29758 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

ENVIRONMENTAL PROTECTION 

AGENCY 

40 CFR Parts 136, 260, 423, 430, and 

435 

[EPA–HQ–OW–2010–0192; FRL–9664–6] 

RIN 2040–AF09 

Guidelines Establishing Test 

Procedures for the Analysis of 

Pollutants Under the Clean Water Act; 

Analysis and Sampling Procedures 

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. 

EPA proposed these changes for public 

comment on September 23, 2010. The 

changes adopted in this final rule fall 

into the following categories: New and 

revised EPA methods and new and 

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 process for EPA 

approval for use of alternate procedures 

for nationwide and Regional use; 

minimum quality control requirements 

to improve consistency across method 

versions; corrections to previously 

approved methods; and revisions to 

sample collection, preservation, and 

holding time requirements. Finally, EPA 

makes changes to three effluent 

guideline regulations. 

DATES: This regulation is effective on 

June 18, 2012. The incorporation by 

reference of these methods is approved 

by the Director of the Federal Register 

on June 18, 2012. For judicial review 

purposes, this final rule is promulgated 

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

2012 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–2010–0192. All 

documents in the docket are listed on 

the http://www.regulations.gov Web 

site. Although listed in the index, some 

information is not publically available, 

e.g., 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 

http://www.regulations.gov or in hard 

copy at the HQ Water Docket Center, 

EPA/DC, EPA West, 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 is 202–566– 

2426 for the HQ Water Docket. 

FOR FURTHER INFORMATION CONTACT: For 

information regarding the changes to 

inorganic chemical methods, contact 

Lemuel Walker, Engineering and 

Analysis Division (4303T), USEPA 

Office of Science and Technology, 1200 

Pennsylvania Ave. NW., Washington, 

DC 20460, 202–566–1077 (email: 

walker.lemuel@epa.gov). For 

information regarding the changes to 

organic chemical methods, contact 

Maria Gomez-Taylor, Engineering and 

Analysis Division (4303T), USEPA 

Office of Science and Technology, 1200 

Pennsylvania Ave. NW., Washington, 

DC 20460, 202–566–1005 (email: gomeztaylor.maria@epa.gov). For information 

regarding the changes to microbiological 

and whole effluent toxicity methods, 

contact Robin Oshiro, Engineering and 

Analysis Division (4303T), USEPA 

Office of Science and Technology, 1200 

Pennsylvania Ave. NW., Washington, 

DC 20460, 202–566–1075 (email: 

oshiro.robin@epa.gov). 

SUPPLEMENTARY INFORMATION: 

A. General Information 

1. Does this action apply to me? 

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. Categories and entities that 

may potentially be affected by the 

requirements of today’s rule include: 

Category Examples of potentially affected entities 

State, Territorial, and Indian Tribal 

Governments.

States, Territories, and Tribes authorized to administer the NPDES permitting program; States, Territories, 

and Tribes providing certification under Clean Water Act section 401; State, Territorial, and Indian Tribal 

owned facilities that must conduct monitoring to comply with NPDES permits. 

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

Municipalities ................................... POTWs or other municipality owned facilities that must conduct monitoring to comply with NPDES permits. 

This table is not intended to be 

exhaustive, but rather provides a guide 

for readers regarding entities likely to be 

affected by this action. This table lists 

types of entities that 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 

today’s 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 June 1, 

2012 as provided at 40 CFR 23.2. The 


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requirements of this regulation may also 

not be challenged later in civil or 

criminal proceedings brought by EPA. 

C. Abbreviations and Acronyms Used 

in the Preamble and Final Rule 

AOAC: AOAC International 

ASTM: ASTM International 

ATP: Alternate Test Procedure 

CFR: Code of Federal Regulations 

CWA: Clean Water Act 

EPA: Environmental Protection Agency 

FLAA: Flame Atomic Absorption 

Spectroscopy 

HRGC: High Resolution Gas Chromatography 

HRMS: High Resolution Mass Spectrometry 

ICP/AES: Inductively Coupled PlasmaAtomic Emission Spectroscopy 

ICP/MS: Inductively Coupled Plasma-Mass 

Spectrometry 

ISO: International Organization for 

Standardization 

MS: Mass Spectrometry 

NIST: National Institute of Standards and 

Technology 

NPDES: National Pollutant Discharge 

Elimination System 

QA: Quality Assurance 

QC: Quality Control 

SDWA: Safe Drinking Water Act 

SM: Standard Methods 

SRM: Standard Reference Material 

STGFAA: Stabilized Temperature Graphite 

Furnace Atomic Absorption Spectroscopy 

USGS: United States Geological Survey 

VCSB: Voluntary Consensus Standards Body 

WET: Whole Effluent Toxicity 

Table of Contents 

I. Statutory Authority 

II. Summary of Final Rule 

A. New EPA Methods and New Versions of 

Previously Approved EPA Methods 

B. New Standard Methods and New 

Versions of Approved Standard Methods 

C. New ASTM Methods and New Versions 

of Previously Approved ASTM Methods 

D. New Alternate Test Procedures at 40 

CFR 136.3 

E. Clarifications and Corrections to 

Previously Approved Methods in 40 CFR 

136.3 

F. Revisions in Table II at 40 CFR 136.3(e) 

to Required Containers, Preservation 

Techniques, and Holding Times 

G. Revisions to 40 CFR 136.4 and 136.5 

H. Revisions to Method Modification 

Provisions at 40 CFR 136.6 

I. New Quality Assurance and Quality 

Control Language at 40 CFR 136.7 

J. Revisions to 40 CFR part 423 (Steam 

Electric Power Generating Point Source 

Category) 

III. Changes Between the Proposed Rule and 

the Final Rule 

A. EPA Is Not Adding EPA Method 1614A 

B. Deferral of Action on EPA Method 

1668C 

C. EPA Is Not Adding ASTM Methods 

D7574–09 and D7485–09 

D. Revisions and Clarifications to EPA 

Method 200.7 

E. Revisions and Corrections to Certain 

Citations in Tables IB and ID 

F. Continued Approval of Method 1664 

Revision A 

G. Revision to Footnote 63 of Table IB at 

40 CFR 136.3 

H. Revision to Footnote 4 of Table IC at 40 

CFR 136.3 

I. Revisions to Table II Language 

J. Approval of Alternate Test Procedures 

for Limited Use at 40 CFR 136.5 

K. Revisions to Language at § 136.6 

L. Revisions to New Quality Assurance and 

Quality Control Language 

M. Withdrawal of Appendices at 40 CFR 

part 136 

N. Revisions to 40 CFR Part 430 (Pulp, 

Paper, and Paperboard Point Source 

Category) 

O. Revisions to 40 CFR Part 435 (Oil and 

Gas Extraction Point Source Category) 

IV. Response to Comments 

A. How Standard Methods are Identified in 

Part 136 Tables 

B. Preservation and Holding Time 

Requirements for EPA Method 624 

C. Quality Assurance and Quality Control 

Requirements 

V. Statutory and Executive Order Reviews 

A. Executive Order 12866: Regulatory 

Planning and Review and Review and 

Executive Order 13563: Improving 

Regulation and Regulatory Review 

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 today’s rule 

pursuant to the authority of sections 

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

Water Act (‘‘CWA’’ or the ‘‘Act’’), 33 

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

301(a) of the Act prohibits the discharge 

of any pollutant into navigable waters 

unless the discharge complies with a 

National Pollutant Discharge 

Elimination System (NPDES) permit 

issued under section 402 of the Act. 

Section 304(h) of the Act 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 this Act] or 

permit application pursuant to [section 

402 of this Act].’’ Section 501(a) of the 

Act authorizes the Administrator to 

‘‘* * * prescribe such regulations as are 

necessary to carry out this function 

under [the Act].’’ 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 today’s final 

rule. 

A. New EPA Methods and New Versions 

of Previously Approved EPA Methods 

This rule approves new EPA methods 

and new versions of already approved 

EPA methods. The following discussion 

briefly describes the EPA methods 

added today to Part 136. 

1. Oil and grease. Today’s rule adds 

a new version of EPA Method 1664, 

1664 Revision B: 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 

for use in CWA programs. Today, EPA 

is also amending the RCRA regulations 

at 40 CFR 260.11, which currently 

specify the use of Method 1664 Rev. A, 

to provide additionally for use of the 

revised version, 1664 Rev. B. As stated 

in the preamble to the proposal (75 FR 

58026, Sept. 23, 2010), EPA encourages 

that future delistings cite ‘‘Method 1664 

Rev. B’’ while delistings already granted 

may continue to use Method 1664 Rev. 

A. 

On December 14, 2011, EPA 

published a notice of data availability 

(NODA) on a new method for oil and 

grease for use in Clean Water Act 

programs (see 76 FR 77742). This 

method, ASTM D–7575–10, uses a 

different extractant (a membrane filter 

instead of n-hexane for the extraction of 

oil and grease material) and a different 

measurement technique (infrared 

absorption instead of gravimetry) from 

the extractant and measurement 

technique of currently approved 

methods for oil and grease. The new 

method was discussed in the September 

23, 2010 notice but EPA did not propose 

it for use as an approved method to be 

codified at 40 CFR 136.3 because oil and 

grease is a method-defined parameter. 

By definition, the measurement results 

of method-defined parameters are 

specific to the described method and are 

not directly comparable to results 

obtained by another method. However, 

since publication of the Methods 

Update Rule proposal, the Agency 

received additional data and 

information about this method and is reconsidering whether it should add this 


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29760 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

method to the list of approved methods 

for oil and grease at 40 CFR 136.3. In the 

NODA, EPA proposed to include ASTM 

D–7575 for the measurement of oil and 

grease based on comments received in 

response to its September 23, 2010 

proposal and the additional data. EPA 

will make a decision on the inclusion of 

the new method once it reviews the 

public comments received in response 

to the NODA and will then publish that 

decision in a separate Federal Register 

notice. 

2. Metals. Today’s rule adds EPA 

Method 200.5 (Revision 4.2): 

‘‘Determination of Trace Elements in 

Drinking Water by Axially Viewed 

Inductively Coupled Plasma—Atomic 

Emission Spectrometry’’ to Table IB. 

The rule also clarifies that the axial 

orientation of the torch is allowed for 

use with EPA Method 200.7. Thus, EPA 

will allow the use of axial instruments 

or radial instruments to measure metals 

in water samples. 

