 divided by the 

mean. Also termed ‘‘coefficient of variation.’’ 

RF—Response factor. See section 7.6.2. 

RPD—Relative percent difference. 

RSD—See relative standard deviation. 

Safety Data Sheet (SDS)—Written 

information on a chemical’s toxicity, health 

hazards, physical properties, fire, and 

reactivity, including storage, spill, and 

handling precautions that meet the 

requirements of OSHA, 29 CFR 1910.1200(g) 

and appendix D to § 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. 

* * * * * 

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Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40899 

Method 611—Haloethers 

1. Scope and Application 

1.1 This method covers the determination 

of certain haloethers. The following 

parameters can be determined by this 

method: 

Parameter STORET No. CAS No. 

Bis(2-chloroethyl) ether ............................................................................................................................................ 34273 111–44–4 

Bis(2-chloroethoxy) methane ................................................................................................................................... 34278 111–91–1 

2, 2′-oxybis (1-chloropropane) ................................................................................................................................. 34283 108–60–1 

4-Bromophenyl phenyl ether ................................................................................................................................... 34636 101–55–3 

4-Chlorophenyl phenyl ether ................................................................................................................................... 34641 7005–72–3 

* * * * * 

Method 624.1—Purgeables by GC/MS 

1. Scope and Application 

1.1 This method is for determination of 

purgeable organic pollutants in industrial 

discharges and other environmental samples 

by gas chromatography combined with mass 

spectrometry (GC/MS), as provided under 40 

CFR 136.1. This revision is based on previous 

protocols (References 1—3), on the revision 

promulgated October 26, 1984, and on an 

interlaboratory method validation study 

(Reference 4). Although this method was 

validated through an interlaboratory study 

conducted in the early 1980s, the 

fundamental chemistry principles used in 

this method remain sound and continue to 

apply. 

1.2 The analytes that may be qualitatively 

and quantitatively determined using this 

method and their CAS Registry numbers are 

listed in Table 1. The method may be 

extended to determine the analytes listed in 

Table 2; however, poor purging efficiency or 

gas chromatography of some of these analytes 

may make quantitative determination 

difficult. For example, an elevated 

temperature may be required to purge some 

analytes from water. If an elevated 

temperature is used, calibration and all 

quality control (QC) tests must be performed 

at the elevated temperature. EPA encourages 

the use of this method to determine 

additional compounds amenable to purgeand-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 (opentubular) columns, allowed laboratories to 

routinely achieve MDLs for the analytes in 

this method that are 2–10 times lower than 

those in the version promulgated in 1984. 

The MDL for a specific wastewater may differ 

from those listed, depending on the nature of 

interferences in the sample matrix. 

1.4.1 EPA has promulgated this method 

at 40 CFR part 136 for use in wastewater 

compliance monitoring under the National 

Pollutant Discharge Elimination System 

(NPDES). The data reporting practices 

described in section 13.2 are focused on such 

monitoring needs and may not be relevant to 

other uses of the method. 

1.4.2 This method includes ‘‘reporting 

limits’’ based on EPA’s ‘‘minimum level’’ 

(ML) concept (see the glossary in section 20). 

Table 1 contains MDL values and ML values 

for many of the analytes. The MDL for an 

analyte in a specific wastewater may differ 

from that listed in Table 1, depending upon 

the nature of interferences in the sample 

matrix. 

1.5 This method is performance-based. It 

may be modified to improve performance 

(e.g., to overcome interferences or improve 

the accuracy of results) provided all 

performance requirements are met. 

1.5.1 Examples of allowed method 

modifications are described at 40 CFR 136.6. 

Other examples of allowed modifications 

specific to this method are described in 

section 8.1.2. 

1.5.2 Any modification beyond those 

expressly allowed at 40 CFR 136.6 or in 

section 8.1.2 of this method shall be 

considered a major modification that is 

subject to application and approval of an 

alternate test procedure under 40 CFR 136.4 

and 136.5. 

1.5.3 For regulatory compliance, any 

modification must be demonstrated to 

produce results equivalent or superior to 

results produced by this method when 

applied to relevant wastewaters (section 8.3). 

1.6 This method is restricted to use by or 

under the supervision of analysts 

experienced in the operation of a purge-andtrap system and a gas chromatograph/mass 

spectrometer and in the interpretation of 

mass spectra. Each analyst must demonstrate 

the ability to generate acceptable results with 

this method using the procedure in section 

8.2. 

1.7 Terms and units of measure used in 

this method are given in the glossary at the 

end of the method. 

2. Summary of Method 

2.1 A gas is bubbled through a measured 

volume of water in a specially-designed 

purging chamber. The purgeables are 

efficiently transferred from the aqueous 

phase to the vapor phase. The vapor is swept 

through a sorbent trap where the purgeables 

are trapped. After purging is completed, the 

trap is heated and backflushed with the gas 

to desorb the purgeables onto a gas 

chromatographic column. The column is 

temperature programmed to separate the 

purgeables which are then detected with a 

mass spectrometer. 

2.2 Different sample sizes in the range of 

5–25 mL are allowed in order to meet 

differing sensitivity requirements. Calibration 

and QC samples must have the same volume 

as field samples. 

3. Interferences 

3.1 Impurities in the purge gas, organic 

compounds outgassing from the plumbing 

ahead of the trap, and solvent vapors in the 

laboratory account for the majority of 

contamination problems. The analytical 

system must be demonstrated to be free from 

contamination under the conditions of the 

analysis by analyzing blanks initially and 

with each analytical batch (samples analyzed 

on a given 12-hour shift, to a maximum of 

20 samples), as described in Section 8.5. 

Fluoropolymer tubing, fittings, and thread 

sealant should be used to avoid 

contamination. 

3.2 Samples can be contaminated by 

diffusion of volatile organics (particularly 

fluorocarbons and methylene chloride) 

through the septum seal into the sample 

during shipment and storage. Protect samples 

from sources of volatiles during collection, 

shipment, and storage. A reagent water field 

blank carried through sampling and analysis 

can serve as a check on such contamination. 

3.3 Contamination by carry-over can 

occur whenever high level and low level 

samples are analyzed sequentially. To reduce 

the potential for carry-over, the purging 

device and sample syringe must be rinsed 

with reagent water between sample analyses. 

Whenever an unusually concentrated sample 

is encountered, it should be followed by an 

analysis of a blank to check for cross 

contamination. For samples containing large 

amounts of water-soluble materials, 

suspended solids, high boiling compounds or 

high purgeable levels, it may be necessary to 

wash the purging device with a detergent 

solution, rinse it with distilled water, and 

then dry it in a 105 °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. 

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4. Safety 

4.1 The toxicity or carcinogenicity of 

each reagent used in this method has not 

been precisely defined; however, each 

chemical compound should be treated as a 

potential health hazard. From this viewpoint, 

exposure to these chemicals must be reduced 

to the lowest possible level. The laboratory 

is responsible for maintaining a current 

awareness file of OSHA regulations regarding 

the safe handling of the chemicals specified 

in this method. A reference file of safety data 

sheets (SDSs, OSHA, 29 CFR 1910.1200(g)) 

should also be made available to all 

personnel involved in sample handling and 

chemical analysis. Additional references to 

laboratory safety are available and have been 

identified (References 7–9) for the 

information of the analyst. 

4.2. The following analytes covered by 

this method have been tentatively classified 

as known or suspected human or mammalian 

carcinogens: Benzene; carbon tetrachloride; 

chloroform; 1,4-dichlorobenzene; 1,2- 

dichloroethane; 1,2-dichloropropane; 

methylene chloride; tetrachloroethylene; 

trichloroethylene; and vinyl chloride. 

Primary standards of these toxic compounds 

should be prepared in a chemical fume hood, 

and a NIOSH/MESA approved toxic gas 

respirator should be worn when handling 

high concentrations of these compounds. 

4.3 This method allows the use of 

hydrogen as a carrier gas in place of helium 

(Section 5.3.1.2). The laboratory should take 

the necessary precautions in dealing with 

hydrogen, and should limit hydrogen flow at 

the source to prevent buildup of an explosive 

mixture of hydrogen in air. 

5. Apparatus and Materials 

Note: Brand names, suppliers, and part 

numbers are cited for illustration purposes 

only. No endorsement is implied. Equivalent 

performance may be achieved using 

equipment and materials other than those 

specified here. Demonstration of equivalent 

performance that meets the requirements of 

this method is the responsibility of the 

laboratory. Suppliers for equipment and 

materials in this method may be found 

through an on-line search. 

5.1 Sampling equipment for discrete 

sampling. 

5.1.1 Vial—25- or 40-mL capacity, or 

larger, with screw cap with a hole in the 

center (Fisher #13075 or equivalent). Unless 

pre-cleaned, detergent wash, rinse with tap 

and reagent water, and dry at 105 ± 5 °C 

before use. 

5.1.2 Septum—Fluoropolymer-faced 

silicone (Fisher #12722 or equivalent). 

Unless pre-cleaned, detergent wash, rinse 

with tap and reagent water, and dry at 105 

± 5 °C for one hour before use. 

5.2 Purge-and-trap system—The purgeand-trap system consists of three separate 

pieces of equipment: A purging device, trap, 

and desorber. Several complete systems are 

commercially available with autosamplers. 

Any system that meets the performance 

requirements in this method may be used. 

5.2.1 The purging device should accept 5- 

to 25-mL samples with a water column at 

least 3 cm deep. The purge gas must pass 

though the water column as finely divided 

bubbles. The purge gas must be introduced 

no more than 5 mm from the base of the 

water column. Purge devices of a different 

volume may be used so long as the 

performance requirements in this method are 

met. 

5.2.2 The trap should be at least 25 cm 

long and have an inside diameter of at least 

0.105 in. The trap should be packed to 

contain the following minimum lengths of 

adsorbents: 1.0 cm of methyl silicone coated 

packing (section 6.3.2), 15 cm of 2,6- 

diphenylene oxide polymer (section 6.3.1), 

and 8 cm of silica gel (section 6.3.3). A trap 

with different dimensions and packing 

materials is acceptable so long as the 

performance requirements in this method are 

met. 

5.2.3 The desorber should be capable of 

rapidly heating the trap to the temperature 

necessary to desorb the analytes of interest, 

and of maintaining this temperature during 

desorption. The trap should not be heated 

higher than the maximum temperature 

recommended by the manufacturer. 

5.2.4 The purge-and-trap system may be 

assembled as a separate unit or coupled to a 

gas chromatograph. 

5.3 GC/MS system. 

5.3.1 Gas chromatograph (GC)—An 

analytical system complete with a 

temperature programmable gas 

chromatograph and all required accessories, 

including syringes and analytical columns. 

Autosamplers designed for purge-and-trap 

analysis of volatiles also may be used. 

5.3.1.1 Injection port—Volatiles interface, 

split, splitless, temperature programmable 

split/splitless (PTV), large volume, oncolumn, backflushed, or other. 

5.3.1.2 Carrier gas—Data in the tables in 

this method were obtained using helium 

carrier gas. If another carrier gas is used, 

analytical conditions may need to be 

adjusted for optimum performance, and 

calibration and all QC tests must be 

performed with the alternative carrier gas. 

See Section 4.3 for precautions regarding the 

use of hydrogen as a carrier gas. 

5.3.2 GC column—See the footnote to 

Table 3. Other columns or column systems 

may be used provided all requirements in 

this method are met. 

5.3.3 Mass spectrometer—Capable of 

repetitively scanning from 35–260 Daltons 

(amu) every 2 seconds or less, utilizing a 70 

eV (nominal) electron energy in the electron 

impact ionization mode, and producing a 

mass spectrum which meets all criteria in 

Table 4 when 50 ng or less of 4- 

bromofluorobenzene (BFB) is injected 

through the GC inlet. If acrolein, 

acrylonitrile, chloromethane, and vinyl 

chloride are to be determined, it may be 

necessary to scan from below 25 Daltons to 

measure the peaks in the 26–35 Dalton range 

for reliable identification. 

5.3.4 GC/MS interface—Any GC to MS 

interface that meets all performance 

requirements in this method may be used. 

5.3.5 Data system—A computer system 

must be interfaced to the mass spectrometer 

that allows continuous acquisition and 

storage of mass spectra throughout the 

chromatographic program. The computer 

must have software that allows searching any 

GC/MS data file for specific m/z’s (masses) 

and plotting m/z abundances versus time or 

scan number. This type of plot is defined as 

an extracted ion current profile (EICP). 

Software must also be available that allows 

integrating the abundance at any EICP 

between specified time or scan number 

limits. 

5.4 Syringes—Graduated, 5–25 mL, glass 

hypodermic with Luerlok tip, compatible 

with the purging device. 

5.5 Micro syringes—Graduated, 25–1000 

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. 

6.3.4 Other trap materials are acceptable 

if performance requirements in this method 

are met. 

6.4 Methanol—Demonstrated to be free 

from the target analytes and potentially 

interfering compounds. 

6.5 Stock standard solutions—Stock 

standard solutions may be prepared from 

pure materials, or purchased as certified 

solutions. Traceability must be to the 

National Institute of Standards and 

Technology (NIST) or other national or 

international standard, when available. Stock 

solution concentrations alternative to those 

below may be used. Prepare stock standard 

solutions in methanol using assayed liquids 

or gases as appropriate. Because some of the 

compounds in this method are known to be 

toxic, primary dilutions should be prepared 

in a hood, and a NIOSH/MESA approved 

toxic gas respirator should be worn when 

high concentrations of neat materials are 

handled. The following procedure may be 

used to prepare standards from neat 

materials: 

6.5.1 Place about 9.8 mL of methanol in 

a 10-mL ground-glass-stoppered volumetric 

flask. Allow the flask to stand, unstoppered, 

for about 10 minutes or until all alcohol 

wetted surfaces have dried. Weigh the flask 

to the nearest 0.1 mg. 

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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. 

Unless stated otherwise in this method, store 

non-aqueous standards in fluoropolymerlined screw-cap, or heat-sealed, glass 

containers, in the dark at ¥20 to ¥10 °C. 

Store aqueous standards; e.g., the aqueous 

LCS (section 8.4.1) in the dark at ≤6 °C (but 

do not freeze) with zero headspace; e.g., in 

VOA vials (section 5.1.1). Standards prepared 

by the laboratory may be stored for up to one 

month, except when comparison with QC 

check standards indicates that a standard has 

degraded or become more concentrated due 

to evaporation, or unless the laboratory has 

data on file to prove stability for a longer 

period. Commercially prepared standards 

may be stored until the expiration date 

provided by the vendor, except when 

comparison with QC check standards 

indicates that a standard has degraded or 

become more concentrated due to 

evaporation, or unless the laboratory has data 

from the vendor on file to prove stability for 

a longer period. 

Note: 2-Chloroethylvinyl ether has been 

shown to be stable for as long as one month 

if prepared as a separate standard, and the 

other analytes have been shown to be stable 

for as long as 2 months if stored at less than 

¥10 °C with minimal headspace in sealed, 

miniature inert-valved vials. 

6.6 Secondary dilution standards—Using 

stock solutions, prepare secondary dilution 

standards in methanol that contain the 

compounds of interest, either singly or 

mixed. Secondary dilution standards should 

be prepared at concentrations such that the 

aqueous calibration standards prepared in 

section 7.3.2 will bracket the working range 

of the analytical system. 

6.7 Surrogate standard spiking solution— 

Select a minimum of three surrogate 

compounds from Table 5. The surrogates 

selected should match the purging 

characteristics of the analytes of interest as 

closely as possible. Prepare a stock standard 

solution for each surrogate in methanol as 

described in section 6.5, and prepare a 

solution for spiking the surrogates into all 

blanks, LCSs, and MS/MSDs. Prepare the 

spiking solution such that spiking a small 

volume will result in a constant 

concentration of the surrogates. For example, 

add 10 mL of a spiking solution containing 

the surrogates at a concentration of 15 mg/mL 

in methanol to a 5-mL aliquot of water to 

produce a concentration of 30 mg/L for each 

surrogate. Other surrogate concentrations 

may be used. Store per section 6.5.4. 

6.8 BFB standard—Prepare a solution of 

BFB in methanol as described in Sections 6.5 

and 6.6. The solution should be prepared 

such that an injection or purging from water 

will result in introduction of ≤ 50 ng into the 

GC. BFB may be included in a mixture with 

the internal standards and/or surrogates. 

6.9 Quality control check sample 

concentrate—See Section 8.2.1. 

7. Calibration 

7.1 Assemble a purge-and-trap system 

that meets the specifications in Section 5.2. 

Prior to first use, condition the trap overnight 

at 180 °C by backflushing with gas at a flow 

rate of at least 20 mL/min. Condition the trap 

after each analysis at a temperature and time 

sufficient to prevent detectable 

concentrations of the analytes or 

contaminants in successive analyses. 

7.2 Connect the purge-and-trap system to 

the gas chromatograph. The gas 

chromatograph should be operated using 

temperature and flow rate conditions 

equivalent to those given in the footnotes to 

Table 3. Alternative temperature and flow 

rate conditions may be used provided that 

performance requirements in this method are 

met. 

7.3 Internal standard calibration. 

7.3.1 Internal standards. 

7.3.1.1 Select three or more internal 

standards similar in chromatographic 

behavior to the compounds of interest. 

Suggested internal standards are listed in 

Table 5. Use the base peak m/z as the 

primary m/z for quantification of the 

standards. If interferences are found at the 

base peak, use one of the next two most 

intense m/z’s for quantitation. Demonstrate 

that measurements of the internal standards 

are not affected by method or matrix 

interferences. 

7.3.1.2 To assure accurate analyte 

identification, particularly when selected ion 

monitoring (SIM) is used, it may be 

advantageous to include more internal 

standards than those suggested in Section 

7.3.1.1. An analyte will be located most 

accurately if its retention time relative to an 

internal standard is in the range of 0.8 to 1.2. 

7.3.1.3 Prepare a stock standard solution 

for each internal standard in methanol as 

described in Section 6.5, and prepare a 

solution for spiking the internal standards 

into all blanks, LCSs, and MS/MSDs. Prepare 

the spiking solution such that spiking a small 

volume will result in a constant 

concentration of the internal standards. For 

example, add 10 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 to produce 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 per 

section 6.5.4. 

7.3.2 Calibration. 

7.3.2.1 Calibration standards. 

7.3.2.1.1 Prepare calibration standards at 

a minimum of five concentration levels for 

each analyte of interest by adding 

appropriate volumes of one or more stock 

standards to a fixed volume (e.g., 40 mL) of 

reagent water in volumetric glassware. Fewer 

levels may be necessary for some analytes 

based on the sensitivity of the MS, but no 

fewer than 3 levels may be used, and only 

the highest or lowest point(s) may be 

dropped from the calibration. One of the 

calibration standards should be at a 

concentration at or below the ML or as 

specified by a regulatory/control authority or 

in a permit. The ML value may be rounded 

to a whole number that is more convenient 

for preparing the standard, but must not 

exceed the ML values listed in Table 1 for 

those analytes which list ML values. 

Alternatively, the laboratory may establish 

the ML for each analyte based on the 

concentration of the lowest calibration 

standard in a series of standards produced in 

the laboratory or obtained from a commercial 

vendor, again, provided that the ML value 

does not exceed the MLs in Table 1, and 

provided that the resulting calibration meets 

the acceptance criteria in Section 7.3.4, based 

on the RSD, RSE, or 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 = 0) calibration. 

Calibrations higher than second order are not 

allowed. 

7.3.2.1.2 To each calibration standard or 

standard mixture, add a known constant 

volume of the internal standard spiking 

solution (section 7.3.1.3) and surrogate 

standard spiking solution (section 6.7) or the 

combined internal standard solution and 

surrogate spiking solution (section 7.3.1.3). 

Aqueous standards may be stored up to 24 

hours, if held in sealed vials with zero 

headspace. If not so stored, they must be 

discarded after one hour. 

7.3.2.2 Prior to analysis of the calibration 

standards, analyze the BFB standard (section 

6.8) and adjust the scan rate of the MS to 

produce a minimum of 5 mass spectra across 

the BFB GC peak, but do not exceed 2 

seconds per scan. Adjust instrument 

conditions until the BFB criteria in Table 4 

are met. Once the scan conditions are 

established, they must be used for analyses 

of all standards, blanks, and samples. 

Note: The BFB spectrum may be evaluated 

by summing the intensities of the m/z’s 

across the GC peak, subtracting the 

background at each m/z in a region of the 

chromatogram within 20 scans of but not 

including any part of the BFB peak. The BFB 

spectrum may also be evaluated by fitting a 

Gaussian to each m/z and using the intensity 

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at the maximum for each Gaussian, or by 

integrating the area at each m/z and using the 

integrated areas. Other means may be used 

for evaluation of the BFB spectrum so long 

as the spectrum is not distorted to meet the 

criteria in Table 4. 

7.3.2.3 Analyze the mid-point standard 

and enter or review the retention time, 

relative retention time, mass spectrum, and 

quantitation m/z in the data system for each 

analyte of interest, surrogate, and internal 

standard. If additional analytes (Table 2) are 

to be quantified, include these analytes in the 

standard. The mass spectrum for each analyte 

must be comprised of a minimum of 2 m/z’s; 

3 to 5 m/z’s assure more reliable analyte 

identification. Suggested quantitation m/z’s 

are shown in Table 6 as the primary m/z. For 

analytes in Table 6 that do not have a 

secondary m/z, acquire a mass spectrum and 

enter one or more secondary m/z’s for more 

reliable identification. If an interference 

occurs at the primary m/z, use one of the 

secondary m/z’s or an alternative m/z. A 

single m/z only is required for quantitation. 

7.3.2.4 For SIM operation, determine the 

analytes in each descriptor, the quantitation 

m/z for each analyte (the quantitation m/z 

can be the same as for full-scan operation; 

Section 7.3.2.3), the dwell time on each m/ 

z for each analyte, and the beginning and 

ending retention time for each descriptor. 

Analyze the verification standard in scan 

mode to verify m/z’s and establish retention 

times for the analytes. There must be a 

minimum of two m/z’s for each analyte to 

assure analyte identification. To maintain 

sensitivity, the number of m/z’s in a 

descriptor should be limited. For example, 

for a descriptor with 10 m/z’s and a 

chromatographic peak width of 5 sec, a dwell 

time of 100 ms at each m/z would result in 

a scan time of 1 second and provide 5 scans 

across the GC peak. The quantitation m/z 

will usually be the most intense peak in the 

mass spectrum. The quantitation m/z and 

dwell time may be optimized for each 

analyte. The acquisition table used for SIM 

must take into account the mass defect 

(usually less than 0.2 Dalton) that can occur 

at each m/z monitored. Refer to the footnotes 

to Table 3 for establishing operating 

conditions and to section 7.3.2.2 for 

establishing scan conditions. 

7.3.2.5 For combined scan and SIM 

operation, set up the scan segments and 

descriptors to meet requirements in sections 

7.3.2.2–7.3.2.4. Analyze unfamiliar samples 

in the scan mode to assure that the analytes 

of interest are determined. 

7.3.3 Analyze each calibration standard 

according to Section 10 and tabulate the area 

at the quantitation m/z against concentration 

for each analyte of interest, surrogate, and 

internal standard. Calculate the response 

factor (RF) for each compound at each 

concentration using Equation 1. 

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 re-calibrated. 

Note: Using capillary columns and current 

instrumentation, it is quite likely that a 

laboratory can calibrate the target analytes in 

this method and achieve a linearity metric 

(either RSD or RSE) well below 35%. 

Therefore, laboratories are permitted to use 

more stringent acceptance criteria for 

calibration than described here, for example, 

to harmonize their application of this method 

with those from other sources. 

7.4 Calibration verification—Because the 

analytical system is calibrated by purge of the 

analytes from water, calibration verification 

is performed using the laboratory control 

sample (LCS). See section 8.4 for 

requirements for calibration verification 

using the LCS, and the Glossary for further 

definition. 

8. Quality Control 

8.1 Each laboratory that uses this method 

is required to operate a formal quality 

assurance program. The minimum 

requirements of this program consist of an 

initial demonstration of laboratory capability 

and ongoing analysis of spiked samples and 

blanks to evaluate and document data quality 

(40 CFR 136.7). The laboratory must maintain 

records to document the quality of data 

generated. Results of ongoing performance 

tests are compared with established QC 

acceptance criteria to determine if the results 

of analyses meet performance requirements 

of this method. When results of spiked 

samples do not meet the QC acceptance 

criteria in this method, a quality control 

check sample (laboratory control sample; 

LCS) must be analyzed to confirm that the 

measurements were performed in an 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. On a continuing 

basis, the laboratory must repeat 

demonstration of capability (DOC) at least 

annually. 

8.1.2 In recognition of advances that are 

occurring in analytical technology, and to 

overcome matrix interferences, the laboratory 

is permitted certain options (section 1.5 and 

40 CFR 136.6(b)) to improve separations or 

lower the costs of measurements. These 

options may include an alternative purgeand-trap device, and changes in both column 

and type of mass spectrometer (see 40 CFR 

136.6(b)(4)(xvi)). Alternative determinative 

techniques, such as substitution of 

spectroscopic or immunoassay techniques, 

and changes that degrade method 

performance, are not allowed. If an analytical 

technique other than GC/MS is used, that 

technique must have a specificity equal to or 

greater than the specificity of GC/MS for the 

analytes of interest. The laboratory is also 

encouraged to participate in intercomparison and performance evaluation 

studies (see section 8.8). 

8.1.2.1 Each time a modification is made 

to this method, the laboratory is required to 

repeat the procedure in section 8.2. If the 

detection limit of the method will be affected 

by the change, the laboratory must 

demonstrate that the MDLs (40 CFR part 136, 

appendix B) are lower than one-third the 

regulatory compliance limit or the MDLs in 

this method, whichever are greater. If 

calibration will be affected by the change, the 

instrument must be recalibrated per section 

7. Once the modification is demonstrated to 

produce results equivalent or superior to 

results produced by this method, that 

modification may be used routinely 

thereafter, so long as the other requirements 

in this method are met (e.g., matrix spike/

matrix spike duplicate recovery and relative 

percent difference). 

8.1.2.1.1 If a modification is to be applied 

to a specific discharge, the laboratory must 

prepare and analyze matrix spike/matrix 

spike duplicate (MS/MSD) samples (Section 

8.3) and LCS samples (section 8.4). The 

laboratory must include internal standards 

and surrogates (section 8.7) in each of the 

samples. The MS/MSD and LCS samples 

must be fortified with the analytes of interest 

(section 1.3.). If the modification is for 

nationwide use, MS/MSD samples must be 

prepared from a minimum of nine different 

discharges (See section 8.1.2.1.2), and all QC 

acceptance criteria in this method must be 

met. This evaluation only needs to be 

performed once, other than for the routine 

QC required by this method (for example it 


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could be performed by the vendor of the 

alternative materials) but any laboratory 

using that specific material must have the 

results of the study available. This includes 

a full data package with the raw data that 

will allow an independent reviewer to verify 

each determination and calculation 

performed by the laboratory (see section 

8.1.2.2.5, items (a)–(l)). 

8.1.2.1.2 Sample matrices on which MS/ 

MSD tests must be performed for nationwide 

use of an allowed modification: 

(a) Effluent from a publicly owned 

treatment works (POTW). 

(b) ASTM D5905 Standard Specification 

for Substitute Wastewater. 

(c) Sewage sludge, if sewage sludge will be 

in the permit. 

(d) ASTM D1141 Standard Specification 

for Substitute Ocean Water, if ocean water 

will be in the permit. 

(e) Untreated and treated wastewaters up to 

a total of nine matrix types (see https://

www.epa.gov/eg/industrial-effluentguidelines for a list of industrial categories 

with existing effluent guidelines). 

(i) At least one of the above wastewater 

matrix types must have at least one of the 

following characteristics: 

(A) Total suspended solids greater than 40 

mg/L. 

(B) Total dissolved solids greater than 100 

mg/L. 

(C) Oil and grease greater than 20 mg/L. 

(D) NaCl greater than 120 mg/L. 

(E) CaCO3 greater than 140 mg/L. 

(ii) Results of MS/MSD tests must meet QC 

acceptance criteria in section 8.3. 

(f) A proficiency testing (PT) sample from 

a recognized provider, in addition to tests of 

the nine matrices (section 8.1.2.1.1). 

8.1.2.2 The laboratory is required to 

maintain records of modifications made to 

this method. These records include the 

following, at a minimum: 

8.1.2.2.1 The names, titles, and business 

street addresses, telephone numbers, and 

email addresses of the analyst(s) that 

performed the analyses and modification, 

and of the quality control officer that 

witnessed and will verify the analyses and 

modifications. 

8.1.2.2.2 A list of analytes, by name and 

CAS Registry Number. 

8.1.2.2.3 A narrative stating reason(s) for 

the modifications. 

8.1.2.2.4 Results from all quality control 

(QC) tests comparing the modified method to 

this method, including: 

(a) Calibration (section 7). 

(b) Calibration verification/LCS (section 

8.4). 

(c) Initial demonstration of capability 

(section 8.2). 

(d) Analysis of blanks (section 8.5). 

(e) Matrix spike/matrix spike duplicate 

analysis (section 8.3). 

(f) Laboratory control sample analysis 

(section 8.4). 

8.1.2.2.5 Data that will allow an 

independent reviewer to validate each 

determination by tracing the instrument 

output (peak height, area, or other signal) to 

the final result. These data are to include: 

(a) Sample numbers and other identifiers. 

(b) Analysis dates and times. 

(c) Analysis sequence/run chronology. 