3. Pesticides. Today’s rule adds EPA 

Method 525.2 to Table IG (Test Methods 

for Pesticide Active Ingredients) as an 

additional approved method for all 

parameters for which EPA has 

previously approved EPA Method 525.1, 

and also adds Methods 525.1 and 525.2 

to Table ID for the same parameters for 

which EPA had previously approved 

Method 525.1 in Table IG. The rule also 

adds some of the methods for Pesticide 

Active Ingredients (Table IG) to 

applicable parameters listed in Table ID 

for general use. These methods are: 

a. EPA Method 608.1, ‘‘The 

Determination of Organochlorine 

Pesticides in Municipal and Industrial 

Wastewater.’’ This method measures 

chlorobenzilate, chloroneb, 

chloropropylate, 

dibromochloropropane, etridiazole, 

PCNB, and propachlor. 

b. EPA Method 608.2, ‘‘The 

Determination of Certain 

Organochlorine Pesticides in Municipal 

and Industrial Wastewater.’’ This 

method measures chlorothalonil, DCPA, 

dichloran, methoxychlor, and 

permethrin. 

c. EPA Method 614, ‘‘The 

Determination of Organophosphorus 

Pesticides in Municipal and Industrial 

Wastewater.’’ This method measures 

azinphos methyl, demeton, diazinon, 

disulfoton, ethion, malathion, parathion 

methyl, and parathion ethyl. 

d. EPA Method 614.1, ‘‘The 

Determination of Organophosphorus 

Pesticides in Municipal and Industrial 

Wastewater.’’ This method measures 

dioxathion, EPN, ethion, and terbufos. 

e. EPA Method 615, ‘‘The 

Determination of Chlorinated 

Herbicides in Municipal and Industrial 

Wastewater.’’ This method measures 

2,4-D, dalapon, 2,4-DB, dicamba, 

dichlorprop, dinoseb, MCPA, MCPP, 

2,4,5-T, and 2,4,5-TP. 

f. EPA Method 617, ‘‘The 

Determination of Organohalide 

Pesticides and PCBs in Municipal and 

Industrial Wastewater.’’ This method 

measures aldrin, a-BHC, b-BHC, g-BHC 

(lindane), captan, carbophenothion, 

chlordane, 4,4′-DDD, 4,4′-DDE, 4,4′- 

DDT, dichloran, dicofol, dieldrin, 

endosulfan I, endosulfan II, endosulfan 

sulfate, endrin, endrin aldehyde, 

heptachlor, heptachlor epoxide, isodrin, 

methoxychlor, mirex, PCNB, perthane, 

strobane, toxaphene, trifluralin, PCB1016, PCB-1221, PCB-1232, PCB-1242, 

PCB-1248, PCB-1254, and PCB-1260. 

g. EPA Method 619, ‘‘The 

Determination of Triazine Pesticides in 

Municipal and Industrial Wastewater.’’ 

This method measures ametryn, atraton, 

atrazine, prometon, prometryn, 

propazine, sec-bumeton, simetryn, 

simazine, terbuthylazine, and terbutryn. 

h. EPA Method 622, ‘‘The 

Determination of Organophosphorus 

Pesticides in Municipal and Industrial 

Wastewater.’’ This method measures 

azinphos methyl, bolstar, chlorpyrifos, 

chlorpyrifos methyl, coumaphos, 

demeton, diazinon, dichlorvos, 

disulfoton, ethoprop, fensulfothion, 

fenthion, merphos, mevinphos, naled, 

parathion methyl, phorate, ronnel, 

stirofos, tokuthion, and trichloronate. 

i. EPA Method 622.1, ‘‘The 

Determination of Thiophosphate 

Pesticides in Municipal and Industrial 

Wastewater.’’ This method measures 

aspon, dichlofenthion, famphur, 

fenitrothion, fonophos, phosmet, and 

thionazin. 

j. EPA Method 632, ‘‘The 

Determination of Carbamate and Urea 

Pesticides in Municipal and Industrial 

Wastewater.’’ This method measures 

aminocarb, barban, carbaryl, carbofuran, 

chlorpropham, diuron, fenuron, 

fenuron-TCA, fluometuron, linuron, 

methiocarb, methomyl, mexacarbate, 

monuron, monuron-TCA, neburon, 

oxamyl, propham, propoxur, siduron, 

and swep. 

4. Microbiologicals. Today’s rule 

approves the 2005 versions of EPA 

Method 1622, ‘‘Cryptosporidium in 

Water by Filtration/IMS/FA’’ and EPA 

Method 1623, ‘‘Cryptosporidium and 

Giardia in Water by Filtration/IMS/FA’’ 

in Table IH for ambient water. 

The rule approves revised versions of 

EPA Methods 1103.1, 1106.1, 1600, 

1603, and 1680 in Table IH. The rule 

also approves the revised version of 

EPA Methods 1600, 1603 and 1680 in 

Table IA. We corrected technical errors 

in these revisions. 

5. Non-Conventionals. Today’s rule 

adds EPA Method 1627, ‘‘Kinetic Test 

Method for the Prediction of Mine 

Drainage Quality’’ to Table IB as a new 

parameter termed ‘‘Acid Mine 

Drainage.’’ 

6. Organics. Today’s rule approves 

EPA Method 624, ‘‘Purgeables,’’ for the 

determination of acrolein and 

acrylonitrile in wastewater and revises 

footnote 4 to Table IC to specify that the 

laboratory must provide documentation 

about its ability to measure these 

analytes at the levels necessary to 

comply with associated regulations. 

B. New Standard Methods and New 

Versions of Approved Standard 

Methods 

This rule approves the following 

Standard Methods (SM) for certain 

pollutants currently listed in Table IB at 

Part 136. Laboratories performing 

measurements using any of the 

approved Standard Methods must 

follow the quality control (QC) 

procedures specified in the 20th or 21st 

edition of Standard Methods. Below is 

a list of the Standard Methods added to 

Table IB in Part 136: 

1. SM 5520 B–2001 and SM 5520 F– 

2001, Oil and Grease, gravimetric 

2. SM 4500–NH3 G–1997, Ammonia (as 

N) and TKN, automated phenate 

method 

3. SM 4500–B B–2000, Boron, curcumin 

method 

4. SM 4140 B–1997, Inorganic Ions 

(Bromide, Chloride, Fluoride, 

Orthophosphate, and Sulfate), 

capillary ion electrophoresis with 

indirect UV detection 

5. SM 3114 B–2009, Arsenic and 

Selenium, AA gaseous hydride 

6. SM 3114 C–2009, Arsenic and 

Selenium, AA gaseous hydride 

7. SM 3111 E–1999, Aluminum and 

Beryllium, direct aspiration atomic 

absorption spectrometry 

8. SM 5220 B–1997, Chemical Oxygen 

Demand (COD), titrimetric 

9. SM 3500–Cr B–2009, Chromium, 

colorimetric method 

10. SM 4500–Norg D–1997, Kjeldahl 

Nitrogen, semi-automated block 

digestor colorimetric 

11. SM 3112 B–2009, Mercury, cold 

vapor, manual 

12. SM 4500–P G–1999 and SM 4500– 

P H–1999, Phosphorus, Total, 

automated ascorbic acid reduction 

13. SM 4500–P E–1999 and SM 4500– 

P F–1999, Phosphorus, Total, 

manual, and automated ascorbic 

acid reduction 

14. SM 4500–O B, D, E and F–2001, 

Oxygen, Dissolved, Winkler 

15. SM 4500–O D–2001, Oxygen, 

Dissolved, Winkler 


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16. SM 4500–O E–2001, Oxygen, 

Dissolved, alum flocculation 

modification 

17. SM 5530 B–2005, Phenols, manual 

distillation 

18. SM 5530 D–2005, Phenols, 

colorimetric 

19. SM 3500–K C–1997, Potassium, 

Total, selective electrode method 

20. SM 2540 E–1997, Residues— 

Volatile, gravimetric 

21. SM 4500–SiO2 E–1997 and SM 

4500–SiO2 F–1997, Silica, 

Dissolved, automated 

molybdosilicate 

22. SM 4500–SO4

2¥ C–1997, D–1997, 

E–1997, F–1997 and G–1997, 

Sulfate, gravimetric, and automated 

colorimetric 

23. SM 4500–S2¥ B–2000 and C–2000, 

Sulfide, sample pretreatment 

C. New ASTM Methods and New 

Versions of Previously Approved ASTM 

Methods 

The rule approves the following 

ASTM methods for existing pollutants 

and ASTM methods for new pollutants 

to 40 CFR part 136, Table IB for 

inorganic compounds, and Table IC for 

organic compounds. 

1. ASTM D2036–09 (B), Cyanide—Total, 

Cyanide amenable to cholorination 

2. ASTM D6888–09, Cyanide— 

Available, flow injection and ligand 

exchange 

3. ASTM D7284–08, Cyanide—Total, 

flow injection 

4. ASTM D7511–09, Cyanide—Total, 

segmented flow injection 

5. Free cyanide is added as a new 

parameter (24A in Table IB); two 

ASTM methods (D4282–02 and 

D7237–10) are approved, in 

addition to a new version of OIA 

1677(2009) for this parameter. 

D4282–02 is a Standard Test 

Method for Determination of Free 

Cyanide in Water and Wastewater 

by Microdiffusion, and Method 

D7237–10 is a Standard Test 

Method for Free Cyanide with Flow 

Injection Analysis (FIA) Utilizing 

Gas Diffusion Separation and 

Amperometric Detection. 

6. ASTM D888–09 (A), Oxygen 

Dissolved, Winkler 

7. ASTM D7573–09, Organic Carbon— 

Total, combustion 

8. ASTM D7065–06, Five new chemicals 

in water: Nonylphenol (NP), 

Bisphenol A (BPA), p-tertOctylphenol (OP), Nonylphenol 

Monoethoxylate (NP1EO), and 

Nonylphenol Diethoxylate 

(NP2EO), Gas Chromatography/ 

Mass Spectrometry 

D. New Alternate Test Procedures at 40 

CFR 136.3 

The rule approves eight 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 eight methods 

approved are added to Table IB: 

1. Hach Company’s Method 10360 

Luminescence Measurement of 

Dissolved Oxygen in Water and 

Wastewater and for Use in the 

Determination of BOD5 and cBOD5, 

Revision 1.2 dated October 2011 

2. In-Situ Incorporated’s Method 1002– 

8–2009 Dissolved Oxygen 

Measurement by Optical Probe 

3. In-Situ Incorporated’s Method 1003– 

8–2009 Biochemical Demand (BOD) 

Measurement by Optical Probe 

4. In-Situ Incorporated’s Method 1004– 

8–2009 Carbonaceous Biochemical 

Oxygen Demand (CBOD) 

Measurement by Optical Probe 

5. Mitchell Method M5271 dated July 

31, 2008 for turbidity 

6. Mitchell Method M5331 dated July 

31, 2008 for turbidity 

7. Thermo Scientific’s Orion Method 

AQ4500 dated March 12, 2009 for 

turbidity 

8. Easy (1–Reagent) Nitrate Method 

dated November 12, 2011 for 

nitrate, nitrite and combined 

nitrate/nitrite 

E. Clarifications and Corrections to 

Previously Approved Methods in 40 CFR 

136.3 

The rule also clarifies the procedures 

for measuring orthophosphate and 

corrects typographical or other citation 

errors in Part 136. Specifically, the rule 

clarifies the purpose of the immediate 

filtration requirement in orthophosphate 

measurements (Table IB, parameter 44), 

which is to assess the dissolved or bioavailable form of orthophosphorus (i.e., 

that portion 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). EPA 

has added a footnote (24) to Table II 

providing this clarification. The rule 

also corrects missing citations to the 

table of microbiological methods for 

ambient water monitoring which are 

specified in Table IH at 40 CFR 136.3. 

When EPA approved the use of certain 

microbiological methods on March 26, 

2007 (72 FR 14220), EPA inadvertently 

omitted fecal coliform, total coliform, 

and fecal streptococcus methods from 

the table. This omission is corrected in 

today’s rule. 

F. Revisions in Table II at 40 CFR 

136.3(e) to Required Containers, 

Preservation Techniques, and Holding 

Times 

The rule revises some of the current 

requirements in Table II at 136.3(e). 

1. The rule revises footnote 4 of Table 

II to clarify the sample holding time for 

the Whole Effluent Toxicity (WET) 

samples for the three toxicity methods 

by adding the following sentence: ‘‘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.’’ In addition, EPA will post on 

the WET Web site corrections to errata 

in the ‘‘Short-term Methods for 

Estimating the Chronic Toxicity of 

Effluents and Receiving Waters to 

Freshwater Organisms’’ manual (EPA 

2010e). 

2. The rule revises the cyanide sample 

handling instructions in Footnote 5 of 

Table II to recommend the treatment 

options for samples containing oxidants 

described in ASTM’s sample handling 

practice for cyanide samples, D7365– 

09a. 

3. The rule revises the cyanide sample 

handling instructions in Footnote 6 of 

Table II to describe options available 

when the interference mitigation 

instructions in D7365–09a are not 

effective, and to allow the use of any 

technique for removal or suppression of 

interference, provided the laboratory 

demonstrates and documents that the 

alternate technique more accurately 

measures cyanide through quality 

control measures described in the 

analytical test method. 

4. The rule revises footnote 16 of 

Table II instructions for handling Whole 

Effluent Toxicity (WET) samples by 

adding two sentences: ‘‘Aqueous 

samples must not be frozen. Handdelivered samples used on the day of 

collection do not need to be cooled to 

0 to 6 °C prior to test initiation.’’ 

5. The rule revises footnote 22 to 

Table II to read ‘‘Sample analysis should 

begin as soon as possible after receipt; 

sample incubation must be started no 

later than 8 hours from time of 

collection.’’ 

6. The rule adds three entries at the 

end of Table II with the containers, 

preservation, and holding times for the 

alkylated phenols, adsorbable organic 

halides, and chlorinated phenolics. 

When EPA proposed ASTM D7065–06 

for the alkylated phenols, commenters 

noted that EPA did not include 

preservation and holding time 

information in Table II. When EPA 

moved EPA Methods 1650 and 1653 


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from 40 CFR part 430 to Table IC, EPA 

inadvertently omitted the associated 

parameters to Table II, and is correcting 

this omission in today’s rule. The Table 

II information for containers, 

preservation, and holding times for 

these three new entries are taken from 

the approved methods. 

G. Revisions to 40 CFR 136.4 and 136.5 

This rule changes §§ 136.4 and 136.5 

to clarify the procedures for obtaining 

review and approval for the use of 

alternate test procedures (alternate 

methods or ATPs) for those methods for 

which EPA has published an ATP 

protocol (there are published protocols 

for chemistry, radiochemical, and 

microbiological culture methods). In 

particular, it establishes separate 

sections outlining the procedures for 

obtaining EPA review and approval for 

nationwide use of an ATP (§§ 136.4), 

and the procedures for obtaining 

approval for limited use of an ATP 

(§§ 136.5). 

In addition, this rule adds language to 

Part 136.5 to clarify the purpose and 

intent of limited use applications. This 

provision only allows use of an alternate 

method for a specific application at a 

facility or type of discharge. The 

Regional Alternate Test Procedure 

(ATP) Coordinator or the permitting 

authority, at his/her discretion, may 

grant approval to all discharges or 

facilities specified in the approval letter. 

However, the appropriate permitting 

authority within a state may request 

supporting test data from each 

discharger or facility prior to allowing 

any such approvals. 

Today’s rule further clarifies that the 

limited use provision cannot be used to 

gain nationwide approval and is not a 

way to avoid the full examination of 

comparability that is required for 

alternate test procedures when EPA 

considers a method for nationwide use 

with the ultimate goal of listing it as an 

approved CWA method at 40 CFR part 

136. As further clarification, in the 

event that EPA decides not to approve 

a method proposed for nationwide use, 

the Regional ATP Coordinator or the 

permitting authority may choose to 

reconsider any previous limited use 

approvals of the alternate method. 

Based on this reconsideration, the 

Regional ATP Coordinator or the 

permitting authority will notify the 

user(s) if the limited use approval is 

withdrawn. Otherwise, the limited use 

approvals remain in effect. 

H. Revisions to Method Modification 

Provisions at 40 CFR 136.6 

This section allows users to make 

certain modifications to an approved 

method to address matrix interferences 

without the extensive review and 

approval process specified for an 

alternate test procedure at 136.4 and 

136.5. Today’s rule revises 136.6 to 

provide more examples of allowed and 

prohibited method modifications. The 

intent of today’s revisions is to clarify 

those situations in which an ATP is 

required and those where it is not. 

Analysts may use the examples to help 

assess the need for a formal ATP, and 

in the event an ATP is not needed to 

document that their modification is 

acceptable and does not depart 

substantially from the chemical 

principles in the method being 

modified. 

In response to comments, EPA has 

included additional examples of 

allowed and prohibited method 

modifications and has made some 

revisions to the text language as 

discussed in Section III below. 

I. New Quality Assurance and Quality 

Control Language at 40 CFR 136.7 

EPA is specifying ‘‘essential’’ quality 

control elements at § 136.7 for use in 

conducting an analysis for CWA 

compliance monitoring. This new 

language is added because auditors, coregulators, laboratory personnel, and the 

regulated community have noted the 

variations in quality assurance (QA) and 

quality control (QC) procedures 

practiced by laboratories that use 

40 CFR part 136 methods for 

compliance monitoring. Some of these 

methods are published by voluntary 

consensus standards bodies, such as the 

Standard Methods Committee, and 

ASTM International. Standard Methods 

and ASTM are available in printed or 

electronic compendia, or as individual 

online files. As mentioned in the 

proposal, each organization has a 

unique compendium structure. QA and 

QC method guidance or requirements 

may be listed directly in the approved 

consensus method, or, as is more often 

the case, these requirements are listed in 

other parts of the compendium. 

Regardless of the publisher, edition, 

or source of an analytical method 

approved for CWA compliance 

monitoring, analysts must use suitable 

QA/QC procedures whether EPA or 

other method publishers have specified 

these procedures in a particular Part 136 

method, or referenced these procedures 

by other means. These records must be 

kept in-house as part of the method 

testing documentation. Consequently, 

today’s rule clarifies that an analyst 

using these consensus standard body 

methods for reporting under the CWA 

must also comply with the quality 

assurance and quality control 

requirements listed in the appropriate 

sections in that consensus standard 

body compendium. EPA’s approval of 

use of these voluntary consensus 

standard body methods contemplated 

that any analysis using such methods 

would also meet the quality assurance 

and quality control requirements 

prescribed for the particular method. 

Thus, not following the applicable and 

appropriate quality assurance and 

quality control requirements of the 

respective method means that the 

analysis does not comply with the 

requirements in EPA’s NPDES 

regulations to monitor in accordance 

with the procedures of 40 CFR part 136 

for analysis of pollutants. 

For methods that lack QA/QC 

requirements (as specified in this new 

section at 40 CFR 136.7), whether 

developed by EPA, a vendor, or a 

consensus standard body, analysts can 

refer to and follow the QA/QC 

published in several public sources. 

Examples of these sources include the 

relevant QA/QC sections of an 

equivalent approved EPA method, or 

voluntary consensus standards 

published as Part 136 approved 

methods (e.g., Standard Methods, ASTM 

International, and AOAC). In addition to 

and regardless of the source of the 

laboratory’s or method’s QA and QC 

instructions, for methods that lack QA/ 

QC requirements, EPA is adding 

requirements at 136.7 to specify twelve 

essential quality control elements that 

must be in the laboratory’s documented 

quality system unless a written rationale 

is provided to explain why these quality 

control elements are inappropriate for a 

specific analytical method or 

application. These twelve essential 

quality control checks must be clearly 

documented in the written SOP (or 

method) along with a performance 

specification or description for each of 

the twelve checks, as applicable to the 

specific method. EPA has clarified the 

language in this section in response to 

public comments. The revised language 

is discussed in section III below. 

J. Revisions at 40 CFR Part 423 (Steam 

Electric Power Generating Point Source 

Category) 

The rule revises the 40 CFR part 423 

definitions for total residual chlorine 

and free available chlorine at 

§§ 423.11(a) and 423.11(l) to allow the 

use of ‘‘chlorine—total residual’’ and 

‘‘chlorine—free available’’ methods in 

§ 136.3(a), Table IB, or other methods 

approved by the permitting authority. 