(d) Sample volume (Section 10). 

(e) Sample dilution (Section 13.2). 

(f) Instrument and operating conditions. 

(g) Column (dimensions, material, etc). 

(h) Operating conditions (temperature 

program, flow rate, etc). 

(i) Detector (type, operating conditions, 

etc). 

(j) Chromatograms, mass spectra, and other 

recordings of raw data. 

(k) Quantitation reports, data system 

outputs, and other data to link the raw data 

to the results reported. 

(l) A written Standard Operating Procedure 

(SOP). 

8.1.2.2.6 Each individual laboratory 

wishing to use a given modification must 

perform the start-up tests in section 8.1.2 

(e.g., DOC, MDL), with the modification as an 

integral part of this method prior to applying 

the modification to specific discharges. 

Results of the DOC must meet the QC 

acceptance criteria in Table 7 for the analytes 

of interest (section 1.3), and the MDLs must 

be equal to or lower than the MDLs in Table3 

for the analytes of interest 

8.1.3 Before analyzing samples, the 

laboratory must analyze a blank to 

demonstrate that interferences from the 

analytical system, labware, and reagents are 

under control. Each time a batch of samples 

is analyzed or reagents are changed, a blank 

must be analyzed as a safeguard against 

laboratory contamination. Requirements for 

the blank are given in section 8.5. 

8.1.4 The laboratory must, on an ongoing 

basis, spike and analyze samples to monitor 

and evaluate method and laboratory 

performance on the sample matrix. The 

procedure for spiking and analysis is given 

in section 8.3. 

8.1.5 The laboratory must, on an ongoing 

basis, demonstrate through analysis of a 

quality control check sample (laboratory 

control sample, LCS; on-going precision and 

recovery sample, OPR) that the measurement 

system is in control. This procedure is given 

in section 8.4. 

8.1.6 The laboratory must maintain 

performance records to document the quality 

of data that is generated. This procedure is 

given in section 8.8. 

8.1.7 The large number of analytes tested 

in performance tests in this method present 

a substantial probability that one or more 

will fail acceptance criteria when many 

analytes are tested simultaneously, and a retest is allowed if this situation should occur. 

If, however, continued re-testing results in 

further repeated failures, the laboratory must 

document and report the failures (e.g., as 

qualifiers on results), unless the failures are 

not required to be reported as determined by 

the regulatory/control authority. Results 

associated with a QC failure for an analyte 

regulated in a discharge cannot be used to 

demonstrate regulatory compliance. QC 

failures do not relieve a discharger or 

permittee of reporting timely results. 

8.2 Initial demonstration of capability 

(DOC)—To establish the ability to generate 

acceptable recovery and precision, the 

laboratory must perform the DOC in sections 

8.2.1 through 8.2.6 for the analytes of 

interest. The laboratory must also establish 

MDLs for the analytes of interest using the 

MDL procedure at 40 CFR part 136, appendix 

B. The laboratory’s MDLs must be equal to 

or lower than those listed in Table 1 for those 

analytes which list MDL values, or lower 

than one-third the regulatory compliance 

limit, whichever is greater. For MDLs not 

listed in Table 1, the laboratory must 

determine the MDLs using the MDL 

procedure at 40 CFR part 136, appendix B 

under the same conditions used to determine 

the MDLs for the analytes listed in Table 1. 

All procedures used in the analysis must be 

included in the DOC. 

8.2.1 For the DOC, a QC check sample 

concentrate (LCS concentrate) containing 

each analyte of interest (section 1.3) is 

prepared in methanol. The QC check sample 

concentrate must be prepared independently 

from those used for calibration, but may be 

from the same source as the second-source 

standard used for calibration verification/

LCS (sections 7.4 and 8.4). The concentrate 

should produce concentrations of the 

analytes of interest in water at the mid-point 

of the calibration range, and may be at the 

same concentration as the LCS (section 8.4). 

Note: QC check sample concentrates are no 

longer available from EPA. 

8.2.2 Using a pipet or micro-syringe, 

prepare four LCSs by adding an appropriate 

volume of the concentrate to each of four 

aliquots of reagent water. The volume of 

reagent water must be the same as the 

volume that will be used for the sample, 

blank (section 8.5), and MS/MSD (section 

8.3). A volume of 5 mL and a concentration 

of 20 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). 

Alternatively, acceptance criteria for analytes 

not listed in Table 7 may be based on 

laboratory control charts. If s and X for all 

analytes of interest meet the acceptance 

criteria, system performance is acceptable 

and analysis of blanks and samples may 

begin. If any individual s exceeds the 

precision limit or any individual X falls 

outside the range for recovery, system 

performance is unacceptable for that analyte. 

Note: The large number of analytes in 

Tables 1 and 2 present a substantial 

probability that one or more will fail at least 

one of the acceptance criteria when many or 

all analytes are determined simultaneously. 

Therefore, the analyst is permitted to conduct 

a ‘‘re-test’’ as described in section 8.2.6. 

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8.2.6 When one or more of the analytes 

tested fail at least one of the acceptance 

criteria, repeat the test for only the analytes 

that failed. If results for these analytes pass, 

system performance is acceptable and 

analysis of samples and blanks may proceed. 

If one or more of the analytes again fail, 

system performance is unacceptable for the 

analytes that failed the acceptance criteria. 

Correct the problem and repeat the test 

(section 8.2). See section 8.1.7 for disposition 

of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between this pair 

of tests. 

8.3 Matrix spike and matrix spike 

duplicate (MS/MSD)—The purpose of the 

MS/MSD requirement is to provide data that 

demonstrate the effectiveness of the method 

as applied to the samples in question by a 

given laboratory, and both the data user 

(discharger, permittee, regulated entity, 

regulatory/control authority, customer, other) 

and the laboratory share responsibility for 

provision of such data. The data user should 

identify the sample and the analytes of 

interest (section 1.3) to be spiked and provide 

sufficient sample volume to perform MS/

MSD analyses. The laboratory must, on an 

ongoing basis, spike at least 5% of the 

samples in duplicate from each discharge 

being monitored to assess accuracy (recovery 

and precision). If direction cannot be 

obtained from the data user, the laboratory 

must spike at least one sample in duplicate 

per extraction batch of up to 20 samples with 

the analytes in Table 1. Spiked sample 

results should be reported only to the data 

user whose sample was spiked, or as 

requested or required by a regulatory/control 

authority, or in a permit. 

8.3.1 If, as in compliance monitoring, the 

concentration of a specific analyte will be 

checked against a regulatory concentration 

limit, the concentration of the spike should 

be at that limit; otherwise, the concentration 

of the spike should be one to five times 

higher than the background concentration 

determined in section 8.3.2, at or near the 

mid-point of the calibration range, or at the 

concentration in the LCS (section 8.4) 

whichever concentration would be larger. 

8.3.2 Analyze one sample aliquot to 

determine the background concentration (B) 

of the each analyte of interest. If necessary, 

prepare a new check sample concentrate 

(section 8.2.1) appropriate for the background 

concentration. Spike and analyze two 

additional sample aliquots, and determine 

the concentration after spiking (A1 and A2) of 

each analyte. Calculate the percent recoveries 

(P1 and P2) as 100 (A1¥B)/T and 100 

(A2¥B)/T, where T is the known true value 

of the spike. Also calculate the relative 

percent difference (RPD) between the 

concentrations (A1 and A2) as 200 √A1¥A2√/ 

(A1 + A2). If necessary, adjust the 

concentrations used to calculate the RPD to 

account for differences in the volumes of the 

spiked aliquots. 

8.3.3 Compare the percent recoveries (P1

and P2) and the RPD for each analyte in the 

MS/MSD aliquots with the corresponding QC 

acceptance criteria in Table 7. A laboratory 

may develop and apply QC acceptance 

criteria more restrictive than the criteria in 

Table 7, if desired. 

8.3.3.1 If any individual P falls outside 

the designated range for recovery in either 

aliquot, or the RPD limit is exceeded, the 

result for the analyte in the unspiked sample 

is suspect. See Section 8.1.7 for disposition 

of failures. 

8.3.3.2 The acceptance criteria in Table 7 

were calculated to include an allowance for 

error in measurement of both the background 

and spike concentrations, assuming a spike 

to background ratio of 5:1. This error will be 

accounted for to the extent that the spike to 

background ratio approaches 5:1 (Reference 

13) and is applied to spike concentrations of 

20 mg/L and higher. If spiking is performed 

at a concentration lower than 20 mg/L, the 

laboratory must use the QC acceptance 

criteria in Table 7, the optional QC 

acceptance criteria calculated for the specific 

spike concentration in Table 8, or optional 

in-house criteria (Section 8.3.4). To use the 

acceptance criteria in Table 8: (1) Calculate 

recovery (X’) using the equation in Table 8, 

substituting the spike concentration (T) for C; 

(2) Calculate overall precision (S’) using the 

equation in Table 8, substituting X’ for X; (3) 

Calculate the range for recovery at the spike 

concentration as (100 X’/T) ± 2.44(100 S’/

T)% (Reference 4). For analytes of interest in 

Tables 1 and 2 not listed in Table 7, QC 

acceptance criteria must be developed by the 

laboratory. EPA has provided guidance for 

development of QC acceptance criteria 

(References 11 and 12). Alternatively, 

acceptance criteria may be based on 

laboratory control charts. In-house LCS QC 

acceptance criteria must be updated at least 

every two years. 

8.3.4 After analysis of a minimum of 20 

MS/MSD samples for each target analyte and 

surrogate, and if the laboratory chooses to 

develop and apply in-house QC limits, the 

laboratory should calculate and apply inhouse 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 inhouse QC limits must be updated at least 

every two years and re-established after any 

major change in the analytical 

instrumentation or process. If in-house QC 

limits are developed, at least 80% of the 

analytes tested in the MS/MSD must have inhouse QC acceptance criteria that are tighter 

than those in Table 7 and the remaining 

analytes (those other than the analytes 

included in the 80%) must meet the 

acceptance criteria in Table 7. If an in-house 

QC limit for the RPD is greater than the limit 

in Table 7, then the limit in Table 7 must be 

used. Similarly, if an in-house lower limit for 

recovery is below the lower limit in Table 7, 

then the lower limit in Table 7 must be used, 

and if an in-house upper limit for recovery 

is above the upper limit in Table 7, then the 

upper limit in Table 7 must be used. 

8.4 Calibration verification/laboratory 

control sample (LCS)—The working 

calibration curve or RF must be verified 

immediately after calibration and at the 

beginning of each 12-hour shift by the 

measurement of an LCS. The LCS must be 

from a source different from the source used 

for calibration (section 7.3.2.1), but may be 

the same as the sample prepared for the DOC 

(section 8.2.1). 

Note: The 12-hour shift begins after 

analysis of BFB, the LCS, and the blank, and 

ends 12 hours later. BFB, the LCS, and blank 

are outside of the 12-hour shift (Section 

11.4). The MS and MSD are treated as 

samples and are analyzed within the 12-hour 

shift. 

8.4.1 Prepare the LCS by adding QC 

check sample concentrate (section 8.2.1) to 

reagent water. Include all analytes of interest 

(Section 1.3) in the LCS. The volume of 

reagent water must be the same as the 

volume used for the sample, blank (Section 

8.5), and MS/MSD (section 8.3). Also add an 

aliquot of the surrogate solution (Section 6.7) 

and internal standard solution (section 

7.3.1.3). The concentration of the analytes in 

reagent water should be the same as the 

concentration in the DOC (section 8.2.2). 

8.4.2 Analyze the LCS prior to analysis of 

field samples in the batch of samples 

analyzed during the 12-hour shift (see the 

Note at section 8.4). Determine the 

concentration (A) of each analyte. Calculate 

the percent recovery (Q) as 100 (A/T) %, 

where T is the true value of the concentration 

in the LCS. 

8.4.3 Compare the percent recovery (Q) 

for each analyte with its corresponding QC 

acceptance criterion in Table 7. For analytes 

of interest in Tables 1 and 2 not listed in 

Table 7, use the QC acceptance criteria 

developed for the LCS (section 8.4.5). If the 

recoveries for all analytes of interest fall 

within their respective QC acceptance 

criteria, analysis of blanks and field samples 

may proceed. If any individual Q falls 

outside the range, proceed according to 

section 8.4.4. 

Note: The large number of analytes in 

Tables 1—2 present a substantial probability 

that one or more will fail the acceptance 

criteria when all analytes are tested 

simultaneously. Because a re-test is allowed 

in event of failure (sections 8.1.7 and 8.4.3), 

it may be prudent to analyze two LCSs 

together and evaluate results of the second 

analysis against the QC acceptance criteria 

only if an analyte fails the first test. 

8.4.4 Repeat the test only for those 

analytes that failed to meet the acceptance 

criteria (Q). If these analytes now pass, 

system performance is acceptable and 

analysis of blanks and samples may proceed. 

Repeated failure, however, will confirm a 

general problem with the measurement 

system. If this occurs, repeat the test (section 

8.4.2). using a fresh LCS (section 8.2.2) or an 

LCS prepared with a fresh QC check sample 

concentrate (section 8.2.1), or perform and 

document system repair. Subsequent to 

repair, repeat the calibration verification/LCS 

test (section 8.4). If the acceptance criteria for 

Q cannot be met, re-calibrate the instrument 

(section 7). See section 8.1.7 for disposition 

of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between the pair 

of tests. 

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8.4.5 After analysis of 20 LCS samples, 

and if the laboratory chooses to develop and 

apply in-house QC limits, the laboratory 

should calculate and apply in-house QC 

limits for recovery to future LCS samples 

(section 8.4). Limits for recovery in the LCS 

calculated as the mean recovery ±3 standard 

deviations. A minimum of 80% of the 

analytes tested for in the LCS must have QC 

acceptance criteria tighter than those in Table 

7, and the remaining analytes (those other 

than the analytes included in the 80%) must 

meet the acceptance criteria in Table 7. If an 

in-house lower limit for recovery is lower 

than the lower limit in Table 7, the lower 

limit in Table 7 must be used, and if an inhouse upper limit for recovery is higher than 

the upper limit in Table 7, the upper limit 

in Table 7 must be used. Many of the 

analytes and surrogates do not have 

acceptance criteria. The laboratory should 

use 60–140% as interim acceptance criteria 

for recoveries of spiked analytes that do not 

have recovery limits specified in Table 7, and 

least 80% of the analytes should meet the 

60–140% interim criteria until in-house LCS 

limits are developed. Alternatively, 

acceptance criteria for analytes that do not 

have recovery limits in Table 7 may be based 

on laboratory control charts. In-house QC 

acceptance criteria must be updated at least 

every two years. 

8.5 Blank—A blank must be analyzed 

prior to each 12-hour shift to demonstrate 

freedom from contamination. A blank must 

also be analyzed after a sample containing a 

high concentration of an analyte or 

potentially interfering compound to 

demonstrate freedom from carry-over. 

8.5.1 Spike the internal standards and 

surrogates into the blank. Analyze the blank 

immediately after analysis of the LCS 

(Section 8.4) and prior to analysis of the MS/ 

MSD and samples to demonstrate freedom 

from contamination. 

8.5.2 If any analyte of interest is found in 

the blank: At a concentration greater than the 

MDL for the analyte, at a concentration 

greater than one-third the regulatory 

compliance limit, or at a concentration 

greater than one-tenth the concentration in a 

sample analyzed during the 12-hour shift 

(section 8.4), whichever is greater; analysis of 

samples must be halted and samples affected 

by the blank must be re-analyzed. If, 

however, continued re-testing results in 

repeated blank contamination, the laboratory 

must document and report the failures (e.g., 

as qualifiers on results), unless the failures 

are not required to be reported as determined 

by the regulatory/control authority. Results 

associated with blank contamination for an 

analyte regulated in a discharge cannot be 

used to demonstrate regulatory compliance. 

QC failures do not relieve a discharger or 

permittee of reporting timely results. 

8.6 Surrogate recoveries—The laboratory 

must evaluate surrogate recovery data in each 

sample against its in-house surrogate 

recovery limits for surrogates that do not 

have acceptance criteria in Table 7. The 

laboratory may use 60–140% as interim 

acceptance criteria for recoveries for 

surrogates not listed in Table 5. At least 80% 

of the surrogates must meet the 60–140% 

interim criteria until in-house limits are 

developed. Alternatively, surrogate recovery 

limits may be developed from laboratory 

control charts. 

8.6.1 Spike the surrogates into all 

samples, blanks, LCSs, and MS/MSDs. 

Compare surrogate recoveries against the QC 

acceptance criteria in Table 7. For surrogates 

in Table 5 without QC acceptance criteria in 

Table 7, and for other surrogates that may be 

used by the laboratory, limits must be 

developed by the laboratory. EPA has 

provided guidance for development of QC 

acceptance criteria (References 11 and 12). 

Alternatively, surrogate recovery limits may 

be developed from laboratory control charts. 

In-house QC acceptance criteria must be 

updated at least every two years. 

8.6.2 If any recovery fails its criteria, 

attempt to find and correct the cause of the 

failure. See section 8.1.7 for disposition of 

failures. 

8.7 Internal standard responses. 

8.7.1 Calibration verification/LCS—The 

responses (GC peak heights or areas) of the 

internal standards in the calibration 

verification/LCS must be within 50% to 

200% (1/2 to 2×) of their respective responses 

in the mid-point calibration standard. If they 

are not, repeat the LCS test using a fresh QC 

check sample (section 8.4.1) or perform and 

document system repair. Subsequent to 

repair, repeat the calibration verification/LCS 

test (section 8.4). If the responses are still not 

within 50% to 200%, re-calibrate the 

instrument (section 7) and repeat the 

calibration verification/LCS test. 

8.7.2 Samples, blanks, and MS/MSDs— 

The responses (GC peak heights or areas) of 

each internal standard in each sample, blank, 

and MS/MSD must be within 50% to 200% 

(1/2 to 2×) of its respective response in the 

mid-point calibration standard. If, as a group, 

all internal standards are not within this 

range, perform and document system repair, 

repeat the calibration verification/LCS test 

(section 8.4), and re-analyze the affected 

samples. If a single internal standard is not 

within the 50% to 200% range, use an 

alternative internal standard for quantitation 

of the analyte referenced to the affected 

internal standard. It may be necessary to use 

the data system to calculate a new response 

factor from calibration data for the alternative 

internal standard/analyte pair. If an internal 

standard fails the 50–200% criteria and no 

analytes are detected in the sample, ignore 

the failure or report it if required by the 

regulatory/control authority. 

8.8 As part of the QC program for the 

laboratory, control charts or statements of 

accuracy for wastewater samples must be 

assessed and records maintained periodically 

(see 40 CFR 136.7(c)(1)(viii)). After analysis 

of five or more spiked wastewater samples as 

in section 8.3, calculate the average percent 

recovery (Px) and the standard deviation of 

the percent recovery (sp). Express the 

accuracy assessment as a percent interval 

from Px¥2sp to Px + 2sp. For example, if Px

= 90% and sp = 10%, the accuracy interval 

is expressed as 70–110%. Update the 

accuracy assessment for each analyte on a 

regular basis (e.g., after each 5–10 new 

accuracy measurements). If desired, 

statements of accuracy for laboratory 

performance, independent of performance on 

samples, may be developed using LCSs. 

8.9 It is recommended that the laboratory 

adopt additional quality assurance practices 

for use with this method. The specific 

practices that are most productive depend 

upon the needs of the laboratory and the 

nature of the samples. Field duplicates may 

be analyzed to assess the precision of 

environmental measurements. Whenever 

possible, the laboratory should analyze 

standard reference materials and participate 

in relevant performance evaluation studies. 

9. Sample Collection, Preservation, and 

Handling 

9.1 Collect the sample as a grab sample in 

a glass container having a total volume of at 

least 25 mL. Fill the sample bottle just to 

overflowing in such a manner that no air 

bubbles pass through the sample as the bottle 

is being filled. Seal the bottle so that no air 

bubbles are entrapped in it. If needed, collect 

additional sample(s) for the MS/MSD 

(section 8.3). 

9.2 Ice or refrigerate samples at ≤6 °C 

from the time of collection until analysis, but 

do not freeze. If residual chlorine is present, 

add sodium thiosulfate preservative (10 mg/ 

40 mL is sufficient for up to 5 ppm Cl2) to 

the empty sample bottle just prior to 

shipping to the sampling site. Any method 

suitable for field use may be employed to test 

for residual chlorine (Reference 14). Field 

test kits are also available for this purpose. 

If sodium thiosulfate interferes in the 

determination of the analytes, an alternative 

preservative (e.g., ascorbic acid or sodium 

sulfite) may be used. If preservative has been 

added, shake the sample vigorously for one 

minute. Maintain the hermetic seal on the 

sample bottle until time of analysis. 

9.3 If acrolein is to be determined, 

analyze the sample within 3 days. To extend 

the holding time to 14 days, acidify a 

separate sample to pH 4–5 with HCl using 

the procedure in section 9.7. 

9.4 Experimental evidence indicates that 

some aromatic compounds, notably benzene, 

toluene, and ethyl benzene are susceptible to 

rapid biological degradation under certain 

environmental conditions (Reference 3). 

Refrigeration alone may not be adequate to 

preserve these compounds in wastewaters for 

more than seven days. To extend the holding 

time for aromatic compounds to 14 days, 

acidify the sample to approximately pH 2 

using the procedure in section 9.7. 

9.5 If halocarbons are to be determined, 

either use the acidified aromatics sample in 

section 9.4 or acidify a separate sample to a 

pH of about 2 using the procedure in section 

9.7. 

9.6 The ethers listed in Table 2 are prone 

to hydrolysis at pH 2 when a heated purge 

is used. Aqueous samples should not be acid 

preserved if these ethers are of interest, or if 

the alcohols they would form upon 

hydrolysis are of interest and the ethers are 

anticipated to present. 

9.7 Sample acidification—Collect about 

500 mL of sample in a clean container and 

adjust the pH of the sample to 4–5 for 

acrolein (section 9.3), or to about 2 for the 

aromatic compounds (section 9.4) by adding 

1+1 HCl while swirling or stirring. Check the 

pH with narrow range pH paper. Fill a 

sample container as described in section 9.1. 

Alternatively, fill a precleaned vial (section 

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5.1.1) that contains approximately 0.25 mL of 

1+1 HCl with sample as in section 9.1. If 

preserved using this alternative procedure, 

the pH of the sample can be verified to be 

<2 after some of the sample is removed for 

analysis. Acidification will destroy 2- 

chloroethylvinyl ether; therefore, determine 

2-chloroethylvinyl ether from the unacidified 

sample. 

9.8 All samples must be analyzed within 

14 days of collection (Reference 3), unless 

specified otherwise in sections 9.3–9.7. 

10. Sample Purging and Gas Chromatography 

10.1 The footnote to Table 3 gives the 

suggested GC column and operating 

conditions MDLs and MLs for many of the 

analytes are given in Table 1. Retention times 

for many of the analytes are given in Table 

3. Sections 10.2 through 10.7 suggest 

procedures that may be used with a manual 

purge-and-trap system. Auto-samplers and 

other columns or chromatographic 

conditions may be used if requirements in 

this method are met. Prior to performing 

analyses, and between analyses, it may be 

necessary to bake the purge-and-trap and GC 

systems (section 3.3). 

10.2 Attach the trap inlet to the purging 

device, and set the purge-and-trap system to 

purge. Open the syringe valve located on the 

purging device sample introduction needle. 

10.3 Allow the sample to come to 

ambient temperature prior to pouring an 

aliquot into the syringe. Remove the plunger 

from a syringe and attach a closed syringe 

valve. Open the sample bottle (or standard) 

and carefully pour the sample into the 

syringe barrel to just short of overflowing. 

Replace the syringe plunger and compress 

the sample. Open the syringe valve and vent 

any residual air while adjusting the sample 

volume. Since this process of taking an 

aliquot destroys the validity of the sample for 

future analysis, the analyst should fill a 

second syringe at this time to protect against 

possible loss of data. Add the surrogate 

spiking solution (section 6.7) and internal 

standard spiking solution (section 7.3.1.3) 

through the valve bore, then close the valve. 

The surrogate and internal standards may be 

mixed and added as a single spiking solution. 

Autosamplers designed for purge-and-trap 

analysis of volatiles also may be used. 

10.4 Attach the syringe valve assembly to 

the syringe valve on the purging device. 

Open the syringe valve and inject the sample 

into the purging chamber. 

10.5 Close both valves and purge the 

sample at a temperature, flow rate, and 

duration sufficient to purge the less-volatile 

analytes onto the trap, yet short enough to 

prevent blowing the more-volatile analytes 

through the trap. The temperature, flow rate, 

and time should be determined by test. The 

same purge temperature, flow rate, and purge 

time must be used for all calibration, QC, and 

field samples. 

10.6 After the purge, set the purge-andtrap system to the desorb mode, and begin 

the temperature program of the gas 

chromatograph. Introduce the trapped 

materials to the GC column by rapidly 

heating the trap to the desorb temperature 

while backflushing the trap with carrier gas 

at the flow rate and for the time necessary to 

desorb the analytes of interest. The optimum 

temperature, flow rate, and time should be 

determined by test. The same temperature, 

desorb time, and flow rate must be used for 

all calibration, QC, and field samples. If 

heating of the trap does not result in sharp 

peaks for the early eluting analytes, the GC 

column may be used as a secondary trap by 

cooling to an ambient or subambient 

temperature. To avoid carry-over and 

interferences, maintain the trap at the desorb 

temperature and flow rate until the analytes, 

interfering compounds, and excess water are 

desorbed. The optimum conditions should be 

determined by test. 

10.7 Start MS data acquisition at the start 

of the desorb cycle and stop data collection 

when the analytes of interest, potentially 

interfering compounds, and water have 

eluted (see the footnote to Table 3 for 

conditions). 

10.8 Cool the trap to the purge 

temperature and return the trap to the purge 

mode. When the trap is cool, the next sample 

can be analyzed. 

11. Performance Tests 

11.1 At the beginning of each 12-hour 

shift during which standards or samples will 

be analyzed, perform the tests in sections 

11.2–11.3 to verify system performance. Use 

the instrument operating conditions in the 

footnotes to Table 3 for these performance 

tests. Alternative conditions may be used so 

as long as all QC requirements are met. 

11.2 BFB—Inject 50 ng of BFB solution 

directly on the column. Alternatively, add 

BFB to reagent water or an aqueous standard 

such that 50 ng or less of BFB will be 

introduced into the GC. Analyze according to 

section 10. Confirm that all criteria in section 

7.3.2.2 and Table 4 are met. If all criteria are 

not met, perform system repair, retune the 

mass spectrometer, and repeat the test until 

all criteria are met. 

11.3 Verify calibration with the LCS 

(section 8.4) after the criteria for BFB are met 

(Reference 15) and prior to analysis of a 

blank or sample. After verification, analyze a 

blank (section 8.5) to demonstrate freedom 

from contamination and carry-over at the 

MDL. Tests for BFB, the LCS, and the blank 

are outside of the 12-hour shift, and the 12- 

hour shift includes samples and matrix 

spikes and matrix spike duplicates (section 

8.4). The total time for analysis of BFB, the 

LCS, the blank, and the 12-hour shift must 

not exceed 14 hours. 

12. Qualitative Identification 

12.1 Identification is accomplished by 

comparison of results from analysis of a 

sample or blank with data stored in the GC/ 

MS data system (section 7.3.2.3). 

Identification of an analyte is confirmed per 

sections 12.1.1 through 12.1.4. 

12.1.1 The signals for the quantitation 

and secondary m/z’s stored in the data 

system (section 7.3.2.3) for each analyte of 

interest must be present and must maximize 

within the same two consecutive scans. 

12.1.2 The retention time for the analyte 

should be within ± 10 seconds of the analyte 

in the LCS run at the beginning of the shift 

(section 8.4). 

Note: Retention time windows other than 

± 10 seconds may be appropriate depending 

on the performance of the gas chromatograph 

or observed retention time drifts due to 

certain types of matrix effects. Relative 

retention time (RRT) may be used as an 

alternative to absolute retention times if 

retention time drift is a concern. RRT is a 

unitless quantity (see section 20.2), although 

some procedures refer to ‘‘RRT units’’ in 

providing the specification for the agreement 

between the RRT values in the sample and 

the LCS or other standard. When significant 

retention time drifts are observed, dilutions 

or spiked samples may help the analyst 

determine the effects of the matrix on elution 

of the target analytes and to assist in 

qualitative identification. 

12.1.3 Either the background corrected 

EICP areas, or the corrected relative 

intensities of the mass spectral peaks at the 

GC peak maximum, must agree within 50% 

to 200% (1⁄2 to 2 times) for the quantitation 

and secondary m/z’s in the reference mass 

spectrum stored in the data system (section 

7.3.2.3), or from a reference library. For 

example, if a peak has an intensity of 20% 

relative to the base peak, the analyte is 

identified if the intensity of the peak in the 

sample is in the range of 10% to 40% of the 

base peak. 

12.1.4 If the acquired mass spectrum is 

contaminated, or if identification is 

ambiguous, an experienced spectrometrist 

(section 1.6) must determine the presence or 

absence of the compound. 

12.2 Structural isomers that produce very 

similar mass spectra should be identified as 

individual isomers if they have sufficiently 

different gas chromatographic retention 

times. Sufficient gas chromatographic 

resolution is achieved if the height of the 

valley between two isomer peaks is less than 

50% of the average of the two peak heights. 

Otherwise, structural isomers are identified 

as isomeric pairs. The resolution should be 

verified on the mid-point concentration of 

the initial calibration as well as the 

laboratory designated continuing calibration 

verification level if closely eluting isomers 

are to be reported. 

13. Calculations 

13.1 When an analyte has been identified, 

quantitation of that analyte is based on the 

integrated abundance from the EICP of the 

primary characteristic m/z in Table 5 or 6. 

Calculate the concentration using the 

response factor (RF) determined in section 

7.3.3 and Equation 2. If a calibration curve 

was used, calculate the concentration using 

the regression equation for the curve. If the 

concentration of an analyte exceeds the 

calibration range, dilute the sample by the 

minimum amount to bring the concentration 

into the calibration range, and re-analyze. 

Determine a dilution factor (DF) from the 

amount of the dilution. For example, if the 

extract is diluted by a factor of 2, DF = 2. 

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Where: 

Cs = Concentration of the analyte in the 

sample, and the other terms are as 

defined in Section 7.3.3. 

13.2 Reporting of results 

As noted in section 1.4.1, EPA has 

promulgated this method at 40 CFR part 136 

for use in wastewater compliance monitoring 

under the National Pollutant Discharge 

Elimination System (NPDES). The data 

reporting practices described here are 

focused on such monitoring needs and may 

not be relevant to other uses of this method. 

13.2.1 Report results for wastewater 

samples in mg/L without correction for 

recovery. (Other units may be used if 

required by a permit.) Report all QC data 

with the sample results. 

13.2.2 Reporting level. Unless otherwise 

specified in by a regulatory authority or in a 

discharge permit, results for analytes that 

meet the identification criteria are reported 

down to the concentration of the ML 

established by the laboratory through 

calibration of the instrument (see section 

7.3.2 and the glossary for the derivation of 

the ML). EPA considers the terms ‘‘reporting 

limit,’’ ‘‘limit of quantitation,’’ ‘‘quantitation 

limit,’’ and ‘‘minimum level’’ to be 

synonymous. 

13.2.2.1 Report a result for each analyte 

in each field sample or QC standard at or 

above the ML to 3 significant figures. Report 

a result for each analyte found in each field 

sample or QC standard below the ML as 

‘‘<ML,’’ where ML is the concentration of the 

analyte at the ML, or as required by the 

regulatory/control authority or permit. Report 

a result for each analyte in a blank at or 

above the MDL to 2 significant figures. 

Report a result for each analyte found in a 

blank below the MDL as ‘‘<MDL,’’ where 

MDL is the concentration of the analyte at the 

MDL, or as required by the regulatory/control 

authority or permit. 

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 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 result 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 any of the QC test in this method) must 

be documented and reported (e.g., as a 

qualifier on results), unless the failure is not 

required to be reported as determined by the 

regulatory/control authority. Results 

associated with a QC failure cannot be used 

to demonstrate regulatory compliance. QC 

failures do not relieve a discharger or 

permittee of reporting timely results. If the 

holding time would be exceeded for a 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 section 1.1, this method 

was validated through an interlaboratory 

study conducted in the early 1980s. 

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 handled and 

disposed of as hazardous waste, or 

neutralized and disposed of in accordance 

with all federal, state, and local regulations. 

It is the laboratory’s responsibility to comply 

with all federal, state, and local regulations 

governing waste management, particularly 

the hazardous waste identification rules and 

land disposal restrictions. The laboratory 

using this method has the responsibility to 

protect the air, water, and land by 

minimizing and controlling all releases from 

fume hoods and bench operations. 

Compliance is also required with any sewage 

discharge permits and regulations. For 

further information on waste management, 

see ‘‘The Waste Management Manual for 

Laboratory Personnel,’’ also available from 

the American Chemical Society at the 

address in Section 15.3. 

16.3 Many analytes in this method 

decompose above 500 °C. Low-level waste 

such as absorbent paper, tissues, and plastic 

gloves may be burned in an appropriate 

incinerator. Gross quantities of neat or highly 

concentrated solutions of toxic or hazardous 

chemicals should be packaged securely and 

disposed of through commercial or 

governmental channels that are capable of 

handling these types of wastes. 

16.4 For further information on waste 

management, consult ‘‘Waste Management 

Manual for Laboratory Personnel and Less is 

Better-Laboratory Chemical Management for 

Waste Reduction,’’ available from the 

American Chemical Society’s Department of 

Government Relations and Science Policy, 

1155 16th Street NW., Washington, DC 

20036, 202–872–4477. 

17. References 

1. Bellar, T.A. and Lichtenberg, J.J. 

‘‘Determining Volatile Organics at 

Microgram-per-Litre Levels by Gas 

Chromatography,’’ Journal American Water 

Works Association, 66: 739 (1974). 

2. ‘‘Sampling and Analysis Procedures for 

Screening of Industrial Effluents for Priority 

Pollutants,’’ U.S. Environmental Protection 

Agency, Environmental Monitoring and 

Support Laboratory, Cincinnati, Ohio 45268, 

March 1977, Revised April 1977. 

3. Bellar, T.A. and Lichtenberg, J.J. ‘‘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. 


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6. ‘‘Method Detection Limit for Methods 

624 and 625,’’ Olynyk, P., Budde, W.L., and 

Eichelberger, J.W. Unpublished report, May 

14, 1980. 

7. ‘‘Carcinogens-Working With 

Carcinogens,’’ Department of Health, 

Education, and Welfare, Public Health 

Service, Center for Disease Control, National 

Institute for Occupational Safety and Health, 

Publication No. 77–206, August 1977. 

8. ‘‘OSHA Safety and Health Standards, 

General Industry,’’ (29 CFR part 1910), 

Occupational Safety and Health 

Administration, OSHA 2206 (Revised, 

January 1976). 

9. ‘‘Safety in Academic Chemistry 

Laboratories,’’ American Chemical Society 

Publication, Committee on Chemical Safety, 

7th Edition, 2003. 

10. 40 CFR 136.6(b)(5)(x). 

11. 40 CFR 136.6(b)(2)(i). 

12. Protocol for EPA Approval of New 

Methods for Organic and Inorganic Analytes 

in Wastewater and Drinking Water (EPA– 

821–B–98–003) March 1999. 

13. Provost, L.P. and Elder, R.S. 

‘‘Interpretation of Percent Recovery Data,’’ 

American Laboratory, 15, 58–63 (1983). 

14. 40 CFR 136.3(a), Table IB, Chlorine— 

Total residual. 

15. Budde, W.L. and Eichelberger, J.W. 

‘‘Performance Tests for the Evaluation of 

Computerized Gas Chromatography/Mass 

Spectrometry Equipment and Laboratories,’’ 

EPA–600/4–80–025, U.S. Environmental 

Protection Agency, Environmental 

Monitoring and Support Laboratory, 

Cincinnati, Ohio 45268, April 1980. 

16. ‘‘Method Performance Data for Method 

624,’’ Memorandum from R. Slater and T. 

Pressley, U.S. Environmental Protection 

Agency, Environmental Monitoring and 

Support Laboratory, Cincinnati, Ohio 45268, 

January 17, 1984. 

18. Tables 

TABLE 1—PURGEABLES 1

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 ........................ ........................

1 All the analytes in this table are Priority Pollutants (40 CFR part 423, appendix A). 2 MDL values from the 1984 promulgated version of Method 624. 3 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 2—ADDITIONAL PURGEABLES

Analyte CAS Registry 

Acetone 1 .............................. 67–64–1 

Acetonitrile 2 .......................... 75–05–8 

Acrolein ................................. 107–02–8 

Acrylonitrile ........................... 107–13–1 

Allyl alcohol 1 ........................ 107–18–6 

Allyl chloride ......................... 107–05–1 

t-Amyl ethyl ether (TAEE) .... 919–94–8 

t-Amyl methyl ether (TAME) 994–058 

Benzyl chloride ..................... 100–44–7 

Bromoacetone 2 .................... 598–31–2 

Bromobenzene ..................... 108–86–1 

Bromochloromethane ........... 74–97–5 

1,3-Butadiene ....................... 106–99–0 

n-Butanol 1 ............................ 71–36–3 

TABLE 2—ADDITIONAL PURGEABLES— 

Continued 

Analyte CAS Registry 

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 

TABLE 2—ADDITIONAL PURGEABLES— 

Continued 

Analyte CAS Registry 

1-Chlorohexanone ................ 20261–68–1 

Chloroprene (2-chloro-1,3- 

butadiene) ......................... 126–99–8 

3-Chloropropene ................... 107–05–1 

3-Chloropropionitrile ............. 542–76–7 

2-Chlorotoluene .................... 95–49–8 

4-Chlorotoluene .................... 106–43–4 

Crotonaldehyde 1 2 ................ 123–73–9 

Cyclohexanone ..................... 108–94–1 

1,2-Dibromo-3-chloropropane 96–12–8 

1,2-Dibromoethane ............... 106–93–4 

Dibromomethane .................. 74–95–3 

cis-1,4-Dichloro-2-butene ..... 1476–11–5 

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TABLE 2—ADDITIONAL PURGEABLES— 

Continued 

Analyte CAS Registry 

trans-1,4-Dichloro-2-butene .. 110–57–6 

cis-1,2-Dichloroethene .......... 156–59–2 

Dichlorodifluoromethane ....... 75–71–8 

1,3-Dichloropropane ............. 142–28–9 

2,2-Dichloropropane ............. 590–20–7 

1,3-Dichloro-2-propanol 2 ...... 96–23–1 

1,1-Dichloropropene ............. 563–58–6 

cis-1,3-Dichloropropene ........ 10061–01–5 

1:2,3:4-Diepoxybutane .......... 1464–53–5 

Diethyl ether ......................... 60–29–7 

Diisopropyl ether (DIPE) ....... 108–20–3 

1,4-Dioxane 2 ........................ 123–91–1 

Epichlorohydrin 2 ................... 106–89–8 

Ethanol 2 ............................... 64–17–5 

Ethyl acetate 2 ....................... 141–78–6 

Ethyl methacrylate ................ 97–63–2 

Ethylene oxide 2 .................... 75–21–8 

Hexachlorobutadiene ............ 87–63–3 

Hexachloroethane ................. 67–72–1 

2-Hexanone 2 ........................ 591–78–6 

Iodomethane ......................... 74–88–4 

Isobutyl alcohol 1 ................... 78–83–1 

Isopropylbenzene ................. 98–82–8 

p-Isopropyltoluene ................ 99–87–6 

Methacrylonitrile 2 ................. 126–98–7 

Methanol 2 ............................. 67–56–1 

Malonitrile 2 ........................... 109–77–3 

Methyl acetate ...................... 79–20–9 

Methyl acrylate ..................... 96–33–3 

Methyl cyclohexane .............. 108–87–2 

Methyl iodide ........................ 74–88–4 

Methyl methacrylate ............. 78–83–1 

4-Methyl-2-pentanone 

(MIBK) 2 ............................. 108–10–1 

Methyl-t-butyl ether (MTBE) 1634–04–4 

Naphthalene ......................... 91–20–3 

Nitrobenzene ........................ 98–95–3 

N-Nitroso-di-n-butylamine 2 ... 924–16–3 

2-Nitropropane ...................... 79–46–9 

Paraldehyde 2 ....................... 123–63–7 

Pentachloroethane 2 ............. 76–01–7 

Pentafluorobenzene .............. 363–72–4 

2-Pentanone 2 ....................... 107–19–7 

2-Picoline 2 ............................ 109–06–8 

1-Propanol 1 .......................... 71–23–8 

2-Propanol 1 .......................... 67–63–0 

Propargyl alcohol 2 ................ 107–19–7 

beta-Propiolactone 2 ............. 57–58–8 

Propionitrile (ethyl cyanide) 1 107–12–0 

n-Propylamine ....................... 107–10–8 

n-Propylbenzene ................... 103–65–1 

Pyridine 2 ............................... 110–86–1 

Styrene ................................. 100–42–5 

1,1,1,2-Tetrachloroethane .... 630–20–6 

Tetrahydrofuran .................... 109–99–9 

o-Toluidine 2 .......................... 95–53–4 

1,2,3-Trichlorobenzene ......... 87–61–6 

Trichlorofluoromethane ......... 75–69–4 

1,2,3-Trichloropropane ......... 96–18–4 

1,2,3-Trimethylbenzene ........ 526–73–8 

TABLE 2—ADDITIONAL PURGEABLES— 

Continued 

Analyte CAS Registry 

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 

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 

TABLE 3—EXAMPLE RETENTION

TIMES—Continued 

Analyte Retention time 

(min) 

2-Chloroethylvinyl ether ........ 13.45 

cis-1,3-Dichloropropene ........ 13.65 

4-Methyl-2-pentanone ........... 13.83 

Toluene ................................. 14.18 

trans-1,3-Dichloropropene .... 14.57 

Ethyl methacrylate ................ 14.70 

1,1,2-Trichloroethane ............ 14.93 

1,3-Dichloropropane ............. 15.18 

Tetrachloroethene ................. 15.22 

2-Hexanone .......................... 15.30 

Dibromochloromethane ........ 15.68 

1,2-Dibromoethane ............... 15.90 

Chlorobenzene ..................... 16.78 

Ethylbenzene ........................ 16.82 

1,1,1,2-Tetrachloroethane .... 16.87 

m+p-Xylene .......................... 17.08 

o-Xylene ................................ 17.82 

Bromoform ............................ 18.27 

Bromofluorobenzene ............ 18.80 

1,1,2,2-Tetrachloroethane .... 18.98 

1,2,3-Trichloropropane ......... 19.08 

trans-1,4-Dichloro-2-butene .. 19.12 

Column: 75 m x 0.53 mm ID x 3.0 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. Alternative tuning criteria 

from other published EPA reference methods 

may be used, provided method performance is 

not adversely affected. Alternative tuning criteria specified by an instrument manufacturer 

may also be used for another type of mass 

spectrometer, or for an alternative carrier gas, 

provided method performance is not adversely 

affected. 

TABLE 5—SUGGESTED SURROGATE AND INTERNAL STANDARDS

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 

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TABLE 5—SUGGESTED SURROGATE AND INTERNAL STANDARDS—Continued 

Analyte Retention time 

(min) 1 Primary m/z Secondary m/z’s 

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. 

TABLE 6—CHARACTERISTIC m/z’s FOR PURGEABLE ORGANICS

Analyte Primary m/z Secondary m/z’s 

Acrolein ......................................................................................................................... 56 55 and 58. 

Acrylonitrile ................................................................................................................... 53 52 and 51. 

Chloromethane ............................................................................................................. 50 52. 

Bromomethane ............................................................................................................. 94 96.

Vinyl chloride ................................................................................................................ 62 64. 

Chloroethane ................................................................................................................ 64 66. 

Methylene chloride ....................................................................................................... 84 49, 51, and 86. 

Trichlorofluoromethane ................................................................................................. 101 103.

1,1-Dichloroethene ....................................................................................................... 96 61 and 98. 

1,1-Dichloroethane ....................................................................................................... 63 65, 83, 85, 98, and 100. 

trans-1,2-Dichloroethene .............................................................................................. 96 61 and 98. 

Chloroform .................................................................................................................... 83 85. 

1,2-Dichloroethane ....................................................................................................... 98 62, 64, and 100. 

1,1,1-Trichloroethane ................................................................................................... 97 99, 117, and 119. 

Carbon tetrachloride ..................................................................................................... 117 119 and 121. 

Bromodichloromethane ................................................................................................ 83 127, 85, and 129. 

1,2-Dichloropropane ..................................................................................................... 63 112, 65, and 114. 

trans-1,3-Dichloropropene ............................................................................................ 75 77. 

Trichloroethene ............................................................................................................. 130 95, 97, and 132. 

Benzene ....................................................................................................................... 78 

Dibromochloromethane ................................................................................................ 127 129, 208, and 206. 

1,1,2-Trichloroethane ................................................................................................... 97 83, 85, 99, 132, and 134. 

cis-1,3-Dichloropropene ............................................................................................... 75 77. 

2-Chloroethylvinyl ether ................................................................................................ 106 63 and 65. 

Bromoform .................................................................................................................... 173 171, 175, 250, 252, 254, and 256. 

1,1,2,2-Tetrachloroethane ............................................................................................ 168 83, 85, 131, 133, and 166. 

Tetrachloroethene ........................................................................................................ 164 129, 131, and 166. 

Toluene ......................................................................................................................... 92 91. 

Chlorobenzene ............................................................................................................. 112 114. 

Ethyl benzene ............................................................................................................... 106 91. 

1,3-Dichlorobenzene .................................................................................................... 146 148 and 111. 

1,2-Dichlorobenzene .................................................................................................... 146 148 and 111. 

1,4-Dichlorobenzene .................................................................................................... 146 148 and 111. 

TABLE 7—LCS (Q), DOC (S AND X), AND MS/MSD (P AND RPD) ACCEPTANCE CRITERIA 1

Analyte Range for Q 

(%) 

Limit for s 

(%) 

Range for X 

(%) 

Range for P1, 

P2

(%) 

Limit for RPD 

Acrolein ................................................................................ 60–140 30 50–150 40–160 60 

Acrylonitrile ........................................................................... 60–140 30 50–150 40–160 60 

Benzene ............................................................................... 65–135 33 75–125 37–151 61 

Benzene-d6 .......................................................................... ........................ ........................ ........................ ........................ ........................

Bromodichloromethane ........................................................ 65–135 34 50–140 35–155 56 

Bromoform ........................................................................... 70–130 25 57–156 45–169 42 

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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 P1, 

P2

(%) 

Limit for RPD 

Bromomethane ..................................................................... 15–185 90 D–206 D–242 61 

2-Butanone-d5 ...................................................................... ........................ ........................ ........................ ........................ ........................

Carbon tetrachloride ............................................................ 70–130 26 65–125 70–140 41 

Chlorobenzene ..................................................................... 65–135 29 82–137 37–160 53 

Chloroethane ........................................................................ 40–160 47 42–202 14–230 78 

Chloroethane-d5 ................................................................... ........................ ........................ ........................ ........................ ........................

2-Chloroethylvinyl ether ....................................................... D–225 130 D–252 D–305 71 

Chloroform ........................................................................... 70–135 32 68–121 51–138 54 

Chloroform-13C .................................................................... ........................ ........................ ........................ ........................ ........................

Chloromethane ..................................................................... D–205 472 D–230 D–273 60 

Dibromochloromethane ........................................................ 70–135 30 69–133 53–149 50 

1,2-Dichlorobenzene ............................................................ 65–135 31 59–174 18–190 57 

1,2-Dichlorobenzene-d4 ....................................................... ........................ ........................ ........................ ........................ ........................

1,3-Dichlorobenzene ............................................................ 70–130 24 75–144 59–156 43 

1,4-Dichlorobenzene ............................................................ 65–135 31 59–174 18–190 57 

1,1-Dichloroethane ............................................................... 70–130 24 71–143 59–155 40 

1,2-Dichloroethane ............................................................... 70–130 29 72–137 49–155 49 

1,2-Dichloroethane-d4 .......................................................... ........................ ........................ ........................ ........................ ........................

1,1-Dichloroethene ............................................................... 50–150 40 19–212 D–234 32 

1,1-Dichloroethene-d2 .......................................................... ........................ ........................ ........................ ........................ ........................

trans-1,2-Dichloroethene ...................................................... 70–130 27 68–143 54–156 45 

1,2-Dichloropropane ............................................................. 35–165 69 19–181 D–210 55 

1,2-Dichloropropane-d6 ........................................................ ........................ ........................ ........................ ........................ ........................

cis-1,3-Dichloropropene ....................................................... 25–175 79 5–195 D–227 58 

trans-1,3-Dichloropropene ................................................... 50–150 52 38–162 17–183 86 

trans-1,3-Dichloropropene-d4 ............................................... ........................ ........................ ........................ ........................ ........................

Ethyl benzene ...................................................................... 60–140 34 75–134 37–162 63 

2-Hexanone-d5 ..................................................................... ........................ ........................ ........................ ........................ ........................

Methylene chloride ............................................................... 60–140 192 D–205 D–221 28 

1,1,2,2-Tetrachloroethane .................................................... 60–140 36 68–136 46–157 61 

1,1,2,2-Tetrachloroethane-d2 ............................................... ........................ ........................ ........................ ........................ ........................

Tetrachloroethene ................................................................ 70–130 23 65–133 64–148 39 

Toluene ................................................................................ 70–130 22 75–134 47–150 41 

Toluene-d8 ............................................................................ ........................ ........................ ........................ ........................ ........................

1,1,1-Trichloroethane ........................................................... 70–130 21 69–151 52–162 36 

1,1,2-Trichloroethane ........................................................... 70–130 27 75–136 52–150 45 

Trichloroethene .................................................................... 65–135 29 75–138 70–157 48 

Trichlorofluoromethane ........................................................ 50–150 50 45–158 17–181 84 

Vinyl chloride ........................................................................ 5–195 100 D–218 D–251 66 

Vinyl chloride-d3 ................................................................... ........................ ........................ ........................ ........................ ........................

1 Criteria were calculated using an LCS concentration of 20 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 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 

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TABLE 8—RECOVERY AND PRECISION AS FUNCTIONS OF CONCENTRATION—Continued 

Analyte Recovery, X′ 

(μg/L) 

Single analyst 

precision, sr′ 

(μg/L) 

Overall 

precision, S′ 

(μg/L) 

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. 

19. Glossary 

These definitions and purposes are specific 

to this method, but have been conformed to 

common usage to the extent possible. 

19.1 Units of weight and measure and 

their abbreviations. 

19.1.1 Symbols. 

°C degrees Celsius 

mg microgram 

mL microliter 

< less than 

> greater than 

% percent 

19.1.2 Abbreviations (in alphabetical 

order). 

cm centimeter 

g gram 

h hour 

ID inside diameter 

in. inch 

L liter 

m mass 

mg milligram 

min minute 

mL milliliter 

mm millimeter 

ms millisecond 

m/z mass-to-charge ratio 

N normal; gram molecular weight of solute 

divided by hydrogen equivalent of solute, 

per liter of solution 

ng nanogram 

pg picogram 

ppb part-per-billion 

ppm part-per-million 

ppt part-per-trillion 

psig pounds-per-square inch gauge 

v/v volume per unit volume 

w/v weight per unit volume 

19.2 Definitions and acronyms (in 

alphabetical order). 

Analyte—A compound tested for by this 

method. The analytes are listed in Tables 1 

and 2. 

Analyte of interest—An analyte of interest 

is an analyte required to be determined by a 

regulatory/control authority or in a permit, or 

by a client. 

Analytical batch—The set of samples 

analyzed on a given instrument during a 12- 

hour period that begins with analysis of a 

calibration verification/LCS. See section 8.4. 

Blank—An aliquot of reagent water that is 

treated exactly as a sample including 

exposure to all glassware, equipment, 

solvents, reagents, internal standards, and 

surrogates that are used with samples. The 

blank is used to determine if analytes or 

interferences are present in the laboratory 

environment, the reagents, or the apparatus. 

See section 8.5. 

Calibration—The process of determining 

the relationship between the output or 

response of a measuring instrument and the 

value of an input standard. Historically, EPA 

has referred to a multi-point calibration as 

the ‘‘initial calibration,’’ to differentiate it 

from a single-point calibration verification. 

Calibration standard—A solution prepared 

from stock solutions and/or a secondary 

standards and containing the analytes of 

interest, surrogates, and internal standards. 

The calibration standard is used to calibrate 

the response of the GC/MS instrument 

against analyte concentration. 

Calibration verification standard—The 

laboratory control sample (LCS) used to 

verify calibration. See Section 8.4. 

Descriptor—In SIM, the beginning and 

ending retention times for the RT window, 

the m/z’s sampled in the RT window, and the 

dwell time at each m/z. 

Extracted ion current profile (EICP)—The 

line described by the signal at a given m/z. 

Field duplicates—Two samples collected 

at the same time and place under identical 

conditions, and treated identically 

throughout field and laboratory procedures. 

Results of analyses of field duplicates 

provide an estimate of the precision 

associated with sample collection, 

preservation, and storage, as well as with 

laboratory procedures. 

Field blank—An aliquot of reagent water or 

other reference matrix that is placed in a 

sample container in the field, and treated as 

a sample in all respects, including exposure 

to sampling site conditions, storage, 

preservation, and all analytical procedures. 

The purpose of the field blank is to 

determine if the field or sample transporting 

procedures and environments have 

contaminated the sample. 

GC—Gas chromatograph or gas 

chromatography. 

Internal standard—A compound added to 

a sample in a known amount and used as a 

reference for quantitation of the analytes of 

interest and surrogates. Internal standards are 

listed in Table 5. Also see Internal standard 

quantitation. 

Internal standard quantitation—A means of 

determining the concentration of an analyte 

of interest (Tables 1 and 2) by reference to 

a compound added to a sample and not 

expected to be found in the sample. 

DOC—Initial demonstration of capability 

(DOC; section 8.2); four aliquots of reagent 

water spiked with the analytes of interest and 

analyzed to establish the ability of the 

laboratory to generate acceptable precision 

and recovery. A DOC is performed prior to 

the first time this method is used and any 

time the method or instrumentation is 

modified. 

Laboratory control sample (LCS; laboratory 

fortified blank (LFB); on-going precision and 

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recovery sample; OPR)—An aliquot of 

reagent water spiked with known quantities 

of the analytes of interest and surrogates. The 

LCS is analyzed exactly like a sample. Its 

purpose is to assure that the results produced 

by the laboratory remain within the limits 

specified in this method for precision and 

recovery. In this method, the LCS is 

synonymous with a calibration verification 

sample (See sections 7.4 and 8.4). 

Laboratory fortified sample matrix—See 

Matrix spike. 

Laboratory reagent blank—See Blank. 

Matrix spike (MS) and matrix spike 

duplicate (MSD) (laboratory fortified sample 

matrix and duplicate)—Two aliquots of an 

environmental sample to which known 

quantities of the analytes of interest and 

surrogates are added in the laboratory. The 

MS/MSD are prepared and analyzed exactly 

like a field sample. Their purpose is to 

quantify any additional bias and imprecision 

caused by the sample matrix. The 

background concentrations of the analytes in 

the sample matrix must be determined in a 

separate aliquot and the measured values in 

the MS/MSD corrected for background 

concentrations. 

May—This action, activity, or procedural 

step is neither required nor prohibited. 

May not—This action, activity, or 

procedural step is prohibited. 

Method blank (laboratory reagent blank)— 

See Blank. 

Method detection limit (MDL)—A 

detection limit determined by the procedure 

at 40 CFR part 136, appendix B. The MDLs 

determined by EPA in the original version of 

the method are listed in Table 1. As noted 

in Sec. 1.4, use the MDLs in Table 1 in 

conjunction with current MDL data from the 

laboratory actually analyzing samples to 

assess the sensitivity of this procedure 

relative to project objectives and regulatory 

requirements (where applicable). 

Minimum level (ML)—The term 

‘‘minimum level’’ refers to either the sample 

concentration equivalent to the lowest 

calibration point in a method or a multiple 

of the method detection limit (MDL), 

whichever is higher. Minimum levels may be 

obtained in several ways: They may be 

published in a method; they may be based on 

the lowest acceptable calibration point used 

by a laboratory; or they may be calculated by 

multiplying the MDL in a method, or the 

MDL determined by a laboratory, by a factor 

of 3. For the purposes of NPDES compliance 

monitoring, EPA considers the following 

terms to be synonymous: ‘‘quantitation 

limit,’’ ‘‘reporting limit,’’ and ‘‘minimum 

level.’’ 

MS—Mass spectrometer or mass 

spectrometry. 

Must—This action, activity, or procedural 

step is required. 

m/z—The ratio of the mass of an ion (m) 

detected in the mass spectrometer to the 

charge (z) of that ion. 

Quality control sample (QCS)—A sample 

containing analytes of interest at known 

concentrations. The QCS is obtained from a 

source external to the laboratory or is 

prepared from standards obtained from a 

different source than the calibration 

standards. 

The purpose is to check laboratory 

performance using test materials that have 

been prepared independent of the normal 

preparation process. 

Reagent water—Water demonstrated to be 

free from the analytes of interest and 

potentially interfering substances at the 

MDLs for the analytes in this method. 

Regulatory compliance limit (or regulatory 

concentration limit)—A limit on the 

concentration or amount of a pollutant or 

contaminant specified in a nationwide 

standard, in a permit, or otherwise 

established by a regulatory/control authority. 

Relative retention time (RRT)—The ratio of 

the retention time of an analyte to the 

retention time of its associated internal 

standard. RRT compensates for small changes 

in the GC temperature program that can affect 

the absolute retention times of the analyte 

and internal standard. RRT is a unitless 

quantity. 

Relative standard deviation (RSD)—The 

standard deviation times 100 divided by the 

mean. Also termed ‘‘coefficient of variation.’’ 

RF—Response factor. See section 7.3.3. 

RSD—See relative standard deviation. 

Safety Data Sheet (SDS)—Written 

information on a chemical’s toxicity, health 

hazards, physical properties, fire, and 

reactivity, including storage, spill, and 

handling precautions that meet the 

requirements of OSHA, 29 CFR 1910.1200(g) 

and appendix D to § 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-andtrap. The surrogate is quantitated with the 

same procedures used to quantitate the 

analytes of interest. The purpose of the 

surrogate is to monitor method performance 

with each sample. 

VOA—Volatile organic analysis: e.g., the 

analysis performed by this method. 