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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. EPA Is Not Adding EPA Method 

1614A 

The Agency proposed to add Method 

1614A, ‘‘Brominated Diphenyl Ethers in 

Water, Soil, Sediment, and Tissue by 

HRGC/HRMS.’’ EPA developed this 

method to determine 49 polybrominated 

diphenyl ether (PBDE) congeners in 

aqueous, solid, tissue, and multi-phase 

matrices. This method uses isotope 

dilution and internal standard high 

resolution gas chromatography/high 

resolution mass spectrometry (HRGC/ 

HRMS). The commenters were divided 

on whether EPA should approve this 

method. Two commenters stated that 

Method 1614A would be a valuable 

addition to the list of approved 

methods, while two other commenters 

stated that the method has not been 

sufficiently validated for use in Clean 

Water Act programs. Upon further 

evaluation of the data supporting the 

use of this test procedure and the peer 

review comments, EPA agrees with 

those commenters who stated that 

additional validation data are needed to 

fully characterize the performance of 

this method for various matrices and 

has decided not to include Method 

1614A in today’s final rule. 

B. Deferral of Action on EPA Method 

1668C 

The Agency proposed to add EPA 

Method 1668C, ‘‘Chlorinated Biphenyl 

Congeners in Water, Soil, Sediment, 

Biosolids, and Tissue by HRGC/HRMS.’’ 

This method measures individual 

chlorinated biphenyl congeners in 

environmental samples by isotope 

dilution and internal standard high 

resolution gas chromatography/high 

resolution mass spectrometry (HRGC/ 

HRMS). As discussed in the proposal, 

Part 136 methods for chlorinated 

biphenyls (PCBs) only measure a 

mixture of congeners in seven 

Aroclors—PCB–1016, PCB–1221, PCB– 

1232, PCB–1242, PCB–1248, PCB–1254, 

and PCB–1260, while Method 1668C 

can measure the 209 PCB congeners in 

these mixtures. 

EPA began development of this 

method in 1995, initially covering 13 

congeners labeled ‘‘toxic’’ by the World 

Health Organization. In 1999, EPA 

expanded the scope of the method to 

include all 209 PCB congeners. The 

method has been used to support 

several studies, including the 2001 

National Sewage Sludge Survey and the 

National Lake Fish Tissue Survey. Since 

1999, EPA has revised the method to 

incorporate additional information and 

data collected such as the results of an 

inter-laboratory validation study, peer 

reviews of the method and the 

validation study data, additional QC 

performance criteria and MDL data, and 

user experiences. In the development 

and subsequent multi-laboratory 

validation of this method, EPA 

evaluated method performance 

characteristics, such as selectivity, 

calibration, bias, precision, quantitation 

and detection limits. The Agency is 

aware that this method is being used in 

some states in their regulatory programs 

and by other groups for some projects 

with good success. For example, in a 

study of data comparability between 

two laboratories on samples collected 

from the Passaic River in New Jersey, in 

which 151 PCB congeners were 

identified and measured, accuracy, as 

measured by analysis of an NIST SRM, 

was 15% or better. Recoveries of the 

PCB congeners ranged from 90% to 

124% and averaged 105%; precision 

ranged from 4.2 to 23% (Passaic River 

2010). This type of data shows that 

recoveries and precision for this method 

are within the performance achievable 

with other approved methods. 

EPA received comments from thirtyfive individuals or organizations on this 

method. Of these commenters, five 

(three states, one laboratory, and one 

laboratory organization) supported the 

approval of this method. Some states 

indicated that they are already requiring 

this method for use in permits and for 

other purposes. On the other hand, 

industry and industry groups/ 

associations were critical of the method 

for various reasons. Commenters 

opposing the method provided a 

detailed critique of the method, the 

inter-laboratory study, the peer reviews 

and the other supporting 

documentation. Among the criticisms of 

the inter-laboratory study, commenters 

argued that: (1) EPA did not produce 

documentation supporting changes to 

the method approved by EPA for the 

interlaboratory study, (2) the raw data 

for wastewater and biosolids was poor 

and is not fit for use in a comprehensive 

interlaboratory study, (3) EPA cited 

certain guidelines such as ASTM but 

deviated from those guidelines (e.g., 

used only one Youden pair per matrix), 

(4) the peer reviewers’ qualifications 

were questioned, (5) the addendum and 

the pooled MDLs/MLs were not 

subjected to peer review, (6) MDL/ML 

are flawed, the process to calculate 

MDLs/MLs for congeners that co-elute 

was flawed, the MDL/ML ignored the 

ubiquitous problem of background 

contamination, and (7) the validation 

study did not include all matrices in the 

method (soil and sediment excluded). In 

addition, some commenters also 

suggested that EPA should first 

promulgate new detection and 

quantitation procedures. Further, 

commenters raised questions about 

possible adverse effects of this new 

method on compliance monitoring as 

well as concerns about data reporting 

and costs. 

EPA is still evaluating the large 

number of public comments and intends 

to make a determination on the approval 

of this method at a later date. In the 

meantime, the Agency has decided to go 

forward with the promulgation of the 

other proposed analytical methods to 

expedite their implementation by the 

regulated community and laboratories. 

This decision does not negate the merits 

of this method for the determination of 

PCB congeners in regulatory programs 

or for other purposes when analyses are 

performed by an experienced laboratory. 

C. EPA Is Not Adding ASTM Methods 

D7574–09 and D7485–09 

In today’s rule, EPA is not adding two 

proposed ASTM methods, ASTM 

D7574–09 ‘‘Standard Test Method for 

Determination of Bisphenol A (BPA),’’ 

and ASTM D7485–09 ‘‘Standard Test 

Method for Determination of NP, OP, 

NP1EO, and NP2EO.’’ These two 

methods involve liquid chromatography 

and tandem mass spectrometry (LC/MS/ 

MS). The methods have been tested by 

a single laboratory in several 

environmental waters, and may be 

useful for many applications. However, 

EPA has decided to postpone approval 

of these two methods for general use 

until completion of a full interlaboratory validation study designed to 

fully characterize the performance of 

these methods across multiple 

laboratories and matrices. 

D. Revisions and Clarifications to EPA 

Method 200.7 

EPA Method 200.5 ‘‘Determination of 

Trace Elements in Drinking Water by 

Axially Viewed Inductively Coupled 

Plasma—Atomic Emission 

Spectrometry’’ employs a plasma torch 

viewed in the axial orientation to 

measure chemical elements (metals). As 

stated earlier in today’s rule, EPA is 

adding Method 200.5 for some metals in 

Table IB. Both Methods 200.5 and 200.7 

are acceptable methods under Part 136 

and both methods employ ICP/AES 

technology. However, Method 200.5 

includes performance data for the axial 

configuration that is not in Method 

200.7 because the axial technology torch 


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results were not available when Method 

200.7 was developed. For some 

parameters listed in Table IB, the axial 

orientation using ICP/AES technology 

results in greater sensitivity and lower 

detection limits than the radial 

orientation. Thus, today’s approval of 

Method 200.5 and the additional 

flexibility to modify Method 200.7 to 

use the axial orientation discussed in 

the proposal will allow laboratories to 

use either axial instruments or radial 

instruments to measure metals in water 

samples with Method 200.7. In response 

to EPA’s proposal to allow the use of the 

axial orientation of the torch with EPA 

Method 200.7, commenters expressed 

support for this added flexibility. Thus, 

today’s rule clarifies that the use of the 

axial orientation of the torch to measure 

metals is an acceptable modification to 

Method 200.7. EPA has added new text 

at Part 136.6(b)(5) to allow the use of the 

axial orientation of the torch for Method 

200.7 as an acceptable method 

modification that does not require an 

ATP application. 

EPA further notes that there was a 

typographical error in Section II.J of the 

proposed rule which stated that the 

version of EPA Method 200.7 (which the 

Agency proposed to remove; with 

Appendix C, see section IIIM below) has 

been superseded by Revision 5.4 of 

Method 200.7. Today’s final rule reflects 

that the correct reference is Revision 4.4 

of EPA Method 200.7. In today’s rule, 

EPA has added Method 200.7 Revision 

4.4 as an additional approved method 

for the measurement of titanium. As 

some commenters pointed out, EPA 

Method 200.7 covers this parameter and 

exclusion of this method for the 

measurement of titanium in Table IB 

was an oversight. 

In addition, EPA has removed EPA 

Method 200.7 from Table IB for the 

measurement of mercury. The addition 

of EPA Method 200.7 to the list of 

approved methods for mercury in Table 

IB was an error. Although this pollutant 

is on the list of analytes in EPA Method 

200.7, mercury may be lost to the 

atmosphere through the use of the 

approved total recoverable metals 

digestion procedures (e.g., EPA Method 

200.2, or the digestion procedures listed 

in EPA Method 200.7) that must be 

applied to the wastewater samples of 

interest under the Clean Water Act 

program. Such losses can lead to poor 

recovery in the samples compared to the 

sample preparation procedures included 

in other mercury methods approved at 

40 CFR part 136. Therefore, EPA 

Method 200.7 has not been included in 

Table IB for mercury. 

E. Revisions and Corrections to Certain 

Citations in Tables IA, IB, IC, ID, and IG 

EPA proposed some additions to 

Table IB which include some new 

Standard Methods or new versions of 

approved Standard Methods. Today’s 

rule revises the applicability of some 

methods and makes some corrections to 

the method citations. Specifically, EPA 

removed SM 3120 and SM 3125 for the 

measurement of mercury because 

mercury is not on the list of analytes for 

these methods. In addition, EPA 

corrected the citation of SM 3113 to SM 

3113B–2004 in the final rule and has 

added SM 3113B–2004 for the 

measurement of cadmium, chromium, 

iron, lead, and silver, because these 

analytes are covered by the method and 

they exhibit acceptable analytical 

performance. These omissions were an 

oversight. 

EPA also deleted from Table ID an 

EPA GC/MS method, Method 525.1, for 

the measurement of ametryn, diazinon, 

disulfoton, prometon, and trifluoralin. 

These analytes are not listed within the 

scope of this method and their inclusion 

in the proposal was an error. 

EPA has corrected a number of 

typographical errors in the tables and 

footnotes, correcting spelling and 

method availability information, 

method title names, and document 

identification numbers. A complete list 

of these changes has been included in 

a memo to the docket. 

F. Continued Approval of Method 1664 

Rev. A 

EPA proposed to replace Method 1664 

Rev. A for the measurement of oil and 

grease with a revised version (Method 

1664 Rev. B). This new version of the 

method describes modifications that are 

allowed and modifications that are not 

allowed when using this method for 

compliance with Clean Water Act 

regulations. Comments were generally 

supportive of the revised method but 

some commenters recommended that 

Method 1664 Rev. A not be withdrawn 

immediately because many permits 

currently specify the use of this method. 

In response to these comments, EPA 

will continue to allow the use of 

Method 1664 Rev. A for current permits 

because this method is not significantly 

different from the revised version of the 

method. However, EPA strongly 

encourages the use of the revised 

method (Method 1664 Rev. B) in the 

future. EPA may revisit this decision in 

a future rulemaking. 