Method 625.1—Base/Neutrals and Acids by 

GC/MS 

1. Scope and Application 

1.1 This method is for determination of 

semivolatile organic pollutants in industrial 

discharges and other environmental samples 

by gas chromatography combined with mass 

spectrometry (GC/MS), as provided under 40 

CFR 136.1. This revision is based on a 

previous protocol (Reference 1), on the basic 

revision promulgated October 26, 1984, and 

on an interlaboratory method validation 

study (Reference 2). Although this method 

was validated through an interlaboratory 

study conducted in the early 1980s, the 

fundamental chemistry principles used in 

this method remain sound and continue to 

apply. 

1.2 The analytes that may be qualitatively 

and quantitatively determined using this 

method and their CAS Registry numbers are 

listed in Tables 1 and 2. The method may be 

extended to determine the analytes listed in 

Table 3; however, extraction or gas 

chromatography of some of these analytes 

may make quantitative determination 

difficult. For example, benzidine is subject to 

oxidative losses during extraction and/or 

solvent concentration. Under the alkaline 

conditions of the extraction, alpha-BHC, 

gamma-BHC, endosulfan I and II, and endrin 

are subject to decomposition. 

Hexachlorocyclopentadiene is subject to 

thermal decomposition in the inlet of the gas 

chromatograph, chemical reaction in acetone 

solution, and photochemical decomposition. 

N-nitrosodiphenylamine and other 

nitrosoamines may decompose in the gas 

chromatographic inlet. The sample may be 

extracted at neutral pH if necessary to 

overcome these or other decomposition 

problems that could occur at alkaline or 

acidic pH. EPA also has provided other 

methods (e.g., Method 607—Nitrosamines) 

that may be used for determination of some 

of these analytes. EPA encourages use of 

Method 625.1 to determine additional 

compounds amenable to extraction and GC/ 

MS. 

1.3 The large number of analytes in 

Tables 1–3 of this method makes testing 

difficult if all analytes are determined 

simultaneously. Therefore, it is necessary to 

determine and perform quality control (QC) 

tests for the ‘‘analytes of interest’’ only. 

Analytes of interest are those required to be 

determined by a regulatory/control authority 

or in a permit, or by a client. If a list of 

analytes is not specified, the analytes in 

Tables 1 and 2 must be determined, at a 

minimum, and QC testing must be performed 

for these analytes. The analytes in Tables 1 

and 2, and some of the analytes in Table 3 

have been identified as Toxic Pollutants (40 

CFR 401.15), expanded to a list of Priority 

Pollutants (40 CFR part 423, appendix A). 

1.4 In this revision to Method 625, the 

pesticides and polychlorinated biphenyls 

(PCBs) have been moved from Table 1 to 

Table 3 (Additional Analytes) to distinguish 

these analytes from the analytes required in 

quality control tests (Tables 1 and 2). QC 

acceptance criteria for pesticides and PCBs 

have been retained in Table 6 and may 

continue to be applied if desired, or if 

requested or required by a regulatory/control 

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authority or in a permit. Method 608.3 

should be used for determination of 

pesticides and PCBs. However, if pesticides 

and/or PCBs are to be determined, an 

additional sample must be collected and 

extracted using the pH adjustment and 

extraction procedures specified in Method 

608.3. Method 1668C may be useful for 

determination of PCBs as individual 

chlorinated biphenyl congeners, and Method 

1699 may be useful for determination of 

pesticides. At the time of writing of this 

revision, Methods 1668C and 1699 had not 

been approved for use at 40 CFR part 136. 

The screening procedure for 2,3,7,8- 

tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) 

contained in the version of Method 625 

promulgated October 26, 1984 has been 

replaced with procedures for selected ion 

monitoring (SIM), and 2,3,7,8-TCDD may be 

determined using the SIM procedures. 

However, EPA Method 613 or 1613B should 

be used for analyte-specific determination of 

2,3,7,8-TCDD because of the focus of these 

methods on this compound. Methods 613 

and 1613B are approved for use at 40 CFR 

part 136. 

1.5 Method detection limits (MDLs; 

Reference 3) for the analytes in Tables 1, 2, 

and 3 are listed in those tables. These MDLs 

were determined in reagent water (Reference 

4). Advances in analytical technology, 

particularly the use of capillary (opentubular) columns, allowed laboratories to 

routinely achieve MDLs for the analytes in 

this method that are 2–10 times lower than 

those in the version promulgated in 1984. 

The MDL for an analyte in a specific 

wastewater may differ from those listed, 

depending upon the nature of interferences 

in the sample matrix. 

1.5.1 EPA has promulgated this method 

at 40 CFR part 136 for use in wastewater 

compliance monitoring under the National 

Pollutant Discharge Elimination System 

(NPDES). The data reporting practices 

described in section 15.2 are focused on such 

monitoring needs and may not be relevant to 

other uses of the method. 

1.5.2 This method includes ‘‘reporting 

limits’’ based on EPA’s ‘‘minimum level’’ 

(ML) concept (see the glossary in section 22). 

Tables 1, 2, and 3 contain MDL values and 

ML values for many of the analytes. 

1.6 This method is performance-based. It 

may be modified to improve performance 

(e.g., to overcome interferences or improve 

the accuracy of results) provided all 

performance requirements are met. 

1.6.1 Examples of allowed method 

modifications are described at 40 CFR 136.6. 

Other examples of allowed modifications 

specific to this method, including solidphase extraction (SPE) are described in 

section 8.1.2. 

1.6.2 Any modification beyond those 

expressly permitted at 40 CFR 136.6 or in 

section 8.1.2 of this method shall be 

considered a major modification subject to 

application and approval of an alternate test 

procedure under 40 CFR 136.4 and 136.5. 

1.6.3 For regulatory compliance, any 

modification must be demonstrated to 

produce results equivalent or superior to 

results produced by this method when 

applied to relevant wastewaters (section 8.3). 

1.7 This method is restricted to use by or 

under the supervision of analysts 

experienced in the use of a gas 

chromatograph/mass spectrometer and in the 

interpretation of mass spectra. Each 

laboratory that uses this method must 

demonstrate the ability to generate acceptable 

results using the procedure in Section 8.2. 

1.8 Terms and units of measure used in 

this method are given in the glossary at the 

end of the method. 

2. Summary of Method 

2.1 A measured volume of sample, 

sufficient to meet an MDL or reporting limit, 

is serially extracted with methylene chloride 

at pH 11–13 and again at a pH less than 2 

using a separatory funnel or continuous 

liquid/liquid extractor. 

2.2 The extract is concentrated to a 

volume necessary to meet the required 

compliance or detection limit, and analyzed 

by GC/MS. Qualitative identification of an 

analyte in the extract is performed using the 

retention time and the relative abundance of 

two or more characteristic masses (m/z’s). 

Quantitative analysis is performed using the 

internal standard technique with a single 

characteristic m/z. 

3. Contamination and Interferences 

3.1 Solvents, reagents, glassware, and 

other sample processing labware may yield 

artifacts, elevated baselines, or matrix 

interferences causing misinterpretation of 

chromatograms and mass spectra. All 

materials used in the analysis must be 

demonstrated to be free from contamination 

and interferences by analyzing blanks 

initially and with each extraction batch 

(samples started through the extraction 

process in a given 24-hour period, to a 

maximum of 20 samples—see Glossary for 

detailed definition), as described in Section 

8.5. Specific selection of reagents and 

purification of solvents by distillation in allglass 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. Do not heat volumetric labware 

above 90 °C. After drying and cooling, store 

inverted or capped with solvent-rinsed or 

baked aluminum foil in a clean environment 

to prevent accumulation of dust or other 

contaminants. 

3.3 Matrix interferences may be caused 

by contaminants co-extracted from the 

sample. The extent of matrix interferences 

will vary considerably from source to source, 

depending upon the nature and diversity of 

the industrial complex or municipality being 

sampled. Interferences extracted from 

samples high in total organic carbon (TOC) 

may result in elevated baselines, or by 

enhancing or suppressing a signal at or near 

the retention time of an analyte of interest. 

Analyses of the matrix spike and duplicate 

(section 8.3) may be useful in identifying 

matrix interferences, and gel permeation 

chromatography (GPC; Section 11.1) and 

sulfur removal (section 11.2) may aid in 

eliminating these interferences. EPA has 

provided guidance that may aid in 

overcoming matrix interferences (Reference 

6). 

3.4 In samples that contain an inordinate 

number of interferences, the use of chemical 

ionization (CI) or triple quadrupole (MRM) 

mass spectrometry may make identification 

easier. Tables 4 and 5 give characteristic CI 

and MRM m/z’s for many of the analytes 

covered by this method. The use of CI or 

MRM mass spectrometry may be utilized to 

support electron ionization (EI) mass 

spectrometry or as a primary method for 

identification and quantification. While the 

use of these enhanced techniques is 

encouraged, it is not required. 

4. Safety 

4.1 Hazards associated with each reagent 

used in this method have not been precisely 

defined; however, each chemical compound 

should be treated as a potential health 

hazard. From this viewpoint, exposure to 

these chemicals must be reduced to the 

lowest possible level by whatever means 

available. The laboratory is responsible for 

maintaining a current awareness file of 

OSHA regulations regarding the safe 

handling of the chemicals specified in this 

method. A reference file of safety data sheets 

(SDSs, OSHA, 29 CFR 1910.1200(g)) should 

also be made available to all personnel 

involved in sample handling and chemical 

analysis. Additional references to laboratory 

safety are available and have been identified 

(References 7–9) for the information of the 

analyst. 

4.2 The following analytes covered by 

this method have been tentatively classified 

as known or suspected human or mammalian 

carcinogens: Benzo(a)anthracene, benzidine, 

3,3′-dichlorobenzidine, benzo(a)pyrene, 

alpha-BHC, beta-BHC, delta-BHC, gammaBHC, Dibenz(a,h)-anthracene, Nnitrosodimethylamine, 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. 

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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 fluoropolymerlined 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, however, rinse the 

compressible tubing with methanol, followed 

by repeated rinsing with reagent water, to 

minimize the potential for sample 

contamination. An integrating flow meter is 

required to collect flow-proportioned 

composites. 

5.2 Glassware. 

5.2.1 Separatory funnel—Size appropriate 

to hold sample volume and extraction 

solvent volume, and equipped with 

fluoropolymer stopcock. 

5.2.2 Drying column—Chromatographic 

column, approximately 400 mm long by 19 

mm ID, with coarse frit, or equivalent, 

sufficient to hold 15 g of anhydrous sodium 

sulfate. 

5.2.3 Concentrator tube, 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, Kuderna-Danish— 

Three-ball macro (Kontes 503000–0121 or 

equivalent). 

5.2.6 Snyder column, Kuderna-Danish— 

Two-ball micro (Kontes 569001–0219 or 

equivalent). 

5.2.7 Vials—10–15 mL, amber glass, with 

Teflon-lined screw cap. 

5.2.8 Continuous liquid-liquid 

extractor—Equipped with fluoropolymer or 

glass connecting joints and stopcocks 

requiring no lubrication. (Hershberg-Wolf 

Extractor, Ace Glass Company, Vineland, NJ, 

P/N 6848–20, or equivalent.) 

5.2.9 In addition to the glassware listed 

above, the laboratory should be equipped 

with all necessary pipets, volumetric flasks, 

beakers, and other glassware listed in this 

method and necessary to perform analyses 

successfully. 

5.3 Boiling chips—Approximately 10/40 

mesh, glass, silicon carbide, or equivalent. 

Heat to 400 °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 

vaporization split/splitless (PTV), solventpurge, 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 × 

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. 

5.9 Muffle furnace or kiln—Capable of 

baking glassware or sodium sulfate in the 

range of 400–450 °C. 

6. Reagents 

6.1 Reagent water—Reagent water is 

defined as water in which the analytes of 

interest and interfering compounds are not 

detected at the MDLs of the analytes of 

interest. 

6.2 Sodium hydroxide solution (10 N)— 

Dissolve 40 g of NaOH (ACS) in reagent water 

and dilute to 100 mL. 

6.3 Sodium thiosulfate—(ACS) granular. 

6.4 Sulfuric acid (1+1)—Slowly add 50 

mL of H2SO4 (ACS, sp. gr. 1.84) to 50 mL of 

reagent water. 

6.5 Acetone, methanol, methylene 

chloride, 2-propanol—High purity pesticide 

quality, or equivalent, demonstrated to be 

free of the analytes of interest and 

interferences (Section 3). Purification of 

solvents by distillation in all-glass systems 

may be required. 

6.6 Sodium sulfate—(ACS) granular, 

anhydrous, rinsed or Soxhlet extracted with 

methylene chloride (20 mL/g), baked in a 

shallow tray at 450 °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 or 

international standard, when available. Stock 

solution concentrations alternate to those 

below may be used. Because of the toxicity 

of some of the compounds, primary dilutions 

should be prepared in a hood, and a NIOSH/ 

MESA approved toxic gas respirator should 

be worn when high concentrations of neat 

materials are handled. The following 

procedure may be used to prepare standards 

from neat materials. 

6.7.1 Prepare stock standard solutions by 

accurately weighing about 0.0100 g of pure 

material. Dissolve the material in pesticide 

quality methanol or other suitable solvent 

and dilute to volume in a 10-mL volumetric 

flask. Larger volumes may be used at the 

convenience of the laboratory. When 

compound purity is assayed to be 96% or 

greater, the weight may be used without 

correction to calculate the concentration of 

the stock standard. Commercially prepared 

stock standards may be used at any 

concentration if they are certified by the 

manufacturer or by an independent source. 

6.7.2 Unless stated otherwise in this 

method, store non-aqueous standards in 

fluoropolymer-lined screw-cap, or heatsealed, glass containers, in the dark at ¥20 

to ¥10 °C. Store aqueous standards; e.g., the 

aqueous LCS (section 8.4.1), in the dark at 

≤ 6 °C, but do not freeze. Standards prepared 

by the laboratory may be stored for up to one 

year, except when comparison with QC 

check standards indicates that a standard has 

degraded or become more concentrated due 

to evaporation, or unless the laboratory has 

data on file to prove stability for a longer 

period. Commercially prepared standards 

may be stored until the expiration date 

provided by the vendor, except when 

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comparison with QC check standards 

indicates that a standard has degraded or 

become more concentrated due to 

evaporation, or unless the laboratory has data 

from the vendor on file to prove stability for 

a longer period. 

6.8 Surrogate standard spiking solution. 

6.8.1 Select a minimum of three surrogate 

compounds from Table 8 that most closely 

match the recovery of the analytes of interest. 

For example, if all analytes tested are 

considered acids, use surrogates that have 

similar chemical attributes. Other 

compounds may be used as surrogates so 

long as they do not interfere in the analysis. 

If only one or two analytes are determined, 

one or two surrogates may be used. 

6.8.2 Prepare a solution containing each 

selected surrogate such that the 

concentration in the sample would match the 

concentration in the mid-point calibration 

standard. For example, if the midpoint of the 

calibration is 100 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. Store per 

section 6.7.2. 

6.9 Internal standard spiking solution. 

6.9.1 Select three or more internal 

standards similar in chromatographic 

behavior to the analytes of interest. Internal 

standards are listed in Table 8. Suggested 

internal standards are: 1,4-dichlorobenzened4; 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. Store per section 6.7.3. 

6.9.3 To assure accurate analyte 

identification, particularly when SIM is used, 

it may be advantageous to include more 

internal standards than those suggested in 

section 6.9.1. An analyte will be located most 

accurately if its retention time relative to an 

internal standard is in the range of 0.8 to 1.2. 

6.10 DFTPP standard—Prepare a solution 

of DFTPP in methanol or other suitable 

solvent such that 50 ng or less will be 

injected (see section 13.2). An alternative 

concentration may be used to compensate for 

specific injection volumes or to assure that 

the operating range of the instrument is not 

exceeded, so long as the total injected is 50 

ng or less. Include benzidine and 

pentachlorophenol in this solution such that 

≤100 ng of benzidine and ≤50 ng of 

pentachlorophenol will be injected. 

6.11 Quality control check sample 

concentrate—See section 8.2.1. 

6.12 GPC calibration solution. 

6.12.1 Prepare a methylene chloride 

solution to contain corn oil, bis(2-ethylhexyl) 

phthalate (BEHP), perylene, and sulfur at the 

concentrations in section 6.12.2, or at 

concentrations appropriate to the response of 

the detector. 

Note: Sulfur does not readily dissolve in 

methylene chloride, but is soluble in warm 

corn oil. The following procedure is 

suggested for preparation of the solution. 

6.12.2 Weigh 8 mg sulfur and 2.5 g corn 

oil into a 100-mL volumetric flask and warm 

to dissolve the sulfur. Separately weigh 100 

mg BEHP, 20 mg pentachlorophenol, and 2 

mg perylene and add to flask. Bring to 

volume with methylene chloride and mix 

thoroughly. 

6.12.3 Store the solution in an amber 

glass bottle with a fluoropolymer-lined screw 

cap at 0–6 °C. Protect from light. 

Refrigeration may cause the corn oil to 

precipitate. Before use, allow the solution to 

stand at room temperature until the corn oil 

dissolves, or warm slightly to aid in 

dissolution. Replace the solution every year, 

or more frequently if the response of a 

component changes. 

6.13 Sulfur removal—Copper foil or 

powder (bright, non-oxidized), or 

tetrabutylammonium sulfite (TBA sulfite). 

6.13.1 Copper foil, or powder—Fisher, 

Alfa Aesar 42455–18, 625 mesh, or 

equivalent. Cut copper foil into 

approximately 1-cm squares. Copper must be 

activated before it may be used, as described 

below: 

6.13.1.1 Place the quantity of copper 

needed for sulfur removal (section 11.2.1.3) 

in a ground-glass-stoppered Erlenmeyer flask 

or bottle. Cover the foil or powder with 

methanol. 

6.13.1.2 Add HCl dropwise (0.5–1.0 mL) 

while swirling, until the copper brightens. 

6.13.1.3 Pour off the methanol/HCl and 

rinse 3 times with reagent water to remove 

all traces of acid, then 3 times with acetone, 

then 3 times with hexane. 

6.13.1.4 For copper foil, cover with 

hexane after the final rinse. Store in a 

stoppered flask under nitrogen until used. 

For the powder, dry on a rotary evaporator 

or under a stream of nitrogen. Store in a 

stoppered flask under nitrogen until used. 

Inspect the copper foil or powder before each 

use. It must have a bright, non-oxidized 

appearance to be effective. Copper foil or 

powder that has oxidized may be reactivated 

using the procedure described above. 

6.13.2 Tetrabutylammonium sodium 

sulfite (TBA sodium sulfite). 

6.13.2.1 Tetrabutylammonium hydrogen 

sulfate, [CH3(CH2)3]4NHSO4. 

6.13.2.2 Sodium sulfite, Na2SO3. 

6.13.2.3 Dissolve approximately 3 g 

tetrabutylammonium hydrogen sulfate in 100 

mL of reagent water in an amber bottle with 

fluoropolymer-lined screw cap. Extract with 

three 20-mL portions of hexane and discard 

the hexane extracts. 

6.13.2.4 Add 25 g sodium sulfite to 

produce a saturated solution. Store at room 

temperature. Replace after 1 month. 

6.14 DDT and endrin decomposition 

(breakdown) solution—Prepare a solution 

containing endrin at a concentration of 1 mg/ 

mL and 4,4′-DDT at a concentration of 2 mg/ 

mL, in isooctane or hexane. A 1-mL injection 

of this standard will contain 1 nanogram (ng) 

of endrin and 2 ng of DDT. The concentration 

of the solution may be adjusted by the 

laboratory to accommodate other injection 

volumes such that the same masses of the 

two analytes are introduced into the 

instrument. 

7. Calibration 

7.1 Establish operating conditions 

equivalent to those in the footnote to Table 

4 or 5 for the base/neutral or acid fraction, 

respectively. If a combined base/neutral/acid 

fraction will be analyzed, use the conditions 

in the footnote to Table 4. Alternative 

temperature program and flow rate 

conditions may be used. It is necessary to 

calibrate the GC/MS for the analytes of 

interest (Section 1.3) only. 

7.2 Internal standard calibration. 

7.2.1 Prepare calibration standards for the 

analytes of interest and surrogates at a 

minimum of five concentration levels by 

adding appropriate volumes of one or more 

stock standards to volumetric flasks. One of 

the calibration standards should be at a 

concentration at or below the ML specified 

in Table 1, 2, or 3, or as specified by a 

regulatory/control authority or in a permit. 

The ML value may be rounded to a whole 

number that is more convenient for preparing 

the standard, but must not exceed the ML in 

Table 1, 2, or 3 for those analytes which list 

ML values. Alternatively, the laboratory may 

establish a laboratory ML for each analyte 

based on the concentration in a nominal 

whole-volume sample that is equivalent to 

the concentration of the lowest calibration 

standard in a series of standards produced in 

the laboratory or obtained from a commercial 

vendor. The laboratory’s ML must not exceed 

the ML in Table 1, 2, or 3, and the resulting 

calibration must meet the acceptance criteria 

in Section 7.2.3, based on the RSD, RSE, or 

R2. The concentrations of the other 

calibration standards should correspond to 

the expected range of concentrations found 

in real samples or should define the working 

range of the GC/MS system for full-scan and/ 

or SIM operation, as appropriate. A 

minimum of six concentration levels is 

required for a second order, non-linear (e.g., 

quadratic; ax2 + bx + c = 0) calibration 

(section 7.2.3). Calibrations higher than 

second order are not allowed. To each 

calibration standard or standard mixture, add 

a known constant volume of the internal 

standard solution (section 6.9), and dilute to 

volume with methylene chloride. 

Note: The large number of analytes in 

Tables 1 through 3 may not be soluble or 

stable in a single solution; multiple solutions 

may be required if a large number of analytes 

are to be determined simultaneously. 

7.2.1.1 Prior to analysis of the calibration 

standards, inject the DFTPP standard 

(Section 6.10) and adjust the scan rate of the 

mass spectrometer to produce a minimum of 

5 mass spectra across the DFTPP GC peak. 

Adjust instrument conditions until the 

DFTPP criteria in Table 9A or 9B are met. 

Calculate peak tailing factors for benzidine 

and pentachlorophenol. Calculation of the 

tailing factor is illustrated in Figure 1. The 

tailing factor for benzidine and 

pentachlorophenol must be <2; otherwise, 

adjust instrument conditions and either 

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replace the column or break off a short 

section of the front end of the column, and 

repeat the test. Once the scan conditions are 

established, they must be used for analyses 

of all standards, blanks, and samples. 

Note: The DFTPP spectrum may be 

evaluated by summing the intensities of the 

m/z’s across the GC peak, subtracting the 

background at each m/z in a region of the 

chromatogram within 20 scans of but not 

including any part of, the DFTPP peak. The 

DFTPP spectrum may also be evaluated by 

fitting a Gaussian to each m/z and using the 

intensity at the maximum for each Gaussian 

or by integrating the area at each m/z and 

using the integrated areas. Other means may 

be used for evaluation of the DFTPP 

spectrum so long as the spectrum is not 

distorted to meet the criteria in Table 9A or 

9B. 

7.2.1.2 Analyze the mid-point combined 

base/neutral and acid calibration standard 

and enter or review the retention time, 

relative retention time, mass spectrum, and 

quantitation m/z in the data system for each 

analyte of interest, surrogate, and internal 

standard. If additional analytes (Table 3) are 

to be quantified, include these analytes in the 

standard. The mass spectrum for each analyte 

must be comprised of a minimum of 2 m/z’s 

(Tables 4 and 5); 3 to 5 m/z’s assure more 

reliable analyte identification. Suggested 

quantitation m/z’s are shown in Tables 4 and 

5 as the primary m/z. If an interference 

occurs at the primary m/z, use one of the 

secondary m/z’s or an alternate m/z. A single 

m/z only is required for quantitation. 

7.2.1.3 For SIM operation, determine the 

analytes in each descriptor, the quantitation 

m/z for each analyte (the quantitation m/z 

can be the same as for full-scan operation; 

section 7.2.1.2), the dwell time on each m/ 

z for each analyte, and the beginning and 

ending retention time for each descriptor. 

Analyze the verification standard in scan 

mode to verify m/z’s and establish retention 

times for the analytes. There must be a 

minimum of two m/z’s for each analyte to 

assure analyte identification. To maintain 

sensitivity, the number of m/z’s in a 

descriptor should be limited. For example, 

for a descriptor with 10 m/z’s and a 

chromatographic peak width of 5 sec, a dwell 

time of 100 ms at each m/z would result in 

a scan time of 1 second and provide 5 scans 

across the GC peak. The quantitation m/z 

will usually be the most intense peak in the 

mass spectrum. The quantitation m/z and 

dwell time may be optimized for each 

analyte. The acquisition table used for SIM 

must take into account the mass defect 

(usually less than 0.2 Dalton) that can occur 

at each m/z monitored. Refer to the footnotes 

to Table 4 or 5 for establishing operating 

conditions and to section 7.2.1.1 for 

establishing scan conditions. 

7.2.1.4 For combined scan and SIM 

operation, set up the scan segments and 

descriptors to meet requirements in sections 

7.2.1.1–7.2.1.3. Analyze unfamiliar samples 

in the scan mode to assure that the analytes 

of interest are determined. 

7.2.2 Analyze each calibration standard 

according to section 12 and tabulate the area 

at the quantitation m/z against concentration 

for each analyte of interest, surrogate, and 

internal standard. If an interference is 

encountered, use a secondary m/z (Table 4 or 

5) for quantitation. Calculate a response 

factor (RF) for each analyte of interest at each 

concentration using Equation 1. 

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. 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 (this value roughly corresponds to the 

RSD limit of 35%). Alternatively, the relative 

standard error (Reference 11) may be used as 

an acceptance criterion. As with the RSD, the 

RSE must be less than 35%. If an RSE less 

than 35% cannot be achieved for a quadratic 

regression, system performance is 

unacceptable and the system must be 

adjusted and re-calibrated. 

Note: Using capillary columns and current 

instrumentation, it is quite likely that a 

laboratory can calibrate the target analytes in 

this method and achieve a linearity metric 

(either RSD or RSE) well below 35%. 

Therefore, laboratories are permitted to use 

more stringent acceptance criteria for 

calibration than described here, for example, 

to harmonize their application of this method 

with those from other sources. 

7.3 Calibration verification—The RF or 

calibration curve must be verified 

immediately after calibration and at the 

beginning of each 12-hour shift, by analysis 

of a standard at or near the concentration of 

the mid-point calibration standard (section 

7.2.1). The standard(s) must be obtained from 

a second manufacturer or a manufacturer’s 

batch prepared independently from the batch 

used for calibration. Traceability must be to 

a national standard, when available. Include 

the surrogates (section 6.8) in this solution. 

It is necessary to verify calibration for the 

analytes of interest (section 1.3) only. 

Note: The 12-hour shift begins after the 

DFTPP (section 13.1) and DDT/endrin tests 

(if DDT and endrin are to be determined), 

and after analysis of the calibration 

verification standard. The 12-hour shift ends 

12 hours later. The DFTPP, DDT/endrin, and 

calibration verification tests are outside of 

the 12-hour shift. 

7.3.1 Analyze the calibration verification 

standard(s) beginning in section 12. Calculate 

the percent recovery of each analyte. 

Compare the recoveries for the analytes of 

interest against the acceptance criteria for 

recovery (Q) in Table 6, and the recoveries 

for the surrogates against the acceptance 

criteria in Table 8. If recovery of the analytes 

of interest and surrogates meet acceptance 

criteria, system performance is acceptable 

and analysis of samples may continue. If any 

individual recovery is outside its limit, 

system performance is unacceptable for that 

analyte. 

Note: The large number of analytes in 

Tables 6 and 8 present a substantial 

probability that one or more will fail 

acceptance criteria when all analytes are 

tested simultaneously. 

7.3.2 When one or more analytes fail 

acceptance criteria, analyze a second aliquot 

of the calibration verification standard and 

compare ONLY those analytes that failed the 

first test (section 7.3.1) with their respective 

acceptance criteria. If these analytes now 

pass, system performance is acceptable and 

analysis of samples may continue. A repeat 

failure of any analyte that failed the first test, 

however, will confirm a general problem 

with the measurement system. If this occurs, 

repair the system (section 7.2.1.1) and repeat 

the test (section 7.3.1), or prepare a fresh 

calibration standard and repeat the test. If 

calibration cannot be verified after 

maintenance or injection of the fresh 

calibration standard, re-calibrate the 

instrument. 

Note: If it is necessary to perform a repeat 

verification test frequently; i.e., perform two 

tests in order to pass, it may be prudent to 

perform two injections in succession and 

review the results, rather than perform one 

injection, review the results, then perform 

the second injection if results from the first 

injection fail. To maintain the validity of the 

test and re-test, system maintenance and/or 

adjustment is not permitted between the 

injections. 

7.3.3 Many of the analytes in Table 3 do 

not have QC acceptance criteria in Table 6, 

and some of the surrogates in Table 8 do not 

have acceptance criteria. If calibration is to 

be verified and other QC tests are to be 

performed for these analytes, acceptance 

criteria must be developed and applied. EPA 

has provided guidance for development of 

QC acceptance criteria (References 12 and 

13). Alternatively, analytes that do not have 

acceptance criteria in Table 6 or Table 8 may 


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be based on laboratory control charts, or 60 

to 140% may be used. 

7.3.4 Internal standard responses—Verify 

that detector sensitivity has not changed by 

comparing the response of each internal 

standard in the calibration verification 

standard (section 7.3) to the response of the 

respective internal standard in the midpoint 

calibration standard (section 7.2.1). The peak 

areas or heights of the internal standards in 

the calibration verification standard must be 

within 50% to 200% (1/2 to 2x) of their 

respective peak areas or heights in the midpoint 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 

vendor of the SPE materials) but any 

laboratory using that specific material must 

have the results of the study available. This 

includes a full data package with the raw 

data that will allow an independent reviewer 

to verify each determination and calculation 

performed by the laboratory (see section 

8.1.2.2.5, items (a)–(q)). 

8.1.2.1.2 Sample matrices on which MS/ 

MSD tests must be performed for nationwide 

use of an allowed modification: 

(a) Effluent from a POTW. 

(b) ASTM D5905 Standard Specification 

for Substitute Wastewater. 

(c) Sewage sludge, if sewage sludge will be 

in the permit. 

(d) ASTM D1141 Standard Specification 

for Substitute Ocean Water, if ocean water 

will be in the permit. 

(e) Untreated and treated wastewaters up to 

a total of nine matrix types (see https://

www.epa.gov/eg/industrial-effluentguidelines for a list of industrial categories 

with existing effluent guidelines). 

(i) At least one of the above wastewater 

matrix types must have at least one of the 

following characteristics: 

(A) Total suspended solids greater than 40 

mg/L. 

(B) Total dissolved solids greater than 100 

mg/L. 

(C) Oil and grease greater than 20 mg/L. 

(D) NaCl greater than 120 mg/L. 

(E) CaCO3 greater than 140 mg/L. 

(ii) Results of MS/MSD tests must meet QC 

acceptance criteria in Section 8.3. 

(f) A proficiency testing (PT) sample from 

a recognized provider, in addition to tests of 

the nine matrices (section 8.1.2.1.1). 

8.1.2.2 The laboratory is required to 

maintain records of modifications made to 

this method. These records include the 

following, at a minimum: 

8.1.2.2.1 The names, titles, and business 

street addresses, telephone numbers, and 

email addresses, of the analyst(s) that 

performed the analyses and modification, 

and of the quality control officer that 

witnessed and will verify the analyses and 

modifications. 

8.1.2.2.2 A list of analytes, by name and 

CAS Registry Number. 

8.1.2.2.3 A narrative stating reason(s) for 

the modifications. 

8.1.2.2.4 Results from all quality control 

(QC) tests comparing the modified method to 

this method, including: 

(a) Calibration (section 7). 

(b) Calibration verification (section 7). 

(c) Initial demonstration of capability 

(section 8.2). 

(d) Analysis of blanks (section 8.5). 

(e) Matrix spike/matrix spike duplicate 

analysis (section 8.3). 

(f) Laboratory control sample analysis 

(section 8.4). 

8.1.2.2.5 Data that will allow an 

independent reviewer to validate each 

determination by tracing the instrument 

output (peak height, area, or other signal) to 

the final result. These data are to include: 

(a) Sample numbers and other identifiers. 

(b) Extraction dates. 

(c) Analysis dates and times. 

(d) Analysis sequence/run chronology. 

(e) Sample weight or volume (ssection 10). 

(f) Extract volume prior to each cleanup 

step (sections 10 and 11). 

(g) Extract volume after each cleanup step 

(section 11). 

(h) Final extract volume prior to injection 

(sections 10 and 12). 

(i) Injection volume (section 12.2.3). 

(j) Sample or extract dilution (section 

12.2.3.2). 

(k) Instrument and operating conditions. 

(l) Column (dimensions, material, etc). 

(m) Operating conditions (temperature 

program, flow rate, etc). 

(n) Detector (type, operating conditions, 

etc). 

(o) Chromatograms, mass spectra, and 

other recordings of raw data. 

(p) Quantitation reports, data system 

outputs, and other data to link the raw data 

to the results reported. 

(q) A written Standard Operating 

Procedure (SOP). 

8.1.2.2.6 Each individual laboratory 

wishing to use a given modification must 

perform the start-up tests in section 8.1.2 

(e.g., DOC, MDL), with the modification as an 

integral part of this method prior to applying 

the modification to specific discharges. 

Results of the DOC must meet the QC 

acceptance criteria in Table 6 for the analytes 

of interest (section 1.3), and the MDLs must 

be equal to or lower than the MDLs in Tables 

1, 2, or 3 for the analytes of interest. 

8.1.3 Before analyzing samples, the 

laboratory must analyze a blank to 

demonstrate that interferences from the 

analytical system, labware, and reagents, are 

under control. Each time a batch of samples 

is extracted or reagents are changed, a blank 

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must be extracted and analyzed as a 

safeguard against laboratory contamination. 

Requirements for the blank are given in 

section 8.5. 

8.1.4 The laboratory must, on an ongoing 

basis, spike and analyze to monitor and 

evaluate method and laboratory performance 

on the sample matrix. The procedure for 

spiking and analysis is given in section 8.3. 

8.1.5 The laboratory must, on an ongoing 

basis, demonstrate through analysis of a 

quality control check sample (laboratory 

control sample, LCS; on-going precision and 

recovery sample, OPR) that the measurement 

system is in control. This procedure is given 

in section 8.4. 

8.1.6 The laboratory must maintain 

performance records to document the quality 

of data that is generated. This procedure is 

given in section 8.9. 

8.1.7 The large number of analytes tested 

in performance tests in this method present 

a substantial probability that one or more 

will fail acceptance criteria when many 

analytes are tested simultaneously, and a retest is allowed if this situation should occur. 

If, however, continued re-testing results in 

further repeated failures, the laboratory must 

document and report the failures (e.g., as 

qualifiers on results), unless the failures are 

not required to be reported as determined by 

the regulatory/control authority. Results 

associated with a QC failure for an analyte 

regulated in a discharge cannot be used to 

demonstrate regulatory compliance. QC 

failures do not relieve a discharger or 

permittee of reporting timely results. 

8.2 Initial demonstration of capability 

(DOC)—To establish the ability to generate 

acceptable recovery and precision, the 

laboratory must perform the DOC in sections 

8.2.1 through 8.2.6 for the analytes of 

interest. The laboratory must also establish 

MDLs for the analytes of interest using the 

MDL procedure at 40 CFR part 136, appendix 

B. The laboratory’s MDLs must be equal to 

or lower than those listed in Tables 1, 2, or 

3 or lower than one third the regulatory 

compliance limit, whichever is greater. For 

MDLs not listed in Tables 4 and 5, the 

laboratory must determine the MDLs using 

the MDL procedure at 40 CFR part 136, 

appendix B under the same conditions used 

to determine the MDLs for the analytes listed 

in Tables 1, 2, and 3. All procedures used in 

the analysis, including cleanup procedures, 

must be included in the DOC. 

8.2.1 For the DOC, a QC check sample 

concentrate (LCS concentrate) containing 

each analyte of interest (section 1.3) is 

prepared in a water-miscible solvent. The QC 

check sample concentrate must be prepared 

independently from those used for 

calibration, but may be from the same source 

as the second-source standard used for 

calibration verification (Section 7.3). The 

concentrate should produce concentrations 

of the analytes of interest in water at the midpoint of the calibration range, and may be at 

the same concentration as the LCS (section 

8.4). Multiple solutions may be required. 

Note: QC check sample concentrates are no 

longer available from EPA. 

8.2.2 Using a pipet or micro-syringe, 

prepare four LCSs by adding an appropriate 

volume of the concentrate to each of four 

aliquots of reagent water, and mix well. The 

volume of reagent water must be the same as 

the volume that will be used for the sample, 

blank (section 8.5), and MS/MSD (section 

8.3). A volume of 1–L and a concentration of 

100 mg/L were used to develop the QC 

acceptance criteria in Table 6. Also add an 

aliquot of the surrogate spiking solution 

(section 6.8) to the reagent-water aliquots. 

8.2.3 Extract and analyze the four LCSs 

according to the method beginning in Section 

10. 

8.2.4 Calculate the average percent 

recovery (X) and the standard deviation of 

the percent recovery (s) for each analyte 

using the four results. 

8.2.5 For each analyte, compare s and (X) 

with the corresponding acceptance criteria 

for precision and recovery in Table 6. For 

analytes in Table 3 not listed in Table 6, DOC 

QC acceptance criteria must be developed by 

the laboratory. EPA has provided guidance 

for development of QC acceptance criteria 

(References 12 and 13). Alternatively, 

acceptance criteria for analytes not listed in 

Table 6 may be based on laboratory control 

charts. If s and (X) for all analytes of interest 

meet the acceptance criteria, system 

performance is acceptable and analysis of 

blanks and samples may begin. If any 

individual s exceeds the precision limit or 

any individual (X) falls outside the range for 

recovery, system performance is 

unacceptable for that analyte. 

Note: The large number of analytes in 

Tables 1–3 present a substantial probability 

that one or more will fail at least one of the 

acceptance criteria when many or all analytes 

are determined simultaneously. Therefore, 

the analyst is permitted to conduct a ‘‘re-test’’ 

as described in section 8.2.6. 

8.2.6 When one or more of the analytes 

tested fail at least one of the acceptance 

criteria, repeat the test for only the analytes 

that failed. If results for these analytes pass, 

system performance is acceptable and 

analysis of samples and blanks may proceed. 

If one or more of the analytes again fail, 

system performance is unacceptable for the 

analytes that failed the acceptance criteria. 

Correct the problem and repeat the test 

(section 8.2). See section 8.1.7 for disposition 

of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between this pair 

of tests. 

8.3 Matrix spike and matrix spike 

duplicate (MS/MSD)—The purpose of the 

MS/MSD requirement is to provide data that 

demonstrate the effectiveness of the method 

as applied to the samples in question by a 

given laboratory, and both the data user 

(discharger, permittee, regulated entity, 

regulatory/control authority, customer, other) 

and the laboratory share responsibility for 

provision of such data. The data user should 

identify the sample and the analytes of 

interest (section 1.3) to be spiked and provide 

sufficient sample volume to perform MS/

MSD analyses. The laboratory must, on an 

ongoing basis, spike at least 5% of the 

samples in duplicate from each discharge 

being monitored to assess accuracy (recovery 

and precision). If direction cannot be 

obtained from the data user, the laboratory 

must spike at least one sample in duplicate 

per extraction batch of up to 20 samples with 

the analytes in Table 1. Spiked sample 

results should be reported only to the data 

user whose sample was spiked, or as 

requested or required by a regulatory/control 

authority, or in a permit. 

8.3.1 If, as in compliance monitoring, the 

concentration of a specific analyte will be 

checked against a regulatory concentration 

limit, the concentration of the spike should 

be at that limit; otherwise, the concentration 

of the spike should be one to five times 

higher than the background concentration 

determined in section 8.3.2, at or near the 

midpoint of the calibration range, or at the 

concentration in the LCS (section 8.4) 

whichever concentration would be larger. 

8.3.2 Analyze one sample aliquot to 

determine the background concentration (B) 

of the each analyte of interest. If necessary, 

prepare a new check sample concentrate 

(section 8.2.1) appropriate for the background 

concentration. Spike and analyze two 

additional sample aliquots, and determine 

the concentration after spiking (A1 and A2) of 

each analyte. Calculate the percent recoveries 

(P1 and P2) as 100 (A1 ¥ B)/T and 100 (A2

¥ B)/T, where T is the known true value of 

the spike. Also calculate the relative percent 

difference (RPD) between the concentrations 

(A1 and A2) as 200 |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. See Section 8.1.7 for disposition 

of failures. 

8.3.3.2 The acceptance criteria in Table 6 

were calculated to include an allowance for 

error in measurement of both the background 

and spike concentrations, assuming a spike 

to background ratio of 5:1. This error will be 

accounted for to the extent that the spike to 

background ratio approaches 5:1 (Reference 

14) and is applied to spike concentrations of 

100 mg/L and higher. If spiking is performed 

at a concentration lower than 100 mg/L, the 

laboratory must use the QC acceptance 

criteria in Table 6, the optional QC 

acceptance criteria calculated for the specific 

spike concentration in Table 7, or optional 

in-house criteria (section 8.3.4). To use the 

acceptance criteria in Table 7: (1) Calculate 

recovery (X′) using the equation in Table 7, 

substituting the spike concentration (T) for C; 

(2) Calculate overall precision (S′) using the 

equation in Table 7, substituting X′ for X; (3) 

Calculate the range for recovery at the spike 

concentration as (100 X′/T) ± 2.44(100 S′/

T)% (Reference 14). For analytes in Table 3 

not listed in Table 6, QC acceptance criteria 

must be developed by the laboratory. EPA 

has provided guidance for development of 

QC acceptance criteria (References 12 and 

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13). Alternatively, acceptance criteria may be 

based on laboratory control charts. 

8.3.4 After analysis of a minimum of 20 

MS/MSD samples for each target analyte and 

surrogate, and if the laboratory chooses to 

develop and apply the optional in-house QC 

limits (Section 8.3.3), the laboratory should 

calculate and apply the optional in-house QC 

limits for recovery and RPD of future MS/

MSD samples (Section 8.3). The QC limits for 

recovery are calculated as the mean observed 

recovery ±3 standard deviations, and the 

upper QC limit for RPD is calculated as the 

mean RPD plus 3 standard deviations of the 

RPDs. The in-house QC limits must be 

updated at least every two years and reestablished after any major change in the 

analytical instrumentation or process. If inhouse QC limits are developed, at least 80% 

of the analytes tested in the MS/MSD must 

have in-house QC acceptance criteria that are 

tighter than those in Table 6, and the 

remaining analytes (those other than the 

analytes included in the 80%) must meet the 

acceptance criteria in Table 6. If an in-house 

QC limit for the RPD is greater than the limit 

in Table 6, then the limit in Table 6 must be 

used. Similarly, if an in-house lower limit for 

recovery is below the lower limit in Table 6, 

then the lower limit in Table 6 must be used, 

and if an in-house upper limit for recovery 

is above the upper limit in Table 6, then the 

upper limit in Table 6 must be used. 

8.4 Laboratory control sample (LCS)—A 

QC check sample (laboratory control sample, 

LCS; on-going precision and recovery 

sample, OPR) containing each analyte of 

interest (Section 1.3) and surrogate must be 

prepared and analyzed with each extraction 

batch of up to 20 samples to demonstrate 

acceptable recovery of the analytes of interest 

from a clean sample matrix. 

8.4.1 Prepare the LCS by adding QC 

check sample concentrate (section 8.2.1) to 

reagent water. Include all analytes of interest 

(section 1.3) in the LCS. The LCS may be the 

same sample prepared for the DOC (section 

8.2.1). The volume of reagent water must be 

the same as the volume used for the sample, 

blank (section 8.5), and MS/MSD (Section 

8.3). Also add an aliquot of the surrogate 

spiking solution (section 6.8). The 

concentration of the analytes in reagent water 

should be the same as the concentration in 

the DOC (section 8.2.2). 

8.4.2 Analyze the LCS prior to analysis of 

field samples in the extraction batch. 

Determine the concentration (A) of each 

analyte. Calculate the percent recovery (PS) 

as 100 (A/T)%, where T is the true value of 

the concentration in the LCS. 

8.4.3 Compare the percent recovery (PS) 

for each analyte with its corresponding QC 

acceptance criterion in Table 6. For analytes 

of interest in Table 3 not listed in Table 6, 

use the QC acceptance criteria developed for 

the LCS (section 8.4.5), or limits based on 

laboratory control charts. If the recoveries for 

all analytes of interest fall within their 

respective QC acceptance criteria, analysis of 

blanks and field samples may proceed. If any 

individual PS falls outside the range, proceed 

according to section 8.4.4. 

Note: The large number of analytes in 

Tables 1–3 present a substantial probability 

that one or more will fail the acceptance 

criteria when all analytes are tested 

simultaneously. Because a re-test is allowed 

in event of failure (sections 8.1.7 and 8.4.3), 

it may be prudent to extract and analyze two 

LCSs together and evaluate results of the 

second analysis against the QC acceptance 

criteria only if an analyte fails the first test. 

8.4.4 Repeat the test only for those 

analytes that failed to meet the acceptance 

criteria (PS). If these analytes now pass, 

system performance is acceptable and 

analysis of blanks and samples may proceed. 

Repeated failure, however, will confirm a 

general problem with the measurement 

system. If this occurs, repeat the test using a 

fresh LCS (section 8.2.2) or an LCS prepared 

with a fresh QC check sample concentrate 

(section 8.2.1), or perform and document 

system repair. Subsequent to analysis of the 

LCS prepared with a fresh sample 

concentrate, or to system repair, repeat the 

LCS test (section 8.4). If failure of the LCS 

indicates a systemic problem with samples in 

the batch, re-extract and re-analyze the 

samples in the batch. See section 8.1.7 for 

disposition of repeated failures. 

Note: To maintain the validity of the test 

and re-test, system maintenance and/or 

adjustment is not permitted between the pair 

of tests. 

8.4.5 After analysis of 20 LCS samples, 

and if the laboratory chooses to develop and 

apply in-house QC limits, the laboratory 

should calculate and apply in-house QC 

limits for recovery to future LCS samples 

(section 8.4). Limits for recovery in the LCS 

should be calculated as the mean recovery ±3 

standard deviations. A minimum of 80% of 

the analytes tested for in the LCS must have 

QC acceptance criteria tighter than those in 

Table 6, and the remaining analytes (those 

other than the analytes included in the 80%) 

must meet the acceptance criteria in Table 6. 

If an in-house lower limit for recovery is 

lower than the lower limit in Table 6, the 

lower limit in Table 6 must be used, and if 

an in-house upper limit for recovery is higher 

than the upper limit in Table 6, the upper 

limit in Table 6 must be used. Many of the 

analytes and surrogates do not contain 

acceptance criteria. The laboratory should 

use 60–140% as interim acceptance criteria 

for recoveries of spiked analytes and 

surrogates that do not have recovery limits 

specified in Table 8, and at least 80% of the 

surrogates must meet the 60–140% interim 

criteria until in-house LCS and surrogate 

limits are developed. Alternatively, 

acceptance criteria for analytes that do not 

have recovery limits in Table 6 may be based 

on laboratory control charts. In-house QC 

acceptance criteria must be updated at least 

every two years. 

8.5 Blank—A blank must be extracted 

and analyzed with each extraction batch to 

demonstrate that the reagents and equipment 

used for preparation and analysis are free 

from contamination. 

8.5.1 Spike the surrogates into the blank. 

Extract and concentrate the blank using the 

same procedures and reagents used for the 

samples, LCS, and MS/MSD in the batch. 

Analyze the blank immediately after analysis 

of the LCS (section 8.4) and prior to analysis 

of the MS/MSD and samples to demonstrate 

freedom from contamination. 

8.5.2 If an analyte of interest is found in 

the blank: At a concentration greater than the 

MDL for the analyte, at a concentration 

greater than one-third the regulatory 

compliance limit, or at a concentration 

greater than one-tenth the concentration in a 

sample in the extraction batch, whichever is 

greater, analysis of samples must be halted, 

and the problem corrected. If the 

contamination is traceable to the extraction 

batch, samples affected by the blank must be 

re-extracted and the extracts re-analyzed. If, 

however, continued re-testing results in 

repeated blank contamination, the laboratory 

must document and report the failures (e.g., 

as qualifiers on results), unless the failures 

are not required to be reported as determined 

by the regulatory/control authority. Results 

associated with blank contamination for an 

analyte regulated in a discharge cannot be 

used to demonstrate regulatory compliance. 

QC failures do not relieve a discharger or 

permittee of reporting timely results. 

8.6 Internal standards responses. 

8.6.1 Calibration verification—The 

responses (GC peak heights or areas) of the 

internal standards in the calibration 

verification must be within 50% to 200% 

(1/2 to 2x) of their respective responses in the 

mid-point calibration standard. If they are 

not, repeat the calibration verification 

(Section 7.4) test or perform and document 

system repair. Subsequent to repair, repeat 

the calibration verification. If the responses 

are still not within 50% to 200%, re-calibrate 

the instrument (Section 7) and repeat the 

calibration verification test. 

8.6.2 Samples, blanks, LCSs, and MS/

MSDs—The responses (GC peak heights or 

areas) of each internal standard in each 

sample, blank, and MS/MSD must be within 

50% to 200% (1/2 to 2x) of its respective 

response in the LCS for the extraction batch. 

If, as a group, all internal standards are not 

within this range, perform and document 

system repair, repeat the calibration 

verification (section 8.4), and re-analyze the 

affected samples. If a single internal standard 

is not within the 50% to 200% range, use an 

alternate internal standard for quantitation of 

the analyte referenced to the affected internal 

standard. It may be necessary to use the data 

system to calculate a new response factor 

from calibration data for the alternate 

internal standard/analyte pair. If an internal 

standard fails the 50–200% criteria and no 

analytes are detected in the sample, ignore 

the failure or report it if required by the 

regulatory/control authority. 

8.7 Surrogate recoveries—The laboratory 

must evaluate surrogate recovery data in each 

sample against its in-house surrogate 

recovery limits. The laboratory may use 60– 

140% as interim acceptance criteria for 

recoveries for surrogates not listed in Table 

8. At least 80% of the surrogates must meet 

the 60–140% interim criteria until in-house 

limits are developed. Alternatively, surrogate 

recovery limits may be developed from 

laboratory control charts, but such limits 

must be at least as restrictive as those in 

Table 8. Spike the surrogates into all 

samples, blanks, LCSs, and MS/MSDs. 

Compare surrogate recoveries against the QC 

acceptance criteria in Table 8 and/or those 

developed in section 7.3.3 or 8.4.5. If any 

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recovery fails its criteria, attempt to find and 

correct the cause of the failure. See section 

8.1.7 for disposition of failures. 

8.8 DDT and endrin decomposition 

(breakdown)—If DDT and/or endrin are to be 

analyzed using this method, the DDT/endrin 

decomposition test in section 13.8 must be 

performed to reliably quantify these two 

pesticides. 

8.9 As part of the QC program for the 

laboratory, control charts or statements of 

accuracy for wastewater samples must be 

assessed and records maintained (40 CFR 

136.7(c)(1)(viii)). After analysis of five or 

more spiked wastewater samples as in 

section 8.3, calculate the average percent 

recovery (Px) and the standard deviation of 

the percent recovery (sp). Express the 

accuracy assessment as a percent interval 

from Px ¥2sp to Px +2sp. For example, if Px

= 90% and sp = 10%, the accuracy interval 

is expressed as 70–110%. Update the 

accuracy assessment for each analyte on a 

regular basis (e.g., after each 5–10 new 

accuracy measurements). If desired, 

statements of accuracy for laboratory 

performance, independent of performance on 

samples, may be developed using LCSs. 

8.10 It is recommended that the 

laboratory adopt additional quality assurance 

practices for use with this method. The 

specific practices that are most productive 

depend upon the needs of the laboratory and 

the nature of the samples. Field duplicates 

may be analyzed to assess the precision of 

environmental measurements. Whenever 

possible, the laboratory should analyze 

standard reference materials and participate 

in relevant performance evaluation studies. 

9. Sample Collection, Preservation, and 

Handling 

9.1 Collect samples as grab samples in 

amber or clear glass bottles, or in refrigerated 

bottles using automatic sampling equipment. 

If clear glass is used, protect samples from 

light. Collect 1–L of ambient waters, 

effluents, and other aqueous samples. If the 

sensitivity of the analytical system is 

sufficient, a smaller volume (e.g., 250 mL), 

but no less than 100 mL, may be used. 

Conventional sampling practices (Reference 

15) should be followed, except that the bottle 

must not be pre-rinsed with sample before 

collection. Automatic sampling equipment 

must be as free as possible of polyvinyl 

chloride or other tubing or other potential 

sources of contamination. If needed, collect 

additional sample(s) for the MS/MSD 

(section 8.3). 

9.2 Ice or refrigerate samples at ≤6 °C 

from the time of collection until extraction, 

but do not freeze. If residual chlorine is 

present, add 80 mg of sodium thiosulfate per 

liter of sample and mix well. Any method 

suitable for field use may be employed to test 

for residual chlorine (Reference 16). Add 

more sodium sulfate if 80 mg/L is insufficient 

but do not add excess sodium thiosulfate. If 

sodium thiosulfate interferes in the 

determination of the analytes, an alternate 

preservative (e.g., ascorbic acid or sodium 

sulfite) may be used. If preservative has been 

added, shake the sample vigorously for one 

minute. Maintain the hermetic seal on the 

sample bottle until time of analysis. 

9.3 All samples must be extracted within 

7 days of collection and sample extracts must 

be analyzed within 40 days of extraction. 

10. Extraction 

10.1 This section contains procedures for 

separatory funnel liquid-liquid extraction 

(SFLLE) and continuous liquid-liquid 

extraction (CLLE). SFLLE is faster, but may 

not be as effective as CLLE for recovery of 

polar analytes such as phenol. SFLLE is labor 

intensive and may result in formation of 

emulsions that are difficult to break. CLLE is 

less labor intensive, avoids emulsion 

formation, but requires more time (18–24 

hours) and more hood space, and may 

require more solvent. The procedures assume 

base-neutral extraction followed by acid 

extraction. For some matrices and analytes of 

interest, improved results may be obtained by 

acid-neutral extraction followed by base 

extraction. A single acid or base extraction 

may also be performed. If an extraction 

scheme alternate to base-neutral followed by 

acid extraction is used, all QC tests must be 

performed and all QC acceptance criteria 

must be met with that extraction scheme as 

an integral part of this method. Solid-phase 

extraction (SPE) may be used provided 

requirements in section 8.1.2 are met. 

10.2 Separatory funnel liquid-liquid 

extraction (SFLLE) and extract concentration. 

10.2.1 The SFLLE procedure below 

assumes a sample volume of 1 L. When a 

different sample volume is extracted, adjust 

the volume of methylene chloride 

accordingly. 

10.2.2 Mark the water meniscus on the 

side of the sample bottle for later 

determination of sample volume. Pour the 

entire sample into the separatory funnel. 

Pipet the surrogate standard spiking solution 

(section 6.8) into the separatory funnel. If the 

sample will be used for the LCS or MS or 

MSD, pipet the appropriate check sample 

concentrate (section 8.2.1 or 8.3.2) into the 

separatory funnel. Mix well. Check the pH of 

the sample with wide-range pH paper and 

adjust to pH 11–13 with sodium hydroxide 

solution. 

10.2.3 Add 60 mL of methylene chloride 

to the sample bottle, seal, and shake for 

approximately 30 seconds to rinse the inner 

surface. Transfer the solvent to the separatory 

funnel and extract the sample by shaking the 

funnel for two minutes with periodic venting 

to release excess pressure. Allow the organic 

layer to separate from the water phase for a 

minimum of 10 minutes. If the emulsion 

interface between layers is more than onethird the volume of the solvent layer, the 

analyst must employ mechanical techniques 

to complete the phase separation. The 

optimum technique depends upon the 

sample, but may include stirring, filtration of 

the emulsion through glass wool or phaseseparation paper, salting, centrifugation, or 

other physical methods. Collect the 

methylene chloride extract in a flask. If the 

emulsion cannot be broken (recovery of 

<80% of the methylene chloride), transfer the 

sample, solvent, and emulsion into a 

continuous extractor and proceed as 

described in section 10.3. 

10.2.4 Add a second 60-mL volume of 

methylene chloride to the sample bottle and 

repeat the extraction procedure a second 

time, combining the extracts in the 

Erlenmeyer flask. Perform a third extraction 

in the same manner. 

10.2.5 Adjust the pH of the aqueous 

phase to less than 2 using sulfuric acid. 

Serially extract the acidified aqueous phase 

three times with 60 mL aliquots of methylene 

chloride. Collect and combine the extracts in 

a flask in the same manner as the base/

neutral extracts. 

Note: Base/neutral and acid extracts may 

be combined for concentration and analysis 

provided all QC tests are performed and all 

QC acceptance criteria met for the analytes of 

interest with the combined extract as an 

integral part of this method, and provided 

that the analytes of interest are as reliably 

identified and quantified as when the 

extracts are analyzed separately. If doubt 

exists as to whether identification and 

quantitation will be affected by use of a 

combined extract, the fractions must be 

analyzed separately. 

10.2.6 For each fraction or the combined 

fractions, assemble a Kuderna-Danish (K–D) 

concentrator by attaching a 10-mL 

concentrator tube to a 500-mL evaporative 

flask. Other concentration devices or 

techniques may be used in place of the K– 

D concentrator so long as the requirements in 

section 8.2 are met. 

10.2.7 For each fraction or the combined 

fractions, pour the extract through a solventrinsed 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 distillation, the balls of the 

column will actively chatter but the 

chambers will not flood with condensed 

solvent. When the apparent volume of liquid 

reaches 1 mL or other determined amount, 

remove the K–D apparatus from the water 

bath and allow to drain and cool for at least 

10 minutes. Remove the Snyder column and 

rinse the flask and its lower joint into the 

concentrator tube with 1–2 mL of methylene 

chloride. A 5-mL syringe is recommended for 

this operation. If the sample will be cleaned 

up, reserve the K–D apparatus for 

concentration of the cleaned up extract. 

Adjust the volume to 5 mL with methylene 

chloride and proceed to section 11 for 

cleanup; otherwise, further concentrate the 

extract for GC/MS analysis per section 10.2.9 

or 10.2.10. 

10.2.9 Micro Kuderna-Danish 

concentration—Add another one or two clean 

boiling chips to the concentrator tube for 

each fraction and attach a two-ball microSnyder column. Pre-wet the Snyder column 

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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 11.2) and are ready 

for analysis are exchanged into methylene 

chloride. 