G. Revision to Footnote 63 of Table IB 

at 40 CFR 136.3 

EPA received comments that the Hach 

Method 10360, described in footnote 63 

of Table IB, is a dissolved oxygen 

procedure, and as such, should only be 

listed as a procedure for dissolved 

oxygen, and not for BOD and CBOD. 

EPA disagrees with these commenters 

because the method on its face is clearly 

applicable to dissolved oxygen 

measurements in conjunction with BOD 

and CBOD analyses, as described in the 

method. As a result, in today’s final 

rule, EPA added language to the end of 

this footnote to clarify that Part 136 

allows the use of Hach Method 10360 

for measurement of dissolved oxygen in 

conjunction with the methods approved 

for measurement of biochemical 

demand (BOD) and carbonaceous 

biochemical oxygen demand (CBOD). 

H. Revision to Footnote 4 of Table IC at 

40 CFR 136.3 

EPA received comments on the 

proposed approval of Method 624 for 

the definitive determination of acrolein 

and acrylonitrile. Commenters agreed 

with the addition of these two analytes, 

but one of these commenters expressed 

concern about a blanket approval 

without requiring a demonstration of 

adequate performance and appropriate 

sample introduction techniques. This 

commenter recommended that 

performance criteria and information 

about appropriate sample introduction 

techniques be added to footnote 4 of 

Table IC. EPA agrees with this 

commenter’s suggestions because this 

requirement would ensure that the 

laboratory has the ability to measure 

these analytes at the levels necessary to 

comply with any associated regulations. 

In response to these concerns, in today’s 

rule, the Agency revised the footnote to 

add a statement requiring 

documentation of the ability to 

quantitatively measure these analytes 

and advising analysts that other sample 

introduction techniques may be 

required to achieve adequate 

performance. 

I. Revisions to Table II Language 

EPA proposed to revise the text at 

136.3(e) to allow any party to modify 

sample preservation and holding times 

after submitting documentation to its 

permitting or other authority that 

supports use of an alternative approach. 

Commenters expressed concern that this 

change would present a burden both to 

permitting authorities to review and 

approve changes, and for laboratories 

that work in different states because 

each state could have different 

requirements. In response to public 

comments, EPA has removed the 

proposed language at 136.3(e) that 

would have allowed such modifications 

based on documentation and procedures 


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determined by individual permitting 

authorities. Instead, such modifications 

must continue to be requested via a 

limited use ATP application to the 

Regional Alternate Test Procedure 

Coordinator or permitting authority, as 

appropriate. Thus, approval of any 

changes in sample preservation 

procedures, container materials, and 

maximum allowable holding time will 

remain unchanged and continue to be 

the responsibility of EPA through its 

Alternate Test Procedure program. EPA 

clarified language regarding the limited 

use application process procedure. 

Additionally, in today’s rule, EPA 

added a clarifying sentence at the end 

of the current language to emphasize 

that an analyst cannot modify any 

sample preservation or holding time 

requirements in an approved method 

unless the requirements in Section 

136.3(e) are met. 

EPA also revised footnote 4 to Table 

II to delete the parenthetical statement 

specifying that samples analyzed for 

fecal coliforms may be held up to six 

hours prior to commencing analysis. 

That statement in footnote 4 is 

inconsistent with the requirement for an 

eight-hour holding time, as pointed out 

by a commenter. 

In response to comments, EPA 

included a new entry in Table II for the 

alkylated phenols (parameters 114 to 

118 in Table IC) that was inadvertently 

omitted from the proposal. Similarly, 

when EPA moved EPA Methods 1650 

and 1653 to Table IC, EPA inadvertently 

omitted to add the parameters 

adsorbable organic halides (AOX) and 

chlorinated phenolics to Table II. The 

Table II information for containers, 

preservation, and holding times for 

these three new entries are taken from 

the approved methods. 

J. Approval of Alternate Test Procedures 

for Limited Use at 40 CFR 136.5 

EPA proposed changes to 40 CFR 

136.4 and 136.5 that establish the 

procedures for obtaining approval for 

use of a nationwide or limited use ATP. 

The proposed revisions established 

separate sections outlining the 

procedures for obtaining EPA review 

and approval for nationwide use of an 

ATP (§§ 136.4), and the procedures for 

obtaining approval for limited use of an 

ATP (§§ 136.5). The proposal also 

included language to clarify that limited 

use approvals do not require the same 

level of supporting data that would be 

required for nationwide approvals and 

that limited use approvals are not 

intended to be used as a means to avoid 

the full examination of comparability 

that is required for an application for 

approval of an alternative test procedure 

for nationwide use. 

Today’s rule finalizes these sections 

as proposed with one exception. EPA 

received comments that the proposed 

language under § 136.5 does not require 

that comparability data be submitted 

when seeking a Regional limited use 

ATP approval. EPA agrees that 

comparability data is an essential 

component of the ATP approval process 

and had inadvertently omitted this 

language. As a result, the Agency added 

language in today’s final rule that 

requires an applicant to provide 

comparability data specific to the 

limited use for the performance of the 

proposed alternative test procedure 

relative to the performance of the 

reference method. 

K. Revisions to Language at § 136.6 

EPA proposed to revise the section on 

method modification provisions at 40 

CFR 136.6 to provide more examples of 

allowed and prohibited method 

modifications. Acceptable reasons for an 

analyst to modify a method include 

analytical practices that lower detection 

limits, improve precision, reduce 

interferences, lower laboratory costs, 

and promote environmental 

stewardship by reducing generation of 

laboratory wastes. Acceptable 

modifications may use existing or 

emerging analytical technologies that 

achieve these ends provided that they 

do not depart substantially from the 

underlying chemical principles in 

methods currently approved in 40 CFR 

part 136. Analysts may use the 

examples in this section to help assess 

whether the modifications require an 

ATP and if not, to document that their 

modification is acceptable. The 

additional examples provide further 

guidance to laboratories and permittees 

on allowable method modifications that 

do not require an application through 

the ATP program. Proposal comments 

generally expressed support for 

allowing the flexibility to make certain 

changes to methods and for the specific 

examples of allowable changes included 

in the proposal. In addition, some 

commenters suggested revisions to 

clarify EPA’s intent in Sections (b)(4) 

and (b)(5) of 40 CFR 136.6. EPA 

reviewed the suggestions and agrees 

with commenters that the revisions will 

provide additional clarity. In addition, 

as discussed in Section III.D of this 

preamble, EPA added the use of axially 

viewed torch as an allowable 

modification to Method 200.7. Today’s 

rule includes the following revisions to 

the regulatory text: 

(a) Adds language to Section (b)(3) to 

clarify that modifications to sample 

collection, preservation, and holding 

time do not fall within the scope of 

136.6, 

(b) Revises the language at (b)(4)(T) be 

more specific with respect to the use of 

gas diffusion across a hydrophobic 

semi-permeable membrane to separate 

the analyte of interest from the sample 

matrix in place of manual or automated 

distillation for the analysis of certain 

analytes, 

(c) Revises the equation for Relative 

Standard Error (RSE) in (b)(4)(J) to make 

it consistent with the description in 

other EPA methods, and 

(d) Adds the use of an axially viewed 

torch with Method 200.7 as an 

allowable modification. 

L. Revisions to New Quality Assurance 

and Quality Control Language 

For today’s rule, EPA added some 

introductory language to this section to 

clarify the new requirements. EPA 

added this language to provide some 

additional clarity as to when the new 

requirements are applicable and, thus, 

must be incorporated into the 

laboratory’s documented standard 

operating procedures. Additional 

discussion of the revisions is provided 

under section IV.C below. 

M. Withdrawal of Appendices at 40 CFR 

Part 136 

EPA proposed to incorporate by 

reference in Table IB all of the methods 

printed in 40 CFR part 136 Appendices 

A and C, and to remove most of the 

information in Appendix D. The 

methods in Appendix A are EPA 

Method Numbers 601 through 613, 624, 

625, 1613B, 1624B, and 1625B. 

Appendix C contains EPA Method 

200.7, ‘‘Determination of Metals and 

Trace Elements in Water and Wastes by 

Inductively Coupled Plasma—Atomic 

Emission Spectrometry’’. However, 

Federal regulations at 1 CFR part 

51.7(c)(1) prohibit the incorporation by 

reference of material previously 

published in the Federal Register. Thus, 

EPA is not withdrawing Appendices A 

or C. Because EPA Method 200.7 has 

been revised, EPA is replacing the 

current version of this method in 

Appendix C with Rev. 4.4 of Method 

200.7. All of these methods are readily 

accessible from a variety of sources, 

including EPA’s CWA methods Web site 

http://water.epa.gov/scitech/methods/ 

cwa/index.cfm. 

The rule also removes most of the 

data from Appendix D for all EPA 

methods that are no longer approved, 

and retains only the Precision and 

Recovery Statements for EPA Method 

279.2 for thallium and EPA Method 

289.2 for zinc, and corrects 


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typographical errors in the Appendix. 

The current version of Appendix D will 

be available online at the CWA methods 

Web site for historical purposes. 

N. Revisions at 40 CFR Part 430 (Pulp, 

Paper, and Paperboard Point Source 

Category) 

EPA also proposed to remove 

Appendix A at 40 CFR part 430 and to 

incorporate by reference the methods in 

this Appendix. Appendix A contains 

two methods, EPA Method 1650 for 

adsorbable organic halides or AOX, and 

EPA Method 1653 for chlorinated 

phenolics. As explained above, we 

cannot incorporate by reference this 

material, so Appendix A remains 

unchanged in the Code of Federal 

Regulations. These methods are also 

readily available from a variety of 

sources, including EPA’s CWA methods 

Web site http://water.epa.gov/scitech/ 

methods/cwa/index.cfm. EPA is also 

adding these two methods to Table IC 

for general use. 

O. Revisions at 40 CFR Part 435 (Oil and 

Gas Extraction Point Source Category) 

The rule makes several changes to 

Part 435, Oil and Gas Extraction Point 

Source Category. First, EPA is moving 

the methods and associated quality 

assurance requirements from 40 CFR 

part 435, Subpart A (Offshore 

Subcategory) to an EPA document 

(‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ 

EPA–821–R–11–004), and incorporating 

by reference this document in the 

revised regulation at 40 CFR part 435. 

This approach organizes the analytical 

methods for the Offshore Subcategory 

into one document and allows for easier 

access to the methods for this category. 

The following table lists the methods 

EPA moved from part 435 to the cited 

document, EPA–821–R–11–004. 

EPA METHOD NUMBERS FOR OIL AND GAS EXTRACTION POINT SOURCE CATEGORY ANALYTICAL METHODS AND PRIOR

CFR REFERENCES

Analytical/Test method EPA Method 

No. 

Date first promulgated Previous CFR references 

Static Sheen Test ................................................................. 1617 1993 Subpart A, Appendix 1. 

Drilling Fluids Toxicity Test ................................................... 1619 1993 Subpart A, Appendix 2. 

Procedure for Mixing Base Fluids With Sediments .............. 1646 2001 Subpart A, Appendix 3. 

Protocol for the Determination of Degradation of NonAqueous Base Fluids in a Marine Closed Bottle Biodegradation Test System: Modified ISO 11734:1995.1647 2001 Subpart A, Appendix 4. 

Determination of Crude Oil Contamination in Non-Aqueous 

Drilling Fluids by Gas Chromatography/Mass Spectrometry (GC/MS).

1655 2001 Subpart A, Appendix 5. 

Reverse Phase Extraction (RPE) Method for Detection of 

Oil Contamination in Non-Aqueous Drilling Fluids (NAF).

1670 2001 Subpart A, Appendix 6. 

Determination of the Amount of Non-Aqueous Drilling Fluid 

(NAF) Base Fluid from Drill Cuttings by a Retort Chamber (Derived from API Recommended Practice 13B–2).

1674 2001 Subpart A, Appendix 7. 

As noticed in the proposed rule, EPA 

is also incorporating additional quality 

assurance procedures in the marine 

anaerobic biodegradation method 

(Appendix 4 of Subpart A of part 435) 

and is correcting some erroneous 

references and omissions in the method 

for identification of crude oil 

contamination (Appendix 5 of Subpart 

A of part 435) into the new document 

(EPA–821–R–11–004). 

EPA promulgated the use of the 

marine anaerobic biodegradation 

method (closed bottle test, ISO 

11734:1995 as clarified by Appendix 4 

to Subpart A of part 435) as an 

Appendix to the rule in 2001 because it 

most closely modeled the ability of a 

drilling fluid to biodegrade 

anaerobically in marine environments 

(January 22, 2001; 66 FR 6864). 

Subsequent to this promulgation, EPA 

incorporated additional quality 

assurance procedures for the marine 

anaerobic biodegradation method in the 

NPDES permit for the Western Gulf of 

Mexico (‘‘Final NPDES General Permit 

for New and Existing Sources and New 

Dischargers in the Offshore Subcategory 

of the Oil and Gas Extraction Category 

for the Western Portion of the Outer 

Continental Shelf of the Gulf of 

Mexico,’’ GMG290000, Appendix B). 

The additional quality assurance 

instructions in the GMG290000 more 

clearly describe the sample preparation 

and compliance determination steps. 

Specifically, these additional quality 

assurance procedures clarify that users 

must only use headspace gas to 

determine compliance with the Part 435 

effluent guidelines. EPA worked with 

the same industry consortium that 

assisted EPA in the development of the 

analytical methods used in the effluent 

guidelines for the Oil and Gas 

Extraction point source category 

(40 CFR part 435) to develop these 

additional quality assurance measures. 

Thus, the quality assurance procedures 

are generally applicable to this industry. 

Additionally, as noticed in the 

proposed rule, EPA is correcting some 

erroneous references and omissions in 

the method for identification of crude 

oil contamination (Appendix 5 of 

Subpart A of Part 435), as follows: 

a. Adding a schematic flow for 

qualitative identification of crude oil, 

which was erroneously omitted in 

Appendix 5 to Subpart A of part 435, 

b. Correcting erroneous citations in 

sections 9.5, 9.6, 11.3, and 11.3.1 of 

Appendix 5, and 

c. Adding a missing ‘‘<’’ (less than) 

sign for identification of crude oil 

contamination in the asphaltene crude 

discussion at Section 11.5.4.2. The 

asphaltene discussion now reads as 

follows: ‘‘Asphaltene crude oils with 

API gravity < 20 may not produce 

chromatographic peaks strong enough to 

show contamination at levels of the 

calibration. Extracted ion peaks should 

be easier to see than increased 

intensities for the C8 to C13 peaks. If a 

sample of asphaltene crude from the 

formation is available, a calibration 

standard shall be prepared.’’ 

EPA received three comments on the 

proposed changes. One commenter was 

concerned that the EPA document 

(EPA–821–R–11–004) would not have 

the same legal status as publishing the 

methods in the CFR. EPA disagrees with 

this comment. The incorporation by 

reference of this document has the same 

legal standing as publishing the text of 

the methods in the CFR. EPA has a long 

standing practice of publishing test 

methods using incorporation by 

reference and the cited test methods are 


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as legally enforceable as those published 

in full in the CFR. EPA is consolidating 

these methods into one document to 

allow for easier access to these methods. 

The incorporation by reference of this 

document also allows for better 

formatting of the methods and 

eliminates the redundant publication of 

these methods each year in the Code of 

Federal Regulations. Two other 

commenters had some 

recommendations for additional 

revisions to the EPA document (EPA– 

821–R–09–013). EPA has not adopted 

these suggestions, given the absence of 

an opportunity for the public generally 

to comment on them. EPA will, 

however, consider these comments and 

may propose additional revisions in a 

future rulemaking. As noticed in the 

proposed rulemaking, the final rule 

consolidates the oil and gas test 

methods into a single document and 

references this document in the effluent 

guidelines (40 CFR part 435). Like any 

other changes to an EPA-approved 

method, any changes to the methods in 

the EPA document (EPA–821–R–11– 

004) will require a rulemaking. 

IV. Summary of EPA’s Response to 

Comments 

The Agency received comments from 

117 different individuals or 

organizations on the September 23, 2010 

proposal (75 FR 58024). Commenters 

represented a variety of different 

interests, including analytical 

laboratories, water utilities, instrument 

manufacturers, State and local 

governments, trade associations, and 

industry. A summary of major public 

comments on the proposed rule and the 

Agency’s responses is presented in this 

section. The public docket for this rule 

includes all of the comments received 

and the Agency’s responses. 

A. Approval of Standard Methods 

EPA proposed to revise how to 

identify EPA-approved Part 136 

methods that are published by the 

Standard Methods Committee (i.e., 

Standard Methods). EPA proposed two 

changes. First, EPA proposed to change 

the way it identifies an EPA-approved 

version of a Standard Method in Part 

136. Second, EPA proposed to identify 

only the most recently EPA-approved 

version of a Standard Method in Part 

136. In the past, EPA listed multiple 

versions of these methods from the 18th, 

19th, 20th editions of the printed 

compendiums, or from the on-line 

editions published by the Standard 

Methods Committee, in one or more 

columns in the Part 136.3 tables. In 

some cases, EPA approved more than 

one version of a Standard Method for a 

particular analyte in Part 136. Approval 

of several versions of the same Standard 

Method for an analyte has led to 

inconsistencies in how laboratories 

conduct these analyses, especially in 

quality assurance/quality control (QA/ 

QC) practices. For this reason, EPA 

proposed to list only the most recently 

EPA-approved version of a Standard 

Method (regardless of the printed or online edition) in Part 136, with few 

exceptions, to identify the method with 

the year of Standard Methods approval 

or adoption designated by the last four 

digits in the method number (e.g., 

Standard Method 3113B–2004). This 

approach clearly identifies the version 

of the standard method approved under 

Part 136 and no longer ties it to a 

particular compendium printing or 

edition of Standard Methods. For 

example, the exact method, Standard 

Method 3113B–2004 appears in the 

18th, 19th, and 20th edition of Standard 

Methods. Because this method is the 

same in all of these editions, a 

laboratory may refer to any of these 

editions when using Standard Method 

3113B–2004 to measure the analytes 

listed in Table IB that are approved for 

this method. Thus, EPA’s proposed 

approach to identify Part 136 approved 

standard methods does not rely on the 

particular edition of a compendium but 

rather on the latest Standard Methods 

approved version (by indicating the year 

of approval). 

EPA received numerous comments 

concerning the proposed changes to 

specify the method with the year of 

publication, rather than specifying the 

editions of Standard Methods in which 

the method is printed, and to list in Part 

136 only the most recent EPA-approved 

version of a Standard Method if 

Standard Methods has multiple versions 

of a method for a pollutant. Some 

commenters expressed concern about 

other economic impacts related to 

laboratory start-up tests, and the need 

for training and revised standard 

operating procedures (SOPs) associated 

with the use of the most recently 

approved method. In response, EPA 

maintains that the economic impacts of 

start-up tests or the need for revised 

SOPs are part of the necessary expenses 

to maintain a laboratory producing data 

of known and acceptable quality and 

these costs are not unusual. Training 

new staff or training current staff on 

new procedures is also a cost that any 

laboratory must consider as part of 

doing business. 

EPA is aware that Standard Methods 

and other voluntary consensus 

organizations such as ASTM and AOAC 

periodically revise existing methods and 

publish them on-line and/or as a 

compendium. In addition to EPAdeveloped methods, the Agency 

approves certain methods developed by 

these and other organizations as 

required under the National Technology 

Transfer and Advancement Act 

(NTTAA) and lists them in Part 136 

periodically. Often, after EPA approves 

a Standard Method for use in Part 136, 

Standard Methods releases or adopts a 

revised version of that method. 

Generally, these revised Standard 

Methods involve the use of new 

technologies or improvements to 

previously approved methods. By 

referencing the year of adoption by 

Standard Methods, EPA’s proposed 

change in its method citations was 

intended to clarify which version of a 

Standard Method is approved by EPA in 

Part 136. The on-line site for Standard 

Methods allows electronic release of 

new methods and revisions to existing 

methods prior to the publication of the 

compendium edition. Currently, 

Standard Methods is on a 5–7 year cycle 

for publication of the compendium and 

is set to release its 22nd edition soon. 

In some cases, an older version of a 

method approved by the Standard 

Methods Committee may appear on the 

on-line or compendium version of 

Standard Methods. The date of adoption 

is on the first page of the compendium 

or on-line method. 

Commenters are correct in pointing 

out that, in the event that they elect to 

use an EPA-approved Standard Method 

for compliance purposes, they would be 

required to use the most recently EPAapproved version of a Standard Method. 

EPA is not requiring any EPA-approved 

Standard Method in today’s rule. 