10.2.10.1 Transfer the vial containing the 

sample extract to the nitrogen evaporation 

(blowdown) device (section 5.8). Lower the 

vial into the water bath and begin 

concentrating. If the more volatile analytes 

(section 1.2) are to be concentrated, use room 

temperature for concentration; otherwise, a 

slightly elevated (e.g., 30–45 °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. Alternative means of compensating the 

loss during GPC are acceptable so long as 

they produce results as accurate as results 

produced using the procedure detailed in 

this Section. An alternative final volume may 

be used, if desired, and the calculations 

adjusted accordingly. 

Note: The difference in the volume fraction 

for an extract cleaned up by GPC accounts for 

the loss in GPC cleanup. Also, by preserving 

the ratio between the volume extracted and 

the final extract volume, the concentrations 

and detection limits do not need to be 

adjusted for differences in the volume 

extracted and the extract volume. 

10.2.11 Transfer the concentrated extract 

to a vial with fluoropolymer-lined cap. Seal 

the vial and label with the sample number. 

Store in the dark at room temperature until 

ready for GC analysis. If GC analysis will not 

be performed on the same day, store the vial 

in the dark at ≤6 °C. Analyze the extract by 

GC/MS per the procedure in section 12. 

10.2.12 Determine the original sample 

volume by refilling the sample bottle to the 

mark and transferring the liquid to an 

appropriately sized graduated cylinder. For 

sample volumes on the order of 1000 mL, 

record the sample volume to the nearest 10 

mL; for sample volumes on the order of 100 

mL, record the volume to the nearest 1 mL. 

Sample volumes may also be determined by 

weighing the container before and after 

filling to the mark with water. 

10.3 Continuous liquid/liquid extraction 

(CLLE). 

Note: With CLLE, phenol, 2,4-dimethyl 

phenol, and some other analytes may be 

preferentially extracted into the base-neutral 

fraction. Determine an analyte in the fraction 

in which it is identified and quantified most 

reliably. Also, the short-chain phthalate 

esters (e.g., dimethyl phthalate, diethyl 

phthalate) and some other compounds may 

hydrolyze during prolonged exposure to 

basic conditions required for continuous 

extraction, resulting in low recovery of these 

analytes. When these analytes are of interest, 

their recovery may be improved by 

performing the acid extraction first. 

10.3.1 Use CLLE when experience with a 

sample from a given source indicates an 

emulsion problem, or when an emulsion is 

encountered during SFLLE. CLLE may be 

used for all samples, if desired. 

10.3.2 Mark the water meniscus on the 

side of the sample bottle for later 

determination of sample volume. Check the 

pH of the sample with wide-range pH paper 

and adjust to pH 11–13 with sodium 

hydroxide solution. Transfer the sample to 

the continuous extractor. Pipet surrogate 

standard spiking solution (section 6.8) into 

the sample. If the sample will be used for the 

LCS or MS or MSD, pipet the appropriate 

check sample concentrate (section 8.2.1 or 

8.3.2) into the extractor. Mix well. Add 60 

mL of methylene chloride to the sample 

bottle, seal, and shake for 30 seconds to rinse 

the inner surface. Transfer the solvent to the 

extractor. 

10.3.3 Repeat the sample bottle rinse with 

an additional 50–100 mL portion of 

methylene chloride and add the rinse to the 

extractor. 

10.3.4 Add a suitable volume of 

methylene chloride to the distilling flask 

(generally 200–500 mL), add sufficient 

reagent water to ensure proper operation, and 

extract for 18–24 hours. A shorter or longer 

extraction time may be used if all QC 

acceptance criteria are met. Test and, if 

necessary, adjust the pH of the water during 

the second or third hour of the extraction. 

After extraction, allow the apparatus to cool, 

then detach the distilling flask. Dry, 

concentrate, and seal the extract per sections 

10.2.6 through 10.2.11. See the note at 

section 10.2.5 regarding combining extracts 

of the base/neutral and acid fractions. 

10.3.5 Charge the distilling flask with 

methylene chloride and attach it to the 

continuous extractor. Carefully, while 

stirring, adjust the pH of the aqueous phase 

to less than 2 using sulfuric acid. Extract for 

18–24 hours. A shorter or longer extraction 

time may be used if all QC acceptance 

criteria are met. Test and, if necessary, adjust 

the pH of the water during the second or 

third hour of the extraction. After extraction, 

allow the apparatus to cool, then detach the 

distilling flask. Dry, concentrate, and seal the 

extract per sections 10.2.6 through 10.2.11. 

Determine the sample volume per section 

10.2.12. 

11. Extract Cleanup 

Note: Cleanup may not be necessary for 

relatively clean samples (e.g., treated 

effluents, groundwater, drinking water). If 

particular circumstances require the use of a 

cleanup procedure, the laboratory may use 

any or all of the procedures below or any 

other appropriate procedure. Before using a 

cleanup procedure, the laboratory must 

demonstrate that the requirements of section 

8.1.2 can be met using the cleanup procedure 

as an integral part of this method. 

11.1 Gel permeation chromatography 

(GPC). 

11.1.1 Calibration. 

11.1.1.1 Load the calibration solution 

(section 6.12) into the sample loop. 

11.1.1.2 Inject the calibration solution 

and record the signal from the detector. The 

elution pattern will be corn oil, bis(2- 

ethylhexyl) phthalate, pentachlorophenol, 

perylene, and sulfur. 

11.1.1.3 Set the ‘‘dump time’’ to allow 

>85% removal of the corn oil and >85% 

collection of the phthalate. 

11.1.1.4 Set the ‘‘collect time’’ to the peak 

minimum between perylene and sulfur. 

11.1.1.5 Verify calibration with the 

calibration solution after every 20 or fewer 

extracts. Calibration is verified if the recovery 

of the pentachlorophenol is greater than 

85%. If calibration is not verified, recalibrate 

using the calibration solution, and re-extract 

and clean up the preceding extracts using the 

calibrated GPC system. 

11.1.2 Extract cleanup—GPC requires that 

the column not be overloaded. The column 

specified in this method is designed to 

handle a maximum of 0.5 g of high molecular 

weight material in a 5-mL extract. If the 

extract is known or expected to contain more 

than 0.5 g, the extract is split into fractions 

for GPC and the fractions are combined after 

elution from the column. The solids content 

of the extract may be obtained 

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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 an additional compound (Table 3) 

is to be determined; sulfur is to be removed; 

copper will be used for sulfur removal; and 

a sulfur matrix is known or suspected to be 

present, the laboratory must demonstrate that 

the additional compound can be successfully 

extracted and treated with copper in the 

sulfur matrix. Some of the additional 

compounds (Table 3) are known not to be 

amenable to sulfur removal with copper (e.g. 

Atrazine and Diazinon). 

11.2.1.1 Quantitatively transfer the 

extract from section 10.2.8 to a 40- to 50-mL 

flask or bottle. If there is evidence of water 

in the concentrator tube after the transfer, 

rinse the tube with small portions of 

hexane:acetone (40:60) and add to the flask 

or bottle. Mark and set aside the concentrator 

tube for use in re-concentrating the extract. 

11.2.1.2 Add 10–20 g of granular 

anhydrous sodium sulfate to the flask. Swirl 

to dry the extract. 

11.2.1.3 Add activated copper (section 

6.13.1.4) and allow to stand for 30—60 

minutes, swirling occasionally. If the copper 

does not remain bright, add more and swirl 

occasionally for another 30–60 minutes. 

11.2.1.4 After drying and sulfur removal, 

quantitatively transfer the extract to a 

nitrogen-evaporation vial or tube and 

proceed to section 10.2.10 for nitrogen 

evaporation and solvent exchange, taking 

care to leave the sodium sulfate and copper 

in the flask. 

11.2.2 Removal with TBA sulfite. 

11.2.2.1 Using small volumes of hexane, 

quantitatively transfer the extract to a 40- to 

50-mL centrifuge tube with fluoropolymerlined 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 nitrogenevaporation vial or tube and proceed to 

section 10.2.10 for nitrogen evaporation and 

solvent exchange. 

12. Gas Chromatography/Mass Spectrometry 

12.1 Establish the operating conditions in 

Table 4 or 5 for analysis of a base/neutral or 

acid extract, respectively. For analysis of a 

combined extract (section 10.2.5, note), use 

the operating conditions in Table 4 MDLs 

and MLs for the analytes are given in Tables 

1, 2, and 3. Retention times for many of the 

analytes are given in Tables 4 and 5. 

Examples of the separations achieved are 

shown in Figure 2 for the combined extract. 

Alternative columns or chromatographic 

conditions may be used if the requirements 

of section 8.2 are met. Verify system 

performance per section 13. 

12.2 Analysis of a standard or extract. 

12.2.1 Bring the standard or concentrated 

extract (section 10.2.9 or 10.2.11) to room 

temperature and verify that any precipitate 

has redissolved. Verify the level on the 

extract and bring to the mark with solvent if 

required. 

12.2.2 Add the internal standard solution 

(section 6.9) to the extract. Mix thoroughly. 

12.2.3 Inject an appropriate volume of the 

sample extract or standard solution using 

split, splitless, solvent purge, large-volume, 

or on-column injection. If the sample is 

injected manually the solvent-flush 

technique should be used. The injection 

volume depends upon the technique used 

and the ability to meet MDLs or reporting 

limits for regulatory compliance. Injected 

volumes must be the same for standards and 

sample extracts. Record the volume injected 

to two significant figures. 

12.2.3.1 Start the GC column oven 

program upon injection. Start MS data 

collection after the solvent peak elutes. Stop 

data collection after benzo(ghi)perylene 

elutes for the base/neutral or combined 

fractions, or after pentachlorophenol elutes 

for the acid fraction. Return the column to 

the initial temperature for analysis of the 

next standard solution or extract. 

12.2.3.2 If the concentration of any 

analyte of interest exceeds the calibration 

range, either extract and analyze a smaller 

sample volume, or dilute and analyze the 

diluted extract after bringing the 

concentrations of the internal standards to 

the levels in the undiluted extract. 

12.2.4 Perform all qualitative and 

quantitative measurements as described in 

Sections 14 and 15. When standards and 

extracts are not being used for analyses, store 

them refrigerated at ≤6 °C protected from 

light in screw-cap vials equipped with unpierced fluoropolymer-lined septa. 

13. Performance Tests 

13.1 At the beginning of each 12-hour 

shift during which standards or extracts will 

be analyzed, perform the tests in sections 

13.2–13.4 to verify system performance. If an 

extract is concentrated for greater sensitivity 

(e.g., by SIM), all tests must be performed at 

levels consistent with the reduced extract 

volume. 

13.2 DFTPP—Inject the DFTPP standard 

(section 6.10) and verify that the criteria for 

DFTPP in section 7.2.1.1 and Table 9A 

(Reference 18) for a quadrupole MS, or Table 

9B (Reference 19) for a time-of-flight MS, are 

met. 

13.3 GC resolution—The resolution 

should be verified on the mid-point 

concentration of the initial calibration as well 

as the laboratory designated continuing 

calibration verification level if closely eluting 

isomers are to be reported (e.g., 

benzo(b)fluoranthene and 

benzo(k)fluoranthene). Sufficient gas 

chromatographic resolution is achieved if the 

height of the valley between two isomer 

peaks is less than 50% of the average of the 

two peak heights. 

13.4 Calibration verification—Verify 

calibration per sections 7.3 and Table 6. 

13.5 Peak tailing—Verify the tailing factor 

specifications are met per Section 7.2.1.1. 

13.6 Laboratory control sample and 

blank—Analyze the extracts of the LCS and 

blank at the beginning of analyses of samples 

in the extraction batch (section 3.1). The LCS 

must meet the requirements in section 8.4, 

and the blank must meet the requirements in 

section 8.5 before sample extracts may be 

analyzed. 

13.7 Analysis of DFTPP, the DDT/Endrin 

decomposition test (if used), the LCS, and the 

blank are outside of the 12-hour analysis shift 

(section 3.1). The total time for DFTPP, DDT/ 

Endrin, the LCS, the blank, and the 12-hour 

shift must not exceed 15 hours. 

13.8 Decomposition of DDT and endrin— 

If DDT and/or endrin are to be determined, 

this test must be performed prior to 

calibration verification (section 13.4). The QC 

acceptance criteria (section 13.8.3) must be 

met before analyzing samples for DDE and/ 

or Endrin. DDT decomposes to DDE and 

DDD. Endrin decomposes to endrin aldehyde 

and endrin ketone. 

13.8.1 Inject 1 mL of the DDT and endrin 

decomposition solution (section 6.14). As 

noted in section 6.14, other injection 

volumes may be used as long as the 

concentrations of DDT and endrin in the 

solution are adjusted to introduce the masses 

of the two analytes into the instrument that 

are listed in section 6.14. 

13.8.2 Measure the areas of the peaks for 

DDT, DDE, DDD, Endrin, Endrin aldehyde, 

and Endrin ketone. Calculate the percent 

breakdown as shown in the equations below: 

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13.8.3 Both the % breakdown of DDT and 

of Endrin must be less than 20%, otherwise 

the system is not performing acceptably for 

DDT and endrin. In this case, repair the GC 

column system that failed and repeat the 

performance tests (sections 13.2 to 13.6) until 

the specification is met. 

Note: DDT and endrin decomposition are 

usually caused by accumulation of 

particulates in the injector and in the front 

end of the column. Cleaning and silanizing 

the injection port liner, and breaking off a 

short section of the front end of the column 

will usually eliminate the decomposition 

problem. Either of these corrective actions 

may affect retention times, GC resolution, 

and calibration linearity. 

14. Qualitative Identification 

14.1 Identification is accomplished by 

comparison of data from analysis of a sample 

or blank with data stored in the GC/MS data 

system (sections 5.6.5 and 7.2.1.2). 

Identification of an analyte is confirmed per 

sections 14.1.1 through 14.1.4. 

14.1.1 The signals for the quantitation 

and secondary m/z’s stored in the data 

system for each analyte of interest must be 

present and must maximize within the same 

two consecutive scans. 

14.1.2 The retention time for the analyte 

should be within ± 10 seconds of the analyte 

in the calibration verification run at the 

beginning of the shift (section 7.3 or 13.4). 

Note: Retention time windows other than 

± 10 seconds may be appropriate depending 

on the performance of the gas chromatograph 

or observed retention time drifts due to 

certain types of matrix effects. Relative 

retention time (RRT) may be used as an 

alternative to absolute retention times if 

retention time drift is a concern. RRT is a 

unitless quantity (see Sec. 22.2), although 

some procedures refer to ‘‘RRT units’’ in 

providing the specification for the agreement 

between the RRT values in the sample and 

the calibration verification or other standard. 

When significant retention time drifts are 

observed, dilutions or spiked samples may 

help the analyst determine the effects of the 

matrix on elution of the target analytes and 

to assist in qualitative identification. 

14.1.3 Either the background corrected 

EICP areas, or the corrected relative 

intensities of the mass spectral peaks at the 

GC peak maximum, must agree within 50% 

to 200% (1/2 to 2 times) for the quantitation 

and secondary m/z’s in the reference mass 

spectrum stored in the data system (section 

7.2.1.2), or from a reference library. For 

example, if a peak has an intensity of 20% 

relative to the base peak, the analyte is 

identified if the intensity of the peak in the 

sample is in the range of 10% to 40% of the 

base peak. If identification is ambiguous, an 

experienced spectrometrist (section 1.7) must 

determine the presence or absence of the 

compound. 

14.2 Structural isomers that produce very 

similar mass spectra should be identified as 

individual isomers if they have sufficiently 

different gas chromatographic retention 

times. Sufficient gas chromatographic 

resolution is achieved if the height of the 

valley between two isomer peaks is less than 

50% of the average of the two peak heights. 

Otherwise, structural isomers are identified 

as isomeric pairs. 

15. Calculations 

15.1 When an analyte has been identified, 

quantitation of that analyte is based on the 

integrated abundance from the EICP of the 

primary characteristic m/z in Table 4 or 5. 

Calculate the concentration in the extract 

using the response factor (RF) determined in 

Section 7.2.2 and Equation 2. If the 

concentration of an analyte exceeds the 

calibration range, dilute the extract by the 

minimum amount to bring the concentration 

into the calibration range, and re-analyze the 

extract. Determine a dilution factor (DF) from 

the amount of the dilution. For example, if 

the extract is diluted by a factor of 2, DF = 

2. 

where: 

Cex = Concentration of the analyte in the 

extract, in mg/mL, and the other terms are 

as defined in section 7.2.2. 

Calculate the concentration of the analyte 

in the sample using the concentration in the 

extract, the extract volume, the sample 

volume, and the dilution factor, per Equation 

3: 

where: 

Csamp = 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 specified 

otherwise by a regulatory authority or in a 

discharge permit, results for analytes that 

meet the identification criteria are reported 


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down to the concentration of the ML 

established by the laboratory through 

calibration of the instrument (see section 

7.3.2 and the glossary for the derivation of 

the ML). EPA considers the terms ‘‘reporting 

limit,’’ ‘‘quantitation limit,’’ ‘‘limit of 

quantitation,’’ and ‘‘minimum level’’ to be 

synonymous. 

15.2.2.1 Report a result for each analyte 

in each field sample or QC standard at or 

above the ML to 3 significant figures. Report 

a result for each analyte found in each field 

sample or QC standard below the ML as 

‘‘ML’’ where ML is the concentration of the 

analyte at the ML, or as required by the 

regulatory/control authority or permit. Report 

a result for each analyte in a blank at or 

above the MDL to 2 significant figures. 

Report a result for each analyte found in a 

blank below the MDL as ‘‘MDL,’’ where MDL 

is the concentration of the analyte at the 

MDL, or as required by the regulatory/control 

authority or permit. 

15.2.2.2 In addition to reporting results 

for samples and blanks separately, the 

concentration of each analyte in a blank 

associated with the sample may be subtracted 

from the result for that sample, but only if 

requested or required by a regulatory 

authority or in a permit. In this case, both the 

sample result and the blank results must be 

reported together. 

15.2.2.3 Report a result for an analyte 

found in a sample or extract that has been 

diluted at the least dilute level at which the 

area at the quantitation m/z is within the 

calibration range (i.e., above the ML for the 

analyte) and the MS/MSD recovery and RPD 

are within their respective QC acceptance 

criteria (Table 6). This may require reporting 

results for some analytes from different 

analyses. 

15.2.3 Results from tests performed with 

an analytical system that is not in control 

(i.e., that does not meet acceptance criteria 

for any QC test in this method) must be 

documented and reported (e.g., as a qualifier 

on results), unless the failure is not required 

to be reported as determined by the 

regulatory/control authority. Results 

associated with a QC failure cannot be used 

to demonstrate regulatory compliance. QC 

failures do not relieve a discharger or 

permittee of reporting timely results. If the 

holding time would be exceeded for a 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 section 1.1, this method 

was validated through an interlaboratory 

study in the early 1980s. However, the 

fundamental chemistry principles used in 

this method remain sound and continue to 

apply. 

16.3 A chromatogram of the combined 

acid/base/neutral calibration standard is 

shown in Figure 2. 

17. Pollution Prevention 

17.1 Pollution prevention encompasses 

any technique that reduces or eliminates the 

quantity or toxicity of waste at the point of 

generation. Many opportunities for pollution 

prevention exist in laboratory operations. 

EPA has established a preferred hierarchy of 

environmental management techniques that 

places pollution prevention as the 

management option of first choice. Whenever 

feasible, the laboratory should use pollution 

prevention techniques to address waste 

generation. When wastes cannot be reduced 

at the source, the Agency recommends 

recycling as the next best option. 

17.2 The analytes in this method are used 

in extremely small amounts and pose little 

threat to the environment when managed 

properly. Standards should be prepared in 

volumes consistent with laboratory use to 

minimize the disposal of excess volumes of 

expired standards. This method utilizes 

significant quantities of methylene chloride. 

Laboratories are encouraged to recover and 

recycle this and other solvents during extract 

concentration. 

17.3 For information about pollution 

prevention that may be applied to 

laboratories and research institutions, consult 

Less is Better: Laboratory Chemical 

Management for Waste Reduction, available 

from the American Chemical Society’s 

Department of Governmental Relations and 

Science Policy, 1155 16th Street NW., 

Washington DC 20036, 202–872–4477. 

18. Waste Management 

18.1 The laboratory is responsible for 

complying with all Federal, State, and local 

regulations governing waste management, 

particularly the hazardous waste 

identification rules and land disposal 

restrictions, and to protect the air, water, and 

land by minimizing and controlling all 

releases from fume hoods and bench 

operations. Compliance is also required with 

any sewage discharge permits and 

regulations. An overview of requirements can 

be found in Environmental Management 

Guide for Small Laboratories (EPA 233–B– 

98–001). 

18.2 Samples at pH <2, or pH >12, are 

hazardous and must be handled and 

disposed of as hazardous waste, or 

neutralized and disposed of in accordance 

with all federal, state, and local regulations. 

It is the laboratory’s responsibility to comply 

with all federal, state, and local regulations 

governing waste management, particularly 

the hazardous waste identification rules and 

land disposal restrictions. The laboratory 

using this method has the responsibility to 

protect the air, water, and land by 

minimizing and controlling all releases from 

fume hoods and bench operations. 

Compliance is also required with any sewage 

discharge permits and regulations. For 

further information on waste management, 

see ‘‘The Waste Management Manual for 

Laboratory Personnel,’’ also available from 

the American Chemical Society at the 

address in section 17.3. 

18.3 Many analytes in this method 

decompose above 500 ßC. Low-level waste 

such as absorbent paper, tissues, and plastic 

gloves may be burned in an appropriate 

incinerator. Gross quantities of neat or highly 

concentrated solutions of toxic or hazardous 

chemicals should be packaged securely and 

disposed of through commercial or 

governmental channels that are capable of 

handling these types of wastes. 

18.4 For further information on waste 

management, consult The Waste 

Management Manual for Laboratory 

Personnel and Less is Better-Laboratory 

Chemical Management for Waste Reduction, 

available from the American Chemical 

Society’s Department of Government 

Relations and Science Policy, 1155 16th 

Street NW., Washington, DC 20036, 202– 

872–4477. 

19. References 

1. ‘‘Sampling and Analysis Procedures for 

Screening of Industrial Effluents for 

Priority Pollutants,’’ U.S. Environmental 

Protection Agency, Environmental 

Monitoring and Support Laboratory, 

Cincinnati, Ohio 45268, March 1977, 

Revised April 1977. 

2. ‘‘EPA Method Study 30, Method 625, Base/ 

Neutrals, Acids, and Pesticides,’’ EPA 

600/4–84–053, National Technical 

Information Service, PB84–206572, 

Springfield, Virginia 22161, June 1984. 

3. 40 CFR part 136, appendix B. 

4. Olynyk, P., Budde, W.L. and Eichelberger, 

J.W. ‘‘Method Detection Limit for 

Methods 624 and 625,’’ Unpublished 

report, May 14, 1980. 

5. Annual Book of ASTM Standards, Volume 

11.02, D3694–96, ‘‘Standard Practices for 

Preparation of Sample Containers and for 

Preservation of Organic Constituents,’’ 

American Society for Testing and 

Materials, Philadelphia. 

6. Solutions to Analytical Chemistry 

Problems with Clean Water Act Methods, 

EPA 821–R–07–002, March 2007. 

7. ‘‘Carcinogens-Working With Carcinogens,’’ 

Department of Health, Education, and 

Welfare, Public Health Service, Center 

for Disease Control, National Institute for 

Occupational Safety and Health, 

Publication No. 77–206, August 1977. 

8. ‘‘OSHA Safety and Health Standards, 

General Industry,’’ (29 CFR part 1910), 

Occupational Safety and Health 

Administration, OSHA 2206 (Revised, 

January 1976). 

9. ‘‘Safety in Academic Chemistry 

Laboratories,’’ American Chemical 

Society Publication, Committee on 

Chemical Safety, 7th Edition, 2003. 

10. Johnson, R.A., and Wichern, D.W., 

‘‘Applied Multivariate Statistical 

Analysis,’’ 3rd edition, Prentice Hall, 

Englewood Cliffs, NJ, 1992. 

11. 40 CFR 136.6(b)(4)(x). 

12. 40 CFR 136.6(b)(2)(i). 

13. Protocol for EPA Approval of New 

Methods for Organic and Inorganic 

Analytes in Wastewater and Drinking 

Water (EPA–821–B–98–003) March 1999. 

14. Provost, L.P. and Elder, R.S. 

‘‘Interpretation of Percent Recovery 

Data,’’ American Laboratory, 15, 58–63 

(1983). (The value 2.44 used in the 

equation in section 8.3.3 is two times the 

value 1.22 derived in this report.) 

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40926 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

15. ASTM Annual Book of Standards, Part 

31, D3370–76. ‘‘Standard Practices for 

Sampling Water,’’ American Society for 

Testing and Materials, Philadelphia. 

16. 40 CFR 136.3(a), Table IB, Chlorine— 

Total Residual. 

17. ‘‘Manual of Analytical Methods for the 

Analysis of Pesticides in Human and 

Environmental Samples,’’ EPA–600/8– 

80–038, U.S. Environmental Protection 

Agency, Health Effects Research 

Laboratory, Research Triangle Park, 

North Carolina. 

18. Eichelberger, J.W., Harris, L.E., and 

Budde, W.L. ‘‘Reference Compound to 

Calibrate Ion Abundance Measurement 

in Gas Chromatography-Mass 

Spectrometry,’’ Analytical Chemistry, 47, 

995 (1975). 

19. Letter of approval of acceptance criteria 

for DFTPP for time-of-flight mass 

spectrometers from William A. Telliard 

and Herb Brass of EPA to Jack Cochran 

of LECO Corporation, February 9, 2005. 

20. Tables 

TABLE 1—NON PESTICIDE/PCB BASE/NEUTRAL EXTRACTABLES 1

Analyte CAS registry MDL 4

(ug/L) 

ML 5

(ug/L) 

Acenaphthene .............................................................................................................................. 83–32–9 1.9 5.7 

Acenaphthylene ........................................................................................................................... 208–96–8 3.5 10.5 

Anthracene ................................................................................................................................... 120–12–7 1.9 5.7 

Benzidine 2 ................................................................................................................................... 92–87–5 44 132 

Benzo(a)anthracene .................................................................................................................... 56–55–3 7.8 23.4 

Benzo(a)pyrene ........................................................................................................................... 50–32–8 2.5 7.5 

Benzo(b)fluoranthene .................................................................................................................. 205–99–2 4.8 14.4 

Benzo(k)fluoranthene ................................................................................................................... 207–08–9 2.5 7.5 

Benzo(ghi)perylene ...................................................................................................................... 191–24–2 4.1 12.3 

Benzyl butyl phthalate ................................................................................................................. 85–68–7 2.5 7.5 

bis(2-Chloroethoxy)methane ........................................................................................................ 111–91–1 5.3 15.9 

bis(2-Ethylhexyl)phthalate ............................................................................................................ 117–81–7 2.5 7.5 

bis(2-Chloroisopropyl) ether (2,2’-Oxybis[1-chloropropane]) ....................................................... 108–60–1 5.7 17.1 

4-Bromophenyl phenyl ether ....................................................................................................... 101–55–3 1.9 5.7 

2-Chloronaphthalene ................................................................................................................... 91–58–7 1.9 5.7 

4-Chlorophenyl phenyl ether ....................................................................................................... 7005–72–3 4.2 12.6 

Chrysene ...................................................................................................................................... 218–01–9 2.5 7.5 

Dibenz(a,h)anthracene ................................................................................................................ 53–70–3 2.5 7.5 

Di-n-butylphthalate ....................................................................................................................... 84–74–2 2.5 7.5 

3,3’-Dichlorobenzidine ................................................................................................................. 91–94–1 16.5 49.5 

Diethyl phthalate .......................................................................................................................... 84–66–2 1.9 5.7 

Dimethyl phthalate ....................................................................................................................... 131–11–3 1.6 4.8 

2,4-Dinitrotoluene ......................................................................................................................... 121–14–2 5.7 17.1 

2,6-Dinitrotoluene ......................................................................................................................... 606–20–2 1.9 5.7 

Di-n-octylphthalate ....................................................................................................................... 117–84–0 2.5 7.5 

Fluoranthene ................................................................................................................................ 206–44–0 2.2 6.6 

Fluorene ....................................................................................................................................... 86–73–7 1.9 5.7 

Hexachlorobenzene ..................................................................................................................... 118–74–1 1.9 5.7 

Hexachlorobutadiene ................................................................................................................... 87–68–3 0.9 2.7 

Hexachloroethane ........................................................................................................................ 67–72–1 1.6 4.8 

Indeno(1,2,3-cd)pyrene ................................................................................................................ 193–39–5 3.7 11.1 

Isophorone ................................................................................................................................... 78–59–1 2.2 6.6 

Naphthalene ................................................................................................................................. 91–20–3 1.6 4.8 

Nitrobenzene ................................................................................................................................ 98–95–3 1.9 5.7 

N-Nitrosodi-n-propylamine 3 ......................................................................................................... 621–64–7 — — 

Phenanthrene .............................................................................................................................. 85–01–8 5.4 16.2 

Pyrene .......................................................................................................................................... 129–00–0 1.9 5.7 

1,2,4-Trichlorobenzene ................................................................................................................ 120–82–1 1.9 5.7 

1All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A). 

2 Included for tailing factor testing. 

3See section 1.2. 

4 MDL values from the 1984 promulgated version of Method 625. 

5 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 2—ACID EXTRACTABLES 1

Analyte CAS registry MDL 3

(ug/L) 

ML 4

(ug/L) 

4-Chloro-3-methylphenol ............................................................................................................. 59–50–7 3.0 9.0 

2-Chlorophenol ............................................................................................................................ 95–57–8 3.3 9.9 

2,4-Dichlorophenol ....................................................................................................................... 120–83–2 2.7 8.1 

2,4-Dimethylphenol ...................................................................................................................... 105–67–9 2.7 8.1 

2,4-Dinitrophenol .......................................................................................................................... 51–28–5 42 126 

2-Methyl-4,6-dinitrophenol ........................................................................................................... 534–52–1 24 72 

2-Nitrophenol ............................................................................................................................... 88–75–5 3.6 10.8 

4-Nitrophenol ............................................................................................................................... 100–02–7 2.4 7.2 

Pentachlorophenol 2 ..................................................................................................................... 87–86–5 3.6 10.8 

Phenol .......................................................................................................................................... 108–95–2 1.5 4.5 

2,4,6-Trichlorophenol ................................................................................................................... 88–06–2 2.7 8.1 

1All analytes in this table are Priority Pollutants (40 CFR part 423, appendix A). 

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2See section 1.2; included for tailing factor testing. 

3 MDL values from the 1984 promulgated version of Method 625. 

4 ML = Minimum Level—see Glossary for definition and derivation. 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1, 2

Analyte CAS registry MDL 7

(ug/L) 

ML 8

(ug/L) 

Acetophenone .............................................................................................................................. 98–86–2 ........................ ........................

2-Acetylaminofluorene ................................................................................................................. 53–96–3 ........................ ........................

1-Acetyl-2-thiourea ....................................................................................................................... 591–08–2 ........................ ........................

Alachlor ........................................................................................................................................ 15972–60–8 ........................ ........................

Aldrin 3 .......................................................................................................................................... 309–00–2 1.9 5.7 

Ametryn ........................................................................................................................................ 834–12–8 ........................ ........................

2-Aminoanthraquinone ................................................................................................................. 117–79–3 ........................ ........................

Aminoazobenzene ....................................................................................................................... 60–09–3 ........................ ........................

4-Aminobiphenyl .......................................................................................................................... 92–67–1 ........................ ........................

3-Amino-9-ethylcarbazole ............................................................................................................ 132–32–1 ........................ ........................

Anilazine ...................................................................................................................................... 101–05–3 ........................ ........................

Aniline .......................................................................................................................................... 62–53–3 ........................ ........................

o-Anisidine ................................................................................................................................... 90–04–0 ........................ ........................

Aramite ......................................................................................................................................... 140–57–8 ........................ ........................

Atraton ......................................................................................................................................... 1610–17–9 ........................ ........................

Atrazine ........................................................................................................................................ 1912–24–9 ........................ ........................

Azinphos-methyl .......................................................................................................................... 86–50–0 ........................ ........................

Barban ......................................................................................................................................... 101–27–9 ........................ ........................

Benzanthrone ............................................................................................................................... 82–05–3 ........................ ........................

Benzenethiol ................................................................................................................................ 108–98–5 ........................ ........................

Benzoic acid ................................................................................................................................ 65–85–0 ........................ ........................

2,3-Benzofluorene ........................................................................................................................ 243–17–4 ........................ ........................

p-Benzoquinone ........................................................................................................................... 106–51–4 ........................ ........................

Benzyl alcohol .............................................................................................................................. 100–51–6 ........................ ........................

alpha-BHC 3,4 ............................................................................................................................... 319–84–6 ........................ ........................

beta-BHC 3 ................................................................................................................................... 319–85–7 3.1 9.3 

gamma-BHC (Lindane) 3,4 ........................................................................................................... 58–89–8 4.2 12.6 

delta-BHC 3 .................................................................................................................................. 319–86–8 ........................ ........................

Biphenyl ....................................................................................................................................... 92–52–4 ........................ ........................

Bromacil ....................................................................................................................................... 314–40–9 ........................ ........................

2-Bromochlorobenzene ................................................................................................................ 694–80–4 ........................ ........................

3-Bromochlorobenzene ................................................................................................................ 108–39–2 ........................ ........................

Bromoxynil ................................................................................................................................... 1689–84–5 ........................ ........................

Butachlor ...................................................................................................................................... 2318–4669 ........................ ........................

Butylate ........................................................................................................................................ 2008–41–5 ........................ ........................

n-C10 (n-decane) ......................................................................................................................... 124–18–5 ........................ ........................

n-C12 (n-undecane) ..................................................................................................................... 112–40–2 ........................ ........................

n-C14 (n-tetradecane) ................................................................................................................. 629–59–4 ........................ ........................

n-C16 (n-hexadecane) ................................................................................................................. 544–76–3 ........................ ........................

n-C18 (n-octadecane) .................................................................................................................. 593–45–3 ........................ ........................

n-C20 (n-eicosane) ...................................................................................................................... 112–95–8 ........................ ........................

n-C22 (n-docosane) ..................................................................................................................... 629–97–0 ........................ ........................

n-C24 (n-tetracosane) .................................................................................................................. 646–31–1 ........................ ........................

n-C26 (n-hexacosane) ................................................................................................................. 630–01–3 ........................ ........................

n-C28 (n-octacosane) .................................................................................................................. 630–02–4 ........................ ........................

n-C30 (n-triacontane) ................................................................................................................... 638–68–6 ........................ ........................

Captafol ........................................................................................................................................ 2425–06–1 ........................ ........................

Captan ......................................................................................................................................... 133–06–2 ........................ ........................

Carbaryl ....................................................................................................................................... 63–25–2 ........................ ........................

Carbazole ..................................................................................................................................... 86–74–8 ........................ ........................

Carbofuran ................................................................................................................................... 1563–66–2 ........................ ........................

Carboxin ....................................................................................................................................... 5234–68–4 ........................ ........................

Carbophenothion ......................................................................................................................... 786–19–6 ........................ ........................

Chlordane 3,5 ................................................................................................................................ 57–74–9 ........................ ........................

bis(2-Chloroethyl) ether 3,4 ........................................................................................................... 111–44–4 5.7 17.1 

Chloroneb .................................................................................................................................... 2675–77–6 ........................ ........................

4-Chloroaniline ............................................................................................................................. 106–47–8 ........................ ........................

Chlorobenzilate ............................................................................................................................ 510–15–6 ........................ ........................

Chlorfenvinphos ........................................................................................................................... 470–90–6 ........................ ........................

4-Chloro-2-methylaniline .............................................................................................................. 95–69–2 ........................ ........................

3-(Chloromethyl)pyridine hydrochloride ....................................................................................... 6959–48–4 ........................ ........................

4-Chloro-2-nitroaniline ................................................................................................................. 89–63–4 ........................ ........................

Chlorpropham .............................................................................................................................. 101–21–3 ........................ ........................

Chlorothalonil ............................................................................................................................... 1897–45–6 ........................ ........................

1-Chloronaphthalene ................................................................................................................... 90–13–1 ........................ ........................

3-Chloronitrobenzene .................................................................................................................. 121–73–3 ........................ ........................

4-Chloro-1,2-phenylenediamine ................................................................................................... 95–83–0 ........................ ........................

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TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1, 2—Continued 

Analyte CAS registry MDL 7

(ug/L) 

ML 8

(ug/L) 

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 ........................ ........................

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 ........................ ........................

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TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1, 2—Continued 

Analyte CAS registry MDL 7

(ug/L) 

ML 8

(ug/L) 

EPN .............................................................................................................................................. 2104–64–5 ........................ ........................

EPTC ........................................................................................................................................... 759–94–4 ........................ ........................

Ethion ........................................................................................................................................... 563–12–2 ........................ ........................

Ethoprop ...................................................................................................................................... 13194–48–4 ........................ ........................

Ethyl carbamate ........................................................................................................................... 51–79–6 ........................ ........................

Ethyl methanesulfonate ............................................................................................................... 65–50–0 ........................ ........................

Ethylenethiourea .......................................................................................................................... 96–45–7 ........................ ........................

Etridiazole .................................................................................................................................... 2593–15–9 ........................ ........................

Ethynylestradiol-3-methyl ether ................................................................................................... 72–33–3 ........................ ........................

Famphur ....................................................................................................................................... 52–85–7 ........................ ........................

Fenamiphos ................................................................................................................................. 22224–92–6 ........................ ........................

Fenarimol ..................................................................................................................................... 60168–88–9 ........................ ........................

Fensulfothion ............................................................................................................................... 115–90–2 ........................ ........................

Fenthion ....................................................................................................................................... 55–38–9 ........................ ........................

Fluchloralin ................................................................................................................................... 33245–39–5 ........................ ........................

Fluridone ...................................................................................................................................... 59756–60–4 ........................ ........................

Heptachlor 3 ................................................................................................................................. 76–44–8 1.9 5.7 

Heptachlor epoxide 3 .................................................................................................................... 1024–57–3 2.2 6.6 

2,2′,3,3′,4,4′,6-Heptachlorobiphenyl ............................................................................................ 52663–71–5 ........................ ........................

2,2′,4,4′,5′,6-Hexachlorobiphenyl ................................................................................................. 60145–22–4 ........................ ........................

Hexachlorocyclopentadiene 3,4 .................................................................................................... 77–47–4 ........................ ........................

Hexachlorophene ......................................................................................................................... 70–30–4 ........................ ........................

Hexachloropropene ...................................................................................................................... 1888–71–7 ........................ ........................

Hexamethylphosphoramide ......................................................................................................... 680–31–9 ........................ ........................

Hexanoic acid .............................................................................................................................. 142–62–1 ........................ ........................

Hexazinone .................................................................................................................................. 51235–04–2 ........................ ........................

Hydroquinone ............................................................................................................................... 123–31–9 ........................ ........................

Isodrin .......................................................................................................................................... 465–73–6 ........................ ........................

2-Isopropylnaphthalene ............................................................................................................... 2027–17–0 ........................ ........................

Isosafrole ..................................................................................................................................... 120–58–1 ........................ ........................

Kepone ......................................................................................................................................... 143–50–0 ........................ ........................

Leptophos .................................................................................................................................... 21609–90–5 ........................ ........................

Longifolene .................................................................................................................................. 475–20–7 ........................ ........................

Malachite green ........................................................................................................................... 569–64–2 ........................ ........................

Malathion ..................................................................................................................................... 121–75–5 ........................ ........................

Maleic anhydride .......................................................................................................................... 108–31–6 ........................ ........................

Merphos ....................................................................................................................................... 150–50–5 ........................ ........................

Mestranol ..................................................................................................................................... 72–33–3 ........................ ........................

Methapyrilene .............................................................................................................................. 91–80–5 ........................ ........................

Methoxychlor ................................................................................................................................ 72–43–5 ........................ ........................

2-Methylbenzothioazole ............................................................................................................... 120–75–2 ........................ ........................

3-Methylcholanthrene .................................................................................................................. 56–49–5 ........................ ........................

4,4′-Methylenebis(2-chloroaniline) ............................................................................................... 101–14–4 ........................ ........................

4,4′-Methylenebis(N,N-dimethylaniline) ....................................................................................... 101–61–1 ........................ ........................

4,5-Methylenephenanthrene ........................................................................................................ 203–64–5 ........................ ........................

1-Methylfluorene .......................................................................................................................... 1730–37–6 ........................ ........................

Methyl methanesulfonate ............................................................................................................. 66–27–3 ........................ ........................

2-Methylnaphthalene ................................................................................................................... 91–57–6 ........................ ........................

Methylparaoxon ........................................................................................................................... 950–35–6 ........................ ........................

Methyl parathion .......................................................................................................................... 298–00–0 ........................ ........................

1-Methylphenanthrene ................................................................................................................. 832–69–9 ........................ ........................

2-(Methylthio)benzothiazole ......................................................................................................... 615–22–5 ........................ ........................

Metolachlor .................................................................................................................................. 5218–45–2 ........................ ........................

Metribuzin .................................................................................................................................... 21087–64–9 ........................ ........................

Mevinphos .................................................................................................................................... 7786–34–7 ........................ ........................

Mexacarbate ................................................................................................................................ 315–18–4 ........................ ........................

MGK 264 ...................................................................................................................................... 113–48–4 ........................ ........................

Mirex ............................................................................................................................................ 2385–85–5 ........................ ........................

Molinate ....................................................................................................................................... 2212–67–1 ........................ ........................

Monocrotophos ............................................................................................................................ 6923–22–4 ........................ ........................

Naled ............................................................................................................................................ 300–76–5 ........................ ........................

Napropamide ............................................................................................................................... 15299–99–7 ........................ ........................

1,4-Naphthoquinone .................................................................................................................... 130–15–4 ........................ ........................

1-Naphthylamine .......................................................................................................................... 134–32–7 ........................ ........................

2-Naphthylamine .......................................................................................................................... 91–59–8 ........................ ........................

1,5-Naphthalenediamine .............................................................................................................. 2243–62–1 ........................ ........................

Nicotine ........................................................................................................................................ 54–11–5 ........................ ........................

5-Nitroacenaphthene ................................................................................................................... 602–87–9 ........................ ........................

2-Nitroaniline ................................................................................................................................ 88–74–4 ........................ ........................

3-Nitroaniline ................................................................................................................................ 99–09–2 ........................ ........................

4-Nitroaniline ................................................................................................................................ 100–01–6 ........................ ........................

mstockstill on DSK30JT082PROD with RULES2

40930 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1, 2—Continued 

Analyte CAS registry MDL 7

(ug/L) 

ML 8

(ug/L) 

5-Nitro-o-anisidine ........................................................................................................................ 99–59–2 ........................ ........................

4-Nitrobiphenyl ............................................................................................................................. 92–93–3 ........................ ........................

Nitrofen ........................................................................................................................................ 1836–75–5 ........................ ........................

5-Nitro-o-toluidine ........................................................................................................................ 99–55–8 ........................ ........................

Nitroquinoline-1-oxide .................................................................................................................. 56–57–5 ........................ ........................

N-Nitrosodi-n-butylamine 4 ..................................................................................................... 924–16–3 ........................ ........................

N-Nitrosodiethylamine 4 ............................................................................................................... 55–18–5 ........................ ........................

N-Nitrosodimethylamine 3,4 .......................................................................................................... 62–75–9 ........................ ........................

N-Nitrosodiphenylamine 3,4 .......................................................................................................... 86–30–6 ........................ ........................

N-Nitrosomethylethylamine 4 ........................................................................................................ 10595–95–6 ........................ ........................

N-Nitrosomethylphenylamine 4 ..................................................................................................... 614–00–6 ........................ ........................

N-Nitrosomorpholine 4 .................................................................................................................. 59–89–2 ........................ ........................

N-Nitrosopiperidine 4 .................................................................................................................... 100–75–5 ........................ ........................

N-Nitrosopyrrolidine 4 ................................................................................................................... 930–55–2 ........................ ........................

trans-Nonachlor ........................................................................................................................... 39765–80–5 ........................ ........................

Norflurazon .................................................................................................................................. 27314–13–2 ........................ ........................

2,2′,3,3′,4,5′,6,6′-Octachlorobiphenyl .......................................................................................... 40186–71–8 ........................ ........................

Octamethyl pyrophosphoramide .................................................................................................. 152–16–9 ........................ ........................

4,4’-Oxydianiline .......................................................................................................................... 101–80–4 ........................ ........................

Parathion ...................................................................................................................................... 56–38–2 ........................ ........................

PCB–1016 3,5 ............................................................................................................................... 12674–11–2 ........................ ........................

PCB–1221 3,5 ............................................................................................................................... 11104–28–2 30 90 

PCB–1232 3,5 ............................................................................................................................... 11141–16–5 ........................ ........................

PCB–1242 3,5 ............................................................................................................................... 53469–21–9 ........................ ........................

PCB–1248 3,5 ............................................................................................................................... 12672–29–6 ........................ ........................

PCB–1254 3,5 ............................................................................................................................... 11097–69–1 36 108 

PCB–1260 3,5 ............................................................................................................................... 11098–82–5 ........................ ........................

PCB–1268 3,5 ............................................................................................................................... 11100–14–4 ........................ ........................

Pebulate ....................................................................................................................................... 1114–71–2 ........................ ........................

Pentachlorobenzene .................................................................................................................... 608–93–5 ........................ ........................

Pentachloronitrobenzene ............................................................................................................. 82–68–8 ........................ ........................

2,2′,3,4′,6-Pentachlorobiphenyl ................................................................................................... 68194–05–8 ........................ ........................

Pentachloroethane ....................................................................................................................... 76–01–7 ........................ ........................

Pentamethylbenzene ................................................................................................................... 700–12–9 ........................ ........................

Perylene ....................................................................................................................................... 198–55–0 ........................ ........................

Phenacetin ................................................................................................................................... 62–44–2 ........................ ........................

cis-Permethrin .............................................................................................................................. 61949–76–6 ........................ ........................

trans-Permethrin .......................................................................................................................... 61949–77–7 ........................ ........................

Phenobarbital ............................................................................................................................... 50–06–6 ........................ ........................

Phenothiazene ............................................................................................................................. 92–84–2 ........................ ........................

1,4-Phenylenediamine ................................................................................................................. 624–18–0 ........................ ........................

1-Phenylnaphthalene ................................................................................................................... 605–02–7 ........................ ........................

2-Phenylnaphthalene ................................................................................................................... 612–94–2 ........................ ........................

Phorate ........................................................................................................................................ 298–02–2 ........................ ........................

Phosalone .................................................................................................................................... 2310–18–0 ........................ ........................

Phosmet ....................................................................................................................................... 732–11–6 ........................ ........................

Phosphamidon ............................................................................................................................. 13171–21–6 ........................ ........................

Phthalic anhydride ....................................................................................................................... 85–44–9 ........................ ........................

alpha-Picoline (2-Methylpyridine) ................................................................................................ 109–06–8 ........................ ........................

Piperonyl sulfoxide ....................................................................................................................... 120–62–7 ........................ ........................

Prometon ..................................................................................................................................... 1610–18–0 ........................ ........................

Prometryn .................................................................................................................................... 7287–19–6 ........................ ........................

Pronamide .................................................................................................................................... 23950–58–5 ........................ ........................

Propachlor .................................................................................................................................... 1918–16–7 ........................ ........................

Propazine ..................................................................................................................................... 139–40–2 ........................ ........................

Propylthiouracil ............................................................................................................................ 51–52–5 ........................ ........................

Pyridine ........................................................................................................................................ 110–86–1 ........................ ........................

Resorcinol (1,3-Benzenediol) ...................................................................................................... 108–46–3 ........................ ........................

Safrole .......................................................................................................................................... 94–59–7 ........................ ........................

Simazine ...................................................................................................................................... 122–34–9 ........................ ........................

Simetryn ....................................................................................................................................... 1014–70–6 ........................ ........................

Squalene ...................................................................................................................................... 7683–64–9 ........................ ........................

Stirofos ......................................................................................................................................... 22248–79–9 ........................ ........................

Strychnine .................................................................................................................................... 57–24–9 ........................ ........................

Styrene 9 ...................................................................................................................................... 100–42–5 ........................ ........................

Sulfallate ...................................................................................................................................... 95–06–7 ........................ ........................

Tebuthiuron .................................................................................................................................. 34014–18–1 ........................ ........................

Terbacil ........................................................................................................................................ 5902–51–2 ........................ ........................

Terbufos ....................................................................................................................................... 13071–79–9 ........................ ........................

Terbutryn ...................................................................................................................................... 886–50–0 ........................ ........................

alpha-Terpineol ............................................................................................................................ 98–55–5 ........................ ........................

mstockstill on DSK30JT082PROD with RULES2

Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40931 

TABLE 3—ADDITIONAL EXTRACTABLE ANALYTES 1, 2—Continued 

Analyte CAS registry MDL 7

(ug/L) 

ML 8

(ug/L) 

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 Detected as azobenzene. 

7 MDL values from the 1984 promulgated version of Method 625. 

8 ML = Minimum Level—see Glossary for definition and derivation. 

9Styrene may be susceptible to losses during sampling, preservation, and/or extraction of full-volume (1 L) water samples. However, styrene is 

not regulated at 40 CFR part 136, and it is also listed as an analyte in EPA Method 624.1 and EPA Method 1625C, where such losses may be 

less than using Method 625.1. 

TABLE 4—CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC m/z’s FOR BASE/NEUTRAL EXTRACTABLES

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 

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 

mstockstill on DSK30JT082PROD with RULES2

40932 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

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 

Fluorene ................................................... 1401 166 165 167 166 167 195 

4-Chlorophenyl phenyl ether .................... 1409 204 206 141 .................... .................... ....................

Diethyl phthalate ...................................... 1414 149 177 150 177 223 251 

N-Nitrosodiphenylamine ........................... 1464 169 168 167 169 170 198 

4-Bromophenyl phenyl ether .................... 1498 248 250 141 249 251 277 

alpha-BHC ................................................ 1514 183 181 109 .................... .................... ....................

Hexachlorobenzene ................................. 1522 284 142 249 284 286 288 

beta-BHC ................................................. 1544 183 181 109 .................... .................... ....................

gamma-BHC ............................................ 1557 181 183 109 .................... .................... ....................

Phenanthrene ........................................... 1583 178 179 176 178 179 207 

Anthracene ............................................... 1592 178 179 176 178 179 207 

delta-BHC ................................................. 1599 183 109 181 .................... .................... ....................

Heptachlor ................................................ 1683 100 272 274 .................... .................... ....................

Di-n-butyl phthalate .................................. 1723 149 150 104 149 205 279 

Aldrin ........................................................ 1753 66 263 220 .................... .................... ....................

Fluoranthene ............................................ 1817 202 101 100 203 231 243 

Heptachlor epoxide .................................. 1820 353 355 351 .................... .................... ....................

gamma-Chlordane ................................... 1834 373 375 377 .................... .................... ....................

Pyrene ...................................................... 1852 202 101 100 203 231 243 

Benzidine 2 .......................................... 1853 184 92 185 185 213 225 

alpha-Chlordane ....................................... 1854 373 375 377 .................... .................... ....................

Endosulfan I ............................................. 1855 237 339 341 .................... .................... ....................

4,4′-DDE .................................................. 1892 246 248 176 .................... .................... ....................

Dieldrin ..................................................... 1907 79 263 279 .................... .................... ....................

Endrin ....................................................... 1935 81 263 82 .................... .................... ....................

Endosulfan II ............................................ 2014 237 339 341 .................... .................... ....................

4,4′-DDD .................................................. 2019 235 237 165 .................... .................... ....................

Endrin aldehyde ....................................... 2031 67 345 250 .................... .................... ....................

Butyl benzyl phthalate .............................. 2060 149 91 206 149 299 327 

Endosulfan sulfate ................................... 2068 272 387 422 .................... .................... ....................

4,4′-DDT ................................................... 2073 235 237 165 .................... .................... ....................

Chrysene .................................................. 2083 228 226 229 228 229 257 

3,3′-Dichlorobenzidine .............................. 2086 252 254 126 .................... .................... ....................

Benzo(a)anthracene ................................. 2090 228 229 226 228 229 257 

bis(2-Ethylhexyl) phthalate ....................... 2124 149 167 279 149 .................... ....................

Di-n-octyl phthalate .................................. 2240 149 43 57 .................... .................... ....................

Benzo(b)fluoranthene ............................... 2286 252 253 125 252 253 281 

Benzo(k)fluoranthene ............................... 2293 252 253 125 252 253 281 

Benzo(a)pyrene ........................................ 2350 252 253 125 252 253 281 

Indeno(1,2,3-cd) pyrene ........................... 2650 276 138 277 276 277 305 

Dibenz(a,h)anthracene ............................. 2660 278 139 279 278 279 307 

Benzo(ghi)perylene .................................. 2750 276 138 277 276 277 305 

Toxaphene ............................................... .................... 159 231 233 .................... .................... ....................

PCB 1016 ................................................. .................... 224 260 294 .................... .................... ....................

PCB 1221 ................................................. .................... 190 224 260 .................... .................... ....................

PCB 1232 ................................................. .................... 190 224 260 .................... .................... ....................

PCB 1242 ................................................. .................... 224 260 294 .................... .................... ....................

PCB 1248 ................................................. .................... 294 330 262 .................... .................... ....................

PCB 1254 ................................................. .................... 294 330 362 .................... .................... ....................

PCB 1260 ................................................. .................... 330 362 394 .................... .................... ....................

1 Column: 30 m x 0.25 mm ID; 94% methyl, 5% phenyl, 1% vinyl bonded phase fused silica capillary. 

Conditions: 5 min at 30 °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. 

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 

Prime Second Second Methane Methane Methane 

2-Chlorophenol ......................................... 705 128 64 130 129 131 157 

Phenol ...................................................... 700 94 65 66 95 123 135 

2-Nitrophenol ............................................ 900 139 65 109 140 168 122 

2,4-Dimethylphenol .................................. 924 122 107 121 123 151 163 

2,4-Dichlorophenol ................................... 947 162 164 98 163 165 167 

mstockstill on DSK30JT082PROD with RULES2

Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 40933 

TABLE 5—CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC m/z’s FOR ACID EXTRACTABLES—Continued 

Analyte 

Retention 

Time 

(sec) 1

Characteristic m/z’s 

Electron impact ionization Chemical ionization 

Prime Second Second Methane Methane Methane 

4-Chloro-3-methylphenol .......................... 1091 142 107 144 143 171 183 

2,4,6-Trichlorophenol ............................... 1165 196 198 200 197 199 201 

2,4-Dinitrophenol ...................................... 1325 184 63 154 185 213 225 

4-Nitrophenol ............................................ 1354 65 139 109 140 168 122 

2-Methyl-4,6-dinitrophenol ....................... 1435 198 182 77 199 227 239 

Pentachlorophenol ................................... 1561 266 264 268 267 265 269 

Column: 30 m x 0.25 mm ID; 94% methyl, 5% phenyl, 1% vinyl bonded phase fused silica capillary. 

Conditions: 5 min at 30 °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 

P1, P2(%) 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 

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 

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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 

P1, P2(%) 3

Limit for 

RPD (%) 

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). 

P1, P2 = MS/MSD recovery (section 8.3.2, section 8.4.2). 

RPD = MS/MSD relative percent difference (RPD; section 8.3.3). 

D = Detected; result must be greater than zero. 