Dischargers may use any approved Part 

136 method for compliance monitoring 

unless the method is specified in its 

discharge permit by the permitting 

authority, or the method is not 

sufficiently sensitive to comply with the 

permit limit. Also, if the discharger 

elects to use an EPA-approved Standard 

Method and does not have the most 

recent EPA-approved version, EPA finds 

the costs would not be significant. The 

discharger/laboratory would need to 

purchase the on-line version for the 

individual method and would not need 

to absorb the cost of a full subscription 

to the on-line service. On-line versions 

of a single method generally cost $69. 

Relative to the costs that laboratories 

charge to run such an analysis 

(generally many times over), this cost is 

negligible. Therefore, EPA does not 

agree with commenters that they will 

have to purchase an on-line 

subscription to Standard Methods nor 

does it conclude that this change will 


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present a significant financial burden to 

laboratories. 

Another concern raised was that any 

changes in Standard Methods in the 

future would be automatically approved 

without EPA review. This assertion is 

incorrect. Any new or revised Standard 

Methods would be proposed in the 

Federal Register for public comment 

before inclusion in Part 136 as required 

under the Clean Water Act. 

Some commenters also expressed 

concern that this change may affect the 

approval status of existing alternate test 

procedures that were evaluated by EPA 

relative to older Standard Methods. 

With respect to this concern, the Agency 

is not withdrawing any approved ATPs. 

EPA’s withdrawal of its earlier approved 

versions of Standard Methods is not 

intended to affect the acceptance of any 

vendor-developed methods based on 

older Standard Methods that EPA 

previously determined to be acceptable 

versions, because the changes in 

Standard Methods are mostly editorial 

(e.g., clarifications, increased flexibility) 

and not procedural changes. 

In making this change in today’s rule, 

EPA also considered that beginning 

with the publication of the 20th edition 

of Standard Methods, the Standard 

Methods Committee included the 

quality control (QC) procedures which 

are similar to the QC procedures that 

have been included by EPA in methods 

published in Part 136 over the last two 

decades for use in compliance 

monitoring programs under the Clean 

Water Act and the Safe Drinking Water 

Act. These procedures are specified in 

Part 1000 of the Standard Methods 

compendium and include the 

‘‘essential’’ quality control checks that 

EPA has added at 40 CFR 136.7 as part 

of this final rule. 

B. Preservation and Holding Time 

Requirements for EPA Method 624 

In response to the proposed use of 

EPA Method 624 as a definitive 

measurement method for acrolein and 

acrylonitrile, EPA received comments 

on the preservation and holding time 

requirements for these two pollutants. 

Commenters noted that the preservation 

and holding time requirements in Part 

136 Table II for these two analytes 

currently differ from the requirements 

for other Method 624 analytes. 

Historically, these two analytes have 

had different preservation and 

requirements than the analytes currently 

listed in EPA Method 624. The current 

requirements in Table II date to 1984 

and specify that samples for acrolein 

and acrylonitrile must be preserved at a 

pH in the range of 4 to 5. This pH range 

is based on concerns about degradation 

of these two analytes in strongly acidic 

samples (e.g., pH < 2). Footnote 10 to 

Table II currently states that pH 

adjustment is not required if acrolein 

will not be measured, but that samples 

for acrolein receiving no pH adjustment 

at all must be analyzed within 3 days of 

sampling. In contrast, samples to be 

analyzed by EPA Method 624 for 

purgeable halocarbons are not preserved 

by adjusting the pH, and samples to be 

analyzed for the purgeable aromatic 

hydrocarbons (benzene, ethylbenzene 

and toluene) are preserved at a pH of 2. 

Thus, in the case where a permittee 

wants to use EPA Method 624 to 

measure acrolein or acrylonitrile in 

addition to other analytes included in 

Method 624, the sampler has to take an 

additional sample, preserve the sample 

for acrolein and acrylonitrile to pH 4 to 

5, and then perform separate analyses. 

Commenters stated that EPA does not 

have a basis for requiring a different 

preservation and holding times for these 

two analytes and submitted data that 

support their assertion that sample 

preservation be allowed at either a pH 

of 7 or a pH of 2. EPA has reviewed the 

data, but the Agency has concluded that 

these data are not sufficient or 

compelling to change the current 

preservation and holding time 

requirements for these analytes because 

the data are anecdotal rather than the 

result of a well-planned and properly 

documented stability study. As a result, 

EPA’s final rule retains the current 

sample preservation and holding time 

requirements for acrolein and 

acrylonitrile. 

C. Quality Assurance and Quality 

Control Requirements 

EPA proposed to specify minimal 

essential quality control requirements at 

Part 136.7 for use in conducting 

analyses to comply with CWA 

monitoring requirements. The purpose 

of this requirement is to ensure that 

laboratories conducting CWA 

compliance monitoring use suitable QA/ 

QC procedures. These QA/QC 

procedures were included in a 

memorandum to EPA’s Regional Quality 

Assurance Managers (May 7, 2009 

memorandum from Richard Reding) and 

have been posted on EPA’s Web page 

since 2009. These requirements do not 

apply in the case of the use of Part 136 

approved methods that contain (or 

reference) their own QA/QC procedures, 

or to any non-compliance analyses. 

Most analytical methods currently listed 

in Part 136 contain QA/QC procedures, 

and permittees/laboratories using those 

methods are not affected by the new 

requirement. However, there are a few 

older methods approved for use in Part 

136 from the 1970s that contain no QA/ 

QC requirements. Examples of Part 136 

methods that lack QA/QC are Method 

283.2 for titanium and Method 289.2 for 

zinc, both furnace atomic absorption 

methods issued in 1978. As explained 

previously, an additional issue 

identified in the May 7, 2009 

memorandum is that approved methods 

from consensus organizations such as 

Standard Methods contain the QA/QC 

requirements in a different section of 

their methods compendium (e.g., 

Standard Methods consolidates general 

QA/QC requirements for all methods in 

Part 1000 of their methods 

compendium). Thus, EPA wants to 

clarify that it expects permittees/ 

laboratories using Part 136 approved 

methods developed by consensus 

organizations for reporting compliance 

under the CWA to also comply with the 

QA/QC requirements listed in the 

appropriate sections in that consensus 

organization’s compendium. 

In addition to following QA/QC 

requirements from consensus 

organizations for Part 136 methods 

without QA/QC procedures, the analyst 

has the option to follow the QA/QC 

published in another EPA-approved 

method for that parameter that contains 

such QA/QC. 

As discussed in Section II.I of this 

preamble, EPA is reiterating the 

requirement to include QA/QC in any 

chemical method used for CWA 

compliance purposes. For those few Part 

136 methods that lack QA/QC 

requirements, EPA is adding quality 

control requirements at § 136.7. EPA 

received numerous comments on this 

aspect of the proposed rule. Although 

some commenters expressed support for 

EPA’s intent to ensure the quality of 

data by adding the new QC language, 

many commenters noted problems with 

the specific language, including that 

many of the QC elements do not apply 

to common parameters (e.g., MDLs 

cannot be calculated for pH or BOD, and 

surrogates and internal standards have 

no counterparts in microbiological 

methods). Other commenters expressed 

concern that the new language was 

either duplicative or contradicted 

language in existing EPA-approved 

methods, or presented conflicts with 

various state or national accreditation 

programs. Other commenters objected to 

the perceived costs associated with this 

new requirement and suggested that the 

QC checks simply will not occur, 

regardless of the new Part 136.7 

requirement. A few commenters 

suggested improvements to the 

proposed language, should EPA decide 

to proceed with this new section. One 

commenter stated that the section was 


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not needed, since EPA should not be 

approving methods at 40 CFR part 136 

that do not already contain appropriate 

QA/QC. EPA addresses these issues 

below. 

With respect to the issue of 

applicability of the QC elements, EPA 

agrees with commenters who stated that 

some QC elements listed in § 136.7 may 

not apply to common parameters (e.g., 

matrix spike and matrix spike 

duplicates do not apply to pH 

measurements). For any of the Part 136 

methods that include (or reference) 

appropriate QC elements for these 

parameters, these new QA/QC 

requirements are not applicable. As a 

result, in today’s final rule, EPA has 

added introductory language in § 136.7 

to clarify how laboratories should 

comply with this new requirement 

when one or more of the twelve 

essential quality control elements is not 

applicable to a method. This new 

introductory language states that in 

cases where one or more of the twelve 

QC elements do not apply to a given 

method, the laboratory may provide a 

written rationale for not including those 

elements in their standard operating 

procedures (SOP) for that analysis. This 

may be something as simple as stating 

that the given QC element does not 

apply to that analysis or is not possible 

to perform (as the example above for pH 

measurements). In addition, the final 

rule states that the twelve QC elements, 

as applicable, must be included in a 

laboratory’s SOP for conducting an 

analysis with an approved method only 

when there are no QA/QC procedures in 

the Part 136 method. Again, as 

discussed above, this QA/QC 

requirement at Part 136 does not apply 

to approved methods containing (or 

referencing) QA/QC procedures. 

In response to the comment that the 

language is either duplicative or 

contradicted in existing approved 

methods or accreditation programs, EPA 

has added this new section to the 

regulations at Part 136.7 to address 

concerns that certain approved methods 

do not contain QA/QC procedures. In 

those cases where an approved method 

incorporates these QC procedures (as 

applicable to that method), the 

laboratory can follow the method as 

written without creating any 

duplication or conflict. As mentioned in 

Section IV.A of this preamble, Standard 

Methods incorporated new QC 

requirements starting with the 20th 

edition of Standard Methods similar to 

the QC requirements included in EPA 

methods for the last two decades. Thus, 

most Standard Methods that are also 

approved methods in Part 136 already 

contain QA/QC requirements, as 

applicable. Similarly, EPA does not 

anticipate conflicts with laboratory 

accreditation programs because these 

programs generally follow the QC 

requirements in the method or as 

otherwise specified in regulatory 

programs. The purpose of this new 

section is to ensure that analyses 

conducted for compliance monitoring 

with CWA regulatory programs contain 

appropriate QA/QC and the Agency’s 

view is that this is already occurring in 

most laboratories (with a few exceptions 

as discussed above). This new 

requirement is added to clarify that 

laboratories must implement proper 

QA/QC, as needed, for all CWA 

compliance related analyses to provide 

quality data that will withstand 

regulatory and legal challenges. 