TABLE 7—PRECISION AND RECOVERY AS FUNCTIONS OF CONCENTRATION—METHOD 625 1

Analyte Recovery, X′ 

(μg/L) 

Single analyst 

precision, sr′ 

(μg/L) 

Overall 

precision, S′ 

(μg/L) 

Acenaphthene ........................................................................................................................ 0.96C + 0.19 0.15 X¥0.12 0.21 X¥0.67 

Acenaphthylene ..................................................................................................................... 0.89C + 0.74 0.24 X¥1.06 0.26 X¥0.54 

Aldrin ...................................................................................................................................... 0.78C + 1.66 0.27 X¥1.28 0.43 X + 1.13 

Anthracene ............................................................................................................................. 0.80C + 0.68 0.21 X¥0.32 0.27 X¥0.64 

Benzo(a)anthracene .............................................................................................................. 0.88C¥0.60 0.15 X + 0.93 0.26 X¥0.28 

Benzo(b)fluoranthene ............................................................................................................ 0.93C¥1.80 0.22 X + 0.43 0.29 X + 0.96 

Benzo(k)fluoranthene ............................................................................................................. 0.87C¥1.56 0.19 X + 1.03 0.35 X + 0.40 

Benzo(a)pyrene ..................................................................................................................... 0.90C¥0.13 0.22 X + 0.48 0.32 X + 1.35 

Benzo(ghi)perylene ................................................................................................................ 0.98C¥0.86 0.29 X + 2.40 0.51 X¥0.44 

Benzyl butyl phthalate ........................................................................................................... 0.66C¥1.68 0.18 X + 0.94 0.53 X + 0.92 

beta-BHC ............................................................................................................................... 0.87C¥0.94 0.20 X¥0.58 0.30 X¥1.94 

delta-BHC .............................................................................................................................. 0.29C¥1.09 0.34 X + 0.86 0.93 X¥0.17 

bis(2-Chloroethyl) ether ......................................................................................................... 0.86C¥1.54 0.35 X¥0.99 0.35 X + 0.10 

bis(2-Chloroethoxy) methane ................................................................................................ 1.12C¥5.04 0.16 X + 1.34 0.26 X + 2.01 

bis(2-Chloroisopropyl) ether .................................................................................................. 1.03C¥2.31 0.24 X + 0.28 0.25 X + 1.04 

bis(2-Ethylhexyl) phthalate .................................................................................................... 0.84C¥1.18 0.26 X + 0.73 0.36 X + 0.67 

4-Bromophenyl phenyl ether ................................................................................................. 0.91C¥1.34 0.13 X + 0.66 0.16 X + 0.66 

2-Chloronaphthalene ............................................................................................................. 0.89C + 0.01 0.07 X + 0.52 0.13 X + 0.34 

4-Chlorophenyl phenyl ether ................................................................................................. 0.91C + 0.53 0.20 X¥0.94 0.30 X¥0.46 

Chrysene ................................................................................................................................ 0.93C¥1.00 0.28 X + 0.13 0.33 X¥0.09 

4,4′-DDD ................................................................................................................................ 0.56C¥0.40 0.29 X¥0.32 0.66 X¥0.96 

4,4′-DDE ................................................................................................................................ 0.70C¥0.54 0.26 X¥1.17 0.39 X¥1.04 

4,4′-DDT ................................................................................................................................. 0.79C¥3.28 0.42 X + 0.19 0.65 X¥0.58 

Dibenz(a,h)anthracene .......................................................................................................... 0.88C + 4.72 0.30 X + 8.51 0.59 X + 0.25 

Di-n-butyl phthalate ................................................................................................................ 0.59C + 0.71 0.13 X + 1.16 0.39 X + 0.60 

3,3’-Dichlorobenzidine ........................................................................................................... 1.23C¥12.65 0.28 X + 7.33 0.47 X + 3.45 

Dieldrin ................................................................................................................................... 0.82C¥0.16 0.20 X¥0.16 0.26 X¥0.07 

Diethyl phthalate .................................................................................................................... 0.43C + 1.00 0.28 X + 1.44 0.52 X + 0.22 

Dimethyl phthalate ................................................................................................................. 0.20C + 1.03 0.54 X + 0.19 1.05 X¥0.92 

2,4-Dinitrotoluene ................................................................................................................... 0.92C¥4.81 0.12 X + 1.06 0.21 X + 1.50 

2,6-Dinitrotoluene ................................................................................................................... 1.06C¥3.60 0.14 X + 1.26 0.19 X + 0.35 

Di-n-octyl phthalate ................................................................................................................ 0.76C¥0.79 0.21 X + 1.19 0.37 X + 1.19 

Endosulfan sulfate ................................................................................................................. 0.39C + 0.41 0.12 X + 2.47 0.63 X¥1.03 

Endrin aldehyde ..................................................................................................................... 0.76C¥3.86 0.18 X + 3.91 0.73 X¥0.62 

Fluoranthene .......................................................................................................................... 0.81C + 1.10 0.22 X + 0.73 0.28 X¥0.60 

Fluorene ................................................................................................................................. 0.90C¥0.00 0.12 X + 0.26 0.13 X + 0.61 

Heptachlor .............................................................................................................................. 0.87C¥2.97 0.24 X¥0.56 0.50 X¥0.23 

Heptachlor epoxide ................................................................................................................ 0.92C¥1.87 0.33 X¥0.46 0.28 X + 0.64 

Hexachlorobenzene ............................................................................................................... 0.74C + 0.66 0.18 X¥0.10 0.43 X¥0.52 

Hexachlorobutadiene ............................................................................................................. 0.71C¥1.01 0.19 X + 0.92 0.26 X + 0.49 

Hexachloroethane .................................................................................................................. 0.73C¥0.83 0.17 X + 0.67 0.17 X + 0.80 

Indeno(1,2,3-cd)pyrene .......................................................................................................... 0.78C¥3.10 0.29 X + 1.46 0.50 X + 0.44 

Isophorone ............................................................................................................................. 1.12C + 1.41 0.27 X + 0.77 0.33 X + 0.26 

Naphthalene ........................................................................................................................... 0.76C + 1.58 0.21 X¥0.41 0.30 X¥0.68 

Nitrobenzene .......................................................................................................................... 1.09C¥3.05 0.19 X + 0.92 0.27 X + 0.21 

N-Nitrosodi-n-propylamine ..................................................................................................... 1.12C¥6.22 0.27 X + 0.68 0.44 X + 0.47 

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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) 

PCB–1260 .............................................................................................................................. 0.81C¥10.86 0.35 X + 3.61 0.43 X + 1.82 

Phenanthrene ........................................................................................................................ 0.87C¥0.06 0.12 X + 0.57 0.15 X + 0.25 

Pyrene .................................................................................................................................... 0.84C¥0.16 0.16 X + 0.06 0.15 X + 0.31 

1,2,4-Trichlorobenzene .......................................................................................................... 0.94C¥0.79 0.15 X + 0.85 0.21 X + 0.39 

4-Chloro-3-methylphenol ....................................................................................................... 0.84C + 0.35 0.23 X + 0.75 0.29 X + 1.31 

2-Chlorophenol ...................................................................................................................... 0.78C + 0.29 0.18 X + 1.46 0.28 X + 0.97 

2,4-Dichlorophenol ................................................................................................................. 0.87C + 0.13 0.15 X + 1.25 0.21 X + 1.28 

2,4-Dimethylphenol ................................................................................................................ 0.71C + 4.41 0.16 X + 1.21 0.22 X + 1.31 

2,4-Dinitrophenol .................................................................................................................... 0.81C¥18.04 0.38 X + 2.36 0.42 X + 26.29 

2-Methyl-4,6-Dinitrophenol ..................................................................................................... 1.04C¥28.04 0.05 X + 42.29 0.26 X + 23.10 

2-Nitrophenol ......................................................................................................................... 1.07C¥1.15 0.16 X + 1.94 0.27 X + 2.60 

4-Nitrophenol ......................................................................................................................... 0.61C¥1.22 0.38 X + 2.57 0.44 X + 3.24 

Pentachlorophenol ................................................................................................................. 0.93C + 1.99 0.24 X + 3.03 0.30 X + 4.33 

Phenol .................................................................................................................................... 0.43C + 1.26 0.26 X + 0.73 0.35 X + 0.58 

2,4,6-Trichlorophenol ............................................................................................................. 0.91C¥0.18 0.16 X + 2.22 0.22 X + 1.81 

1 Regressions based on data from Reference 2. 

X′ = Expected recovery for one or more measurements of a sample containing a concentration of C, in 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. 

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 

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. 

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TABLE 9A—DFTPP KEY m/z’s AND ABUNDANCE CRITERIA FOR QUADRUPOLE INSTRUMENTS 1

m/z Abundance criteria 

51 ............................... 30–60 percent of m/z 198. 

68 ............................... Less than 2 percent of m/z 69. 

70 ............................... Less than 2 percent of m/z 69. 

127 ............................. 40–60 percent of base peak m/z 198. 

197 ............................. Less than 1 percent of m/z 198. 

198 ............................. Base peak, 100 percent relative abundance. 

199 ............................. 5–9 percent of m/z 198. 

275 ............................. 10–30 percent of m/z 198. 

365 ............................. Greater than 1 percent of m/z 198. 

441 ............................. Present but less than m/z 443. 

442 ............................. 40–100 percent of m/z 198. 

443 ............................. 17–23 percent of m/z 442. 

1 Criteria in these tables are for quadrupole and time-of-flight instruments. Alternative tuning criteria from other published EPA reference methods may be used provided method performance is not adversely affected. Alternative tuning criteria specified by an instrument manufacturer may 

also be used for another type of mass spectrometer, provided method performance is not adversely affected. 

TABLE 9B—DFTPP KEY m/z’s AND ABUNDANCE CRITERIA FOR TIME-OF-FLIGHT INSTRUMENTS 1

m/z Abundance criteria 

51 ............................... 10–85 percent of the base peak. 

68 ............................... Less than 2 percent of m/z 69. 

70 ............................... Less than 2 percent of m/z 69. 

127 ............................. 10–80 percent of the base peak. 

197 ............................. Less than 2 percent of Mass 198. 

198 ............................. Base peak, or greater than 50% of m/z 442. 

199 ............................. 5–9 percent of m/z 198. 

275 ............................. 10–60 percent of the base peak. 

365 ............................. Greater than 0.5 percent of m/z 198. 

441 ............................. Less than 150 percent of m/z 443. 

442 ............................. Base peak or greater than 30 percent of m/z 198. 

443 ............................. 15–24 percent of m/z 442. 

1 Criteria in these tables are for quadrupole and time-of-flight instruments. Alternative tuning criteria from other published EPA reference methods may be used provided method performance is not adversely affected. Alternative tuning criteria specified by an instrument manufacturer may 

also be used for another type of mass spectrometer, or for an alternative carrier gas, provided method performance is not adversely affected. 

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21. Figures 


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E 

B 

D 

TAILING FACTOR:!£ 

AB 

Example calculation: Peak Height:: DE= 100 mm 

10% Peak Height= BD =10mm 

Peak Width at 10% Peak Height:AC=23mm 

AB=11 mm 

BC=12 mm 

Therefore: Tailing Factor= 12 :1.1 

11 

Figure 1 Tailing factor calculation 
40938 Federal Register / Vol. 82, No. 165 / Monday, August 28, 2017 / Rules and Regulations 

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. 

°C 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 mass or meter 

mg milligram 

min minute 

mL milliliter 

mm millimeter 

ms millisecond 

m/z mass-to-charge ratio 

N normal; gram molecular weight of solute 

divided by hydrogen equivalent of solute, 

per liter of solution 

ng nanogram 

pg picogram 

ppb part-per-billion 

ppm part-per-million 

ppt part-per-trillion 

psig pounds-per-square inch gauge 

22.2 Definitions and acronyms (in 

alphabetical order). 

Analyte—A compound or mixture of 

compounds (e.g., PCBs) tested for by this 

method. The analytes are listed in Tables 

1–3. 

Batch—See Extraction. 

Blank—An aliquot of reagent water that is 

treated exactly as a sample including 

exposure to all glassware, equipment, 

solvents, reagents, internal standards, and 

surrogates that are used with samples. The 

blank is used to determine if analytes or 

interferences are present in the laboratory 

environment, the reagents, or the apparatus. 

Calibration—The process of determining 

the relationship between the output or 

response of a measuring instrument and the 

value of an input standard. Historically, EPA 

has referred to a multi-point calibration as 

the ‘‘initial calibration,’’ to differentiate it 

from a single-point calibration verification. 

Calibration standard—A solution prepared 

from stock solutions and/or a secondary 

standards and containing the analytes of 

interest, surrogates, and internal standards. 

The calibration standard is used to calibrate 

the response of the GC/MS instrument 

against analyte concentration. 

Calibration verification standard—The 

mid-point calibration standard used to verify 

calibration. See sections 7.3 and 13.4. 

Descriptor—In SIM, the beginning and 

ending retention times for the RT window, 

the m/z’s sampled in the RT window, and the 

dwell time at each m/z. 

Extracted ion current profile (EICP)—The 

line described by the signal at a given m/z. 

Extraction Batch—A set of up to 20 field 

samples (not including QC samples) started 

through the extraction process on a given 24- 

hour shift (section 3.1). Each extraction batch 

must be accompanied by a blank (section 

8.5), a laboratory control sample (LCS, 

section 8.4), and a matrix spike and duplicate 

(MS/MSD; Section 8.3), resulting in a 

minimum of five analyses (1 sample, 1 blank, 

1 LCS, 1 MS, and 1 MSD) and a maximum 

of 24 analyses (20 field samples, 1 blank, 1 

LCS, 1 MS, and 1 MSD) for the batch. If 

greater than 20 samples are to be extracted 

in a 24-hour shift, the samples must be 

separated into extraction batches of 20 or 

fewer samples. 

Field Duplicates—Two samples collected 

at the same time and placed under identical 

conditions, and treated identically 

throughout field and laboratory procedures. 

Results of analyses of the field duplicates 

provide an estimate of the precision 

associated with sample collection, 

preservation, and storage, as well as with 

laboratory procedures. 

Field blank—An aliquot of reagent water or 

other reference matrix that is placed in a 

sample container in the field, and treated as 

a sample in all respects, including exposure 

to sampling site conditions, storage, 

preservation, and all analytical procedures. 

The purpose of the field blank is to 


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determine if the field or sample transporting 

procedures and environments have 

contaminated the sample. 

GC—Gas chromatograph or gas 

chromatography. 

Internal standard—A compound added to 

an extract or standard solution in a known 

amount and used as a reference for 

quantitation of the analytes of interest and 

surrogates. In this method the internal 

standards are stable isotopically labeled 

analogs of selected method analytes (Table 

8). Also see Internal standard quantitation. 

Internal standard quantitation—A means of 

determining the concentration of an analyte 

of interest (Tables 1–3) by reference to a 

compound not expected to be found in a 

sample. 

DOC—Initial demonstration of capability 

(section 8.2); four aliquots of reagent water 

spiked with the analytes of interest and 

analyzed to establish the ability of the 

laboratory to generate acceptable precision 

and recovery. A DOC is performed prior to 

the first time this method is used and any 

time the method or instrumentation is 

modified. 

Laboratory Control Sample (LCS; 

laboratory fortified blank; section 8.4)—An 

aliquot of reagent water spiked with known 

quantities of the analytes of interest and 

surrogates. The LCS is analyzed exactly like 

a sample. Its purpose is to assure that the 

results produced by the laboratory remain 

within the limits specified in this method for 

precision and recovery. 

Laboratory fortified sample matrix—See 

Matrix spike. 

Laboratory reagent blank—A blank run on 

laboratory reagents; e.g., methylene chloride 

(section 11.1.5). 

Matrix spike (MS) and matrix spike 

duplicate (MSD) (laboratory fortified sample 

matrix and duplicate)—Two aliquots of an 

environmental sample to which known 

quantities of the analytes of interest and 

surrogates are added in the laboratory. The 

MS/MSD are prepared and analyzed exactly 

like a field sample. Their purpose is to 

quantify any additional bias and imprecision 

caused by the sample matrix. The 

background concentrations of the analytes in 

the sample matrix must be determined in a 

separate aliquot and the measured values in 

the MS/MSD corrected for background 

concentrations. 

May—This action, activity, or procedural 

step is neither required nor prohibited. 

May not—This action, activity, or 

procedural step is prohibited. 

Method blank—See blank. 

Method detection limit (MDL)—A 

detection limit determined by the procedure 

at 40 CFR part 136, appendix B. The MDLs 

determined by EPA in the original version of 

the method are listed in Tables 1, 2 and 3. 

As noted in section 1.5, use the MDLs in 

Tables 1, 2, and 3 in conjunction with 

current MDL data from the laboratory 

actually analyzing samples to assess the 

sensitivity of this procedure relative to 

project objectives and regulatory 

requirements (where applicable). 

Minimum level (ML)—The term 

‘‘minimum level’’ refers to either the sample 

concentration equivalent to the lowest 

calibration point in a method or a multiple 

of the method detection limit (MDL), 

whichever is higher. Minimum levels may be 

obtained in several ways: They may be 

published in a method; they may be based on 

the lowest acceptable calibration point used 

by a laboratory; or they may be calculated by 

multiplying the MDL in a method, or the 

MDL determined by a laboratory, by a factor 

of 3. For the purposes of NPDES compliance 

monitoring, EPA considers the following 

terms to be synonymous: ‘‘quantitation 

limit,’’ ‘‘reporting limit,’’ and ‘‘minimum 

level.’’ 

MS—Mass spectrometer or mass 

spectrometry, or matrix spike (a QC sample 

type). 

MSD—Matrix spike duplicate (a QC 

sample type). 

Must—This action, activity, or procedural 

step is required. 

m/z—The ratio of the mass of an ion (m) 

detected in the mass spectrometer to the 

charge (z) of that ion. 

Preparation blank—See blank. 

Quality control check sample (QCS)—See 

Laboratory Control Sample. 

Reagent water—Water demonstrated to be 

free from the analytes of interest and 

potentially interfering substances at the 

MDLs for the analytes in this method. 

Regulatory compliance limit (or regulatory 

concentration limit)—A limit on the 

concentration or amount of a pollutant or 

contaminant specified in a nationwide 

standard, in a permit, or otherwise 

established by a regulatory/control authority. 

Relative retention time (RRT)—The ratio of 

the retention time of an analyte to the 

retention time of its associated internal 

standard. RRT compensates for small changes 

in the GC temperature program that can affect 

the absolute retention times of the analyte 

and internal standard. RRT is a unitless 

quantity. 

Relative standard deviation (RSD)—The 

standard deviation times 100 divided by the 

mean. Also termed ‘‘coefficient of variation.’’ 

RF—Response factor. See section 7.2.2. 

RSD—See relative standard deviation. 

Safety Data Sheet (SDS)—Written 

information on a chemical’s toxicity, health 

hazards, physical properties, fire, and 

reactivity, including storage, spill, and 

handling precautions that meet the 

requirements of OSHA, 29 CFR 1910.1200(g) 

and appendix D to § 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 liquidsolid extraction. 

Stock solution—A solution containing an 

analyte that is prepared using a reference 

material traceable to EPA, the National 

Institute of Science and Technology (NIST), 

or a source that will attest to the purity, 

authenticity, and concentration of the 

standard. 

Surrogate—A compound unlikely to be 

found in a sample, and which is spiked into 

sample in a known amount before extraction 

or other processing, and is quantitated with 

the same procedures used to quantify other 

sample components. The purpose of the 

surrogate is to monitor method performance 

with each sample. 

* * * * * 

■ 9. Appendix B to part 136 is revised 

to read as follows: 

Appendix B to Part 136—Definition and 

Procedure for the Determination of the 

Method Detection Limit—Revision 2 

Definition 

The method detection limit (MDL) is 

defined as the minimum measured 

concentration of a substance that can be 

reported with 99% confidence that the 

measured concentration is distinguishable 

from method blank results. 

I. Scope and Application 

(1) The MDL procedure is designed to be 

a straightforward technique for estimation of 

the detection limit for a broad variety of 

physical and chemical methods. The 

procedure requires a complete, specific, and 

well-defined analytical method. It is essential 

that all sample processing steps used by the 

laboratory be included in the determination 

of the method detection limit. 

(2) The MDL procedure is not applicable to 

methods that do not produce results with a 

continuous distribution, such as, but not 

limited to, methods for whole effluent 

toxicity, presence/absence methods, and 

microbiological methods that involve 

counting colonies. The MDL procedure also 

is not applicable to measurements such as, 

but not limited to, biochemical oxygen 

demand, color, pH, specific conductance, 

many titration methods, and any method 

where low-level spiked samples cannot be 

prepared. Except as described in the 

addendum, for the purposes of this 

procedure, ‘‘spiked samples’’ are prepared 

from a clean reference matrix, such as reagent 

water, spiked with a known and consistent 

quantity of the analyte. MDL determinations 

using spiked samples may not be appropriate 

for all gravimetric methods (e.g., residue or 

total suspended solids), but an MDL based on 

method blanks can be determined in such 

instances. 

II. Procedure 

(1) Estimate the initial MDL using one or 

more of the following: 

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(a) The mean determined concentration 

plus three times the standard deviation of a 

set of method blanks. 

(b) The concentration value that 

corresponds to an instrument signal-to-noise 

ratio in the range of 3 to 5. 

(c) The concentration equivalent to three 

times the standard deviation of replicate 

instrumental measurements of spiked blanks. 

(d) That region of the calibration where 

there is a significant change in sensitivity, 

i.e., a break in the slope of the calibration. 

(e) Instrumental limitations. 

(f) Previously determined MDL. 

Note: It is recognized that the experience 

of the analyst is important to this process. 

However, the analyst should include some or 

all of the above considerations in the initial 

estimate of the MDL. 

(2) Determine the initial MDL. 

Note: The Initial MDL is used when the 

laboratory does not have adequate data to 

perform the Ongoing Annual Verification 

specified in Section (4), typically when a 

new method is implemented or if a method 

was rarely used in the last 24 months. 

(a) Select a spiking level, typically 2—10 

times the estimated MDL in Section 1. 

Spiking levels in excess of 10 times the 

estimated detection limit may be required for 

analytes with very poor recovery (e.g., for an 

analyte with 10% recovery, spiked at 100 

micrograms/L, with mean recovery of 10 

micrograms/L; the calculated MDL may be 

around 3 micrograms/L. Therefore, in this 

example, the spiking level would be 33 times 

the MDL, but spiking lower may result in no 

recovery at all). 

(b) Process a minimum of seven spiked 

samples and seven method blank samples 

through all steps of the method. The samples 

used for the MDL must be prepared in at least 

three batches on three separate calendar 

dates and analyzed on three separate 

calendar dates. (Preparation and analysis 

may be on the same day.) Existing data may 

be used, if compliant with the requirements 

for at least three batches, and generated 

within the last twenty four months. The most 

recent available data for method blanks and 

spiked samples must be used. Statistical 

outlier removal procedures should not be 

used to remove data for the initial MDL 

determination, since the total number of 

observations is small and the purpose of the 

MDL procedure is to capture routine method 

variability. However, documented instances 

of gross failures (e.g., instrument 

malfunctions, mislabeled samples, cracked 

vials) may be excluded from the calculations, 

provided that at least seven spiked samples 

and seven method blanks are available. (The 

rationale for removal of specific outliers must 

be documented and maintained on file with 

the results of the MDL determination.) 

(i) If there are multiple instruments that 

will be assigned the same MDL, then the 

sample analyses must be distributed across 

all of the instruments. 

(ii) A minimum of two spiked samples and 

two method blank samples prepared and 

analyzed on different calendar dates is 

required for each instrument. Each analytical 

batch may contain one spiked sample and 

one method blank sample run together. A 

spiked sample and a method blank sample 

may be analyzed in the same batch, but are 

not required to be. 

(iii) The same prepared extract may be 

analyzed on multiple instruments so long as 

the minimum requirement of seven 

preparations in at least three separate batches 

is maintained. 

(c) Evaluate the spiking level: If any result 

for any individual analyte from the spiked 

samples does not meet the method 

qualitative identification criteria or does not 

provide a numerical result greater than zero, 

then repeat the spiked samples at a higher 

concentration. (Qualitative identification 

criteria are a set of rules or guidelines for 

establishing the identification or presence of 

an analyte using a measurement system. 

Qualitative identification does not ensure 

that quantitative results for the analyte can be 

obtained.) 

(d) Make all computations as specified in 

the analytical method and express the final 

results in the method-specified reporting 

units. 

(i) Calculate the sample standard deviation 

(S) of the replicate spiked sample 

measurements and the sample standard 

deviation of the replicate method blank 

measurements from all instruments to which 

the MDL will be applied. 

(ii) Compute the MDLs (the MDL based on 

spiked samples) as follows: 

MDLS = t(n ¥1, 1¥α = 0.99)Ss

Where: 

MDLs = the method detection limit based on 

spiked samples 

t(n-1, 1¥α = 0.99) = the Student’s t-value 

appropriate for a single-tailed 99th 

percentile t statistic and a standard 

deviation estimate with n-1 degrees of 

freedom. See Addendum Table 1. 

Ss = sample standard deviation of the 

replicate spiked sample analyses. 

(iii) Compute the MDLb (the MDL based on 

method blanks) as follows: 

(A) If none of the method blanks give 

numerical results for an individual analyte, 

the MDLb does not apply. A numerical result 

includes both positive and negative results, 

including results below the current MDL, but 

not results of ‘‘ND’’ (not detected) commonly 

observed when a peak is not present in 

chromatographic analysis. 

(B) If some (but not all) of the method 

blanks for an individual analyte give 

numerical results, set the MDLb equal to the 

highest method blank result. If more than 100 

method blanks are available, set MDLb to the 

level that is no less than the 99th percentile 

of the method blank results. For ‘‘n’’ method 

blanks where n ≥ 100, sort the method blanks 

in rank order. The (n * 0.99) ranked method 

blank result (round to the nearest whole 

number) is the MDLb. For example, to find 

MDLb from a set of 164 method blanks where 

the highest ranked method blank results are 

. . . 1.5, 1.7, 1.9, 5.0, and 10, then 164 × 0.99 

= 162.36 which rounds to the 162nd method 

blank result. Therefore, MDLb is 1.9 for n = 

164 (10 is the 164th result, 5.0 is the 163rd 

result, and 1.9 is the 162nd result). 

Alternatively, you may use spreadsheet 

algorithms to calculate the 99th percentile to 

interpolate between the ranks more precisely. 

(C) If all of the method blanks for an 

individual analyte give numerical results, 

then calculate the MDLb as: 

MDLb = X + tn¥1,1¥α=(0.99)Sb

Where: 

MDLb = the MDL based on method blanks 

X = mean of the method blank results (use 

zero in place of the mean if the mean is 

negative) 

t(n¥1, 1α = 0.99) = the Student’s t-value 

appropriate for the single-tailed 99th 

percentile t statistic and a standard 

deviation estimate with n¥1 degrees of 

freedom. See Addendum Table 1. 

Sb = sample standard deviation of the 

replicate method blank sample analyses. 

Note: If 100 or more method blanks are 

available, as an option, MDLb may be set to 

the concentration that is greater than or equal 

to the 99th percentile of the method blank 

results, as described in Section (2)(d)(iii)(B). 

(e) Select the greater of MDLs or MDLb as 

the initial MDL. 

(3) Ongoing Data Collection. 

(a) During any quarter in which samples 

are being analyzed, prepare and analyze a 

minimum of two spiked samples on each 

instrument, in separate batches, using the 

same spiking concentration used in Section 

2. If any analytes are repeatedly not detected 

in the quarterly spiked sample analyses, or 

do not meet the qualitative identification 

criteria of the method (see section 2(c) of this 

procedure), then this is an indication that the 

spiking level is not high enough and should 

be adjusted upward. Note that it is not 

necessary to analyze additional method 

blanks together with the spiked samples, the 

method blank population should include all 

of the routine method blanks analyzed with 

each batch during the course of sample 

analysis. 

(b) Ensure that at least seven spiked 

samples and seven method blanks are 

completed for the annual verification. If only 

one instrument is in use, a minimum of 

seven spikes are still required, but they may 

be drawn from the last two years of data 

collection. 

(c) At least once per year, re-evaluate the 

spiking level. 

(i) If more than 5% of the spiked samples 

do not return positive numerical results that 

meet all method qualitative identification 

criteria, then the spiking level must be 

increased and the initial MDL re-determined 

following the procedure in section 2. 

(ii) [Reserved] 

(d) If the method is altered in a way that 

can be reasonably expected to change its 

sensitivity, then re-determine the initial MDL 

according to section 2, and the restart the 

ongoing data collection. 

(e) If a new instrument is added to a group 

of instruments whose data are being pooled 

to create a single MDL, analyze a minimum 

of two spiked replicates and two method 

blank replicates on the new instrument. If 

both method blank results are below the 

existing MDL, then the existing MDLb is 

validated. Combine the new spiked sample 

results to the existing spiked sample results 

and recalculate the MDLs as in Section 4. If 

the recalculated MDLs does not vary by more 

than the factor specified in section 4(f) of this 

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procedure, then the existing MDLs is 

validated. If either of these two conditions is 

not met, then calculate a new MDL following 

the instructions in section 2. 

(4) Ongoing Annual Verification. 

(a) At least once every thirteen months, recalculate MDLs and MDLb from the collected 

spiked samples and method blank results 

using the equations in section 2. 

(b) Include data generated within the last 

twenty four months, but only data with the 

same spiking level. Only documented 

instances of gross failures (e.g., instrument 

malfunctions, mislabeled samples, cracked 

vials) may be excluded from the calculations. 

(The rationale for removal of specific outliers 

must be documented and maintained on file 

with the results of the MDL determination.) 

If the laboratory believes the sensitivity of the 

method has changed significantly, then the 

most recent data available may be used, 

maintaining compliance with the 

requirement for at least seven replicates in 

three separate batches on three separate days 

(see section 2b). 

(c) Include the initial MDL spiked samples, 

if the data were generated within twenty four 

months. 

(d) Only use data associated with 

acceptable calibrations and batch QC. 

Include all routine data, with the exception 

of batches that are rejected and the associated 

samples reanalyzed. If the method has been 

altered in a way that can be reasonably 

expected to change its sensitivity, then use 

only data collected after the change. 

(e) Ideally, use all method blank results 

from the last 24 months for the MDLb

calculation. The laboratory has the option to 

use only the last six months of method blank 

data or the fifty most recent method blanks, 

whichever criteria yields the greater number 

of method blanks. 

(f) The verified MDL is the greater of the 

MDLs or MDLb. If the verified MDL is within 

0.5 to 2.0 times the existing MDL, and fewer 

than 3% of the method blank results (for the 

individual analyte) have numerical results 

above the existing MDL, then the existing 

MDL may optionally be left unchanged. 

Otherwise, adjust the MDL to the new 

verification MDL. (The range of 0.5 to 2.0 

approximates the 95th percentile confidence 

interval for the initial MDL determination 

with six degrees of freedom.) 

Addendum to Section II: Determination of 

the MDL for a Specific Matrix 

The MDL may be determined in a specific 

sample matrix as well as in reagent water. 

(1) Analyze the sample matrix to determine 

the native (background) concentration of the 

analyte(s) of interest. 

(2) If the response for the native 

concentration is at a signal-to-noise ratio of 

approximately 5–20, determine the matrixspecific MDL according to Section 2 but 

without spiking additional analyte. 

(3) Calculate MDLb using the method 

blanks, not the sample matrix. 

(4) If the signal-to-noise ratio is less than 

5, then the analyte(s) should be spiked into 

the sample matrix to obtain a concentration 

that will give results with a signal-to-noise 

ratio of approximately 10–20. 

(5) If the analytes(s) of interest have signalto-noise ratio(s) greater than approximately 

20, then the resulting MDL is likely to be 

biased high. 

TABLE 1—SINGLE-TAILED 99th PERCENTILE t STATISTIC

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 

32 ............................................................................................................................................................................. 31 2.453 

48 ............................................................................................................................................................................. 47 2.408 

50 ............................................................................................................................................................................. 49 2.405 

61 ............................................................................................................................................................................. 60 2.390 

64 ............................................................................................................................................................................. 63 2.387 

80 ............................................................................................................................................................................. 79 2.374 

96 ............................................................................................................................................................................. 95 2.366 

100 ........................................................................................................................................................................... 99 2.365 

III. Documentation 

The analytical method used must be 

specifically identified by number or title and 

the MDL for each analyte expressed in the 

appropriate method reporting units. Data and 

calculations used to establish the MDL must 

be able to be reconstructed upon request. The 

sample matrix used to determine the MDL 

must also be identified with MDL value. 

Document the mean spiked and recovered 

analyte levels with the MDL. The rationale 

for removal of outlier results, if any, must be 

documented and maintained on file with the 

results of the MDL determination. 

[FR Doc. 2017–17271 Filed 8–25–17; 8:45 am] 

BILLING CODE 6560–50–P 

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