In response to the comment that this 

new requirement will be costly, proper 

QA/QC is essential for obtaining results 

of known and acceptable quality. In the 

long run, it could be much more costly 

to use data which lacks proper QC in 

demonstrating or enforcing discharge 

requirements. In the short run, 

laboratories would only incur costs 

associated with this new requirement 

when the method lacks QA/QC and 

when they have not included QA/QC as 

part of their SOPs. EPA estimates that 

this would not have a significant impact 

on laboratories because the vast majority 

of Part 136 methods already include or 

reference QA/QC requirements. Further, 

most laboratories already implement the 

QC checks prescribed by the newer 

methods and are already documenting 

these QC checks in the laboratory SOPs. 

Some of the QC checks are a one-time 

or infrequent expense (e.g., 

demonstration of capability and 

determination of a method detection 

limit), while other checks are routine 

(e.g., running a method blank). 

Typically, laboratories include QC as 

part of the overall analysis costs, and 

these costs generally add 10–20% to the 

analysis cost initially for an analyst 

demonstration of capability, and less (5– 

10%) after the initial cost for routine QC 

(e.g., running a blank with every batch 

of samples). For a typical analysis of a 

metal using furnace atomic absorption, 

at a cost of $35–50 per sample, the QC 

costs would be typically 5–10% of the 

total costs, and are generally included in 

the laboratory pricing schedule. Thus, 

EPA expects that any costs associated 

with this aspect of today’s rule will be 

minimal and limited to a few older 

methods that some laboratories may still 

elect to use rather than the many other 

methods that contain QA/QC 

requirements. EPA considers these QC 

checks to be an essential part of an 

overall approach to producing data of 

known quality and defensibility when a 

particular method is used to measure 

pollutants for compliance monitoring 

purposes. Ignoring these QC checks, as 

a commenter suggested, is inconsistent 

with EPA’s NPDES permit requirements. 

Thus, 40 CFR 122.41(e) of EPA’s NPDES 

permitting regulations provides that the 

permittee ‘‘shall at all times properly 

operate and maintain all facilities and 

systems of treatment and control * * * 

Proper operation and maintenance also 

includes adequate laboratory controls 

and appropriate quality assurance 

procedures * * *.’’ In most cases, these 

procedures are already a part of the 

quality control practices of most 

laboratories and will not create an 

additional burden. However, in 

codifying QC requirements, EPA 

provides clarification that these 

procedures are mandatory, as 

applicable, and not merely optional. 

V. 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 

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 


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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 today’s 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. 

Although EPA expects that in some 

cases the analytical costs could increase 

slightly due to additional QC 

requirements for a few old EPAapproved methods that lack QA/QC, 

EPA has determined that most 

laboratories that analyze samples for 

EPA compliance monitoring have 

already instituted QC requirements as 

part of their laboratory practices and 

this rule will not have a significant 

economic impact on a substantial 

number of small entities. 

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, today’s 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 EO 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 EO has the potential to influence the 

regulation. This action is not subject to 

EO 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 

ASTM International for use in 

compliance monitoring where the 

Agency has determined that those 

standards meet the needs of Clean Water 

Act programs. EPA is not adding two of 

the proposed ASTM methods to this 

final rule because these methods have 

not undergone full inter-laboratory 

validation as recommended in current 

Agency guidance (see Section III.C of 

this preamble). All other proposed 

voluntary consensus standards are 

approved in today’s rule. 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29771 

J. Executive Order 12898: Federal 

Actions To Address Environmental 

Justice in Minority Populations and 

Low-Income Populations 

Executive Order (EO) 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 June 

18, 2012. 

List of Subjects 

40 CFR Part 136 

Environmental protection, Test 

procedures, Incorporation by reference, 

Reporting and recordkeeping 

requirements, Water pollution control. 

40 CFR Part 260 

Environmental protection, 

Administrative practice and procedure, 

Confidential business information, 

Hazardous waste, Incorporation by 

reference, Reporting and recordkeeping 

requirements. 

40 CFR Part 423 

Environmental protection, Steam 

Electric Power Generating Point Source 

Category, Incorporation by reference, 

Reporting and recordkeeping 

requirements, Water pollution control. 

40 CFR Part 430 

Environmental protection, Pulp, 

Paper, and Paperboard Point Source 

Category, Incorporation by reference, 

Reporting and recordkeeping 

requirements, Water pollution control. 

40 CFR Part 435 

Environmental protection, Oil and 

Gas Extraction Point Source Category, 

Incorporation by reference, Reporting 

and recordkeeping requirements, Water 

pollution control. 

Dated: April 17, 2012. 

Lisa P. Jackson, 

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 

Administrator, or to a State having an 

approved NPDES program for a permit 

under section 402 of the Clean Water 

Act of 1977, as amended (CWA), and/or 

to reports required to be submitted 

under NPDES permits or other requests 

for quantitative or qualitative effluent 

data under parts 122 to 125 of title 40; 

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 CWA, as 

amended. 

* * * * * 

■ 3. Section 136.3 is amended: 

■ a. By revising paragraph (a) 

introductory text and Tables IA, IB, IC, 

ID, IG, and IH; 

■ b. By revising paragraph (b); 

■ c. By revising paragraph (e) 

introductory text; 

■ d. By revising Table II to paragraph 

(e). 

These 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. 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, 625, 

1613, 1624, and 1625. The full texts of 

Methods 601–613, 624, 625, 1613, 1624, 

and 1625 are printed in appendix A of 

this part 136, and the full text of Method 

200.7 is printed in appendix C of this 

part 136. The full text for determining 

the method detection limit when using 

the test procedures is given in appendix 

B of this part 136. The full text of 

Method 200.7 is printed in appendix C 

of this part 136. In the event of a conflict 

between the reporting requirements of 

40 CFR Parts 122 and 125 and any 

reporting requirements associated with 

the methods listed in these tables, the 

provisions of 40 CFR Parts 122 and 125 

are controlling and will determine a 

permittee’s reporting requirements. The 

full text of the referenced test 

procedures are incorporated by 

reference into Tables IA, IB, IC, ID, IE, 

IF, IG, and IH. The discharge parameter 

values for which reports are required 

must be determined by one of the 

standard analytical test procedures 

incorporated by reference and described 

in Tables IA, IB, IC, ID, IE, IF, IG, and 

IH or by any alternate test procedure 

which has been approved by the 

Administrator under the provisions of 

paragraph (d) of this section and 

§§ 136.4 and 136.5. Under certain 

circumstances paragraph (c) of this 

section, § 136.5(a) through (d) or 40 CFR 

401.13, other additional or alternate test 

procedures may be used. 


srobinson on DSK4SPTVN1PROD with RULES2
29772 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

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. 

Membrane filter (MF) 2, 

single step 

p. 124 3 ....................... 9222 D–1997 .............. 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–1997. 

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–1997 .............. 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 + B.5c)¥1997 

5. E. coli, number per 

100 mL 21.

MPN 6,8,16 multiple 

tube, or.

..................................... 9221B.1–2006/9221F– 

2006 12,14.

multiple tube/multiple 

well, or 

..................................... 9223 B–200 413 ........... 991.15 10 ........... Colilert®13,18

Colilert-18®13,17,18

MF 2,6,7,8 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 22.

MPN 6,8, multiple tube/ 

multiple well, or 

..................................... ..................................... D6503–99 9 ....... Enterolert®13,24

MF 2,6,7,8 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


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

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

USGS Other 

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

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, embryolarval survival and 

teratogenicity.

1005.0.28

Inland silverside, 

Menidia beryllina, 

larval survival and 

growth.

1006.0.28

Mysid, Mysidopsis 

bahia, survival, 

growth, and fecundity.

1007.0.28

Sea urchin, Arbacia 

punctulata, fertilization.

1008.0.28

Table IA notes: 

1The method must be specified when results are reported. 

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

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

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

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

required to resolve any controversies. 6Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes to account for the quality, character, consistency, and anticipated organism density of the water sample. 7When the MF method has been used previously to test waters with high turbidity, large numbers of noncoliform bacteria, or samples that may 

contain organisms stressed by chlorine, a parallel test should be conducted with a multiple-tube technique to demonstrate applicability and comparability of results. 8To assess the comparability of results obtained with individual methods, it is suggested that side-by-side tests be conducted across seasons 

of the year with the water samples routinely tested in accordance with the most current Standard Methods for the Examination of Water and 

Wastewater or EPA alternate test procedure (ATP) guidelines. 9Annual Book of ASTM Standards–Water and Environmental Technology, Section 11.02. 2000, 1999, 1996. ASTM International. 

10Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998. AOAC International. 11 Recommended for enumeration of target organism in sewage sludge. 12The multiple-tube fermentation test is used in 9221B.1–2006. 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. 


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29774 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

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.1–2006, 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–10–003. April 2010. 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®, Quanti-Tray®/2000, 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®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories, Inc. 19A description of the mColiBlue24® test, is available from Hach Company. 20 Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation using A–1 Medium, EPA–821–R–06–013. July 

2006. U.S. EPA. 21 Recommended for enumeration of target organism in wastewater effluent. 22 Method 1603: Escherichia coli (E. coli ) in Water by Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar 

(modified mTEC), EPA–821–R–09–007. December 2009. U.S. EPA. 23 Method 1682: Salmonella in Sewage Sludge (Biosolids) by Modified Semisolid Rappaport-Vassiliadis (MSRV) Medium, EPA–821–R–06–014. 

July 2006. 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– 

09–016. December 2009. 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. 

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–1997 ........... D1067–06 ................ I–1020–85.2

2. Alkalinity, as 

CaCO3, mg/L.

Electrometric or Colorimetric titration to pH 

4.5, Manual.

.................................. 2320 B–1997 ........... D1067–06 ................ 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–1999 or 

3111 E–1999.

.................................. I–3051–85.2

AA furnace .............. .................................. 3113 B–2004.

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

(1994).

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

(2003) 68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4471– 

97.50

Direct Current Plasma (DCP) 36................................... .................................. D4190–08 ................ See footnote.34

Colorimetric 

(Eriochrome 

cyanine R).

.................................. 3500–Al B–2001.

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–1997 .. .................................. 973.493. 

Nesslerization .......... .................................. .................................. D1426–08 (A) .......... 973.493, I–3520–85.2

Titration ................... .................................. 4500–NH3 C–1997.

Electrode ................. .................................. 4500–NH3 D–1997 

or E–1997.

D1426–08 (B).

Manual phenate, salicylate, or other 

substituted phenols in Berthelot 

reaction based 

methods.

.................................. 4500–NH3 F–1997 ... .................................. See footnote.60

Automated phenate, 

salicylate, or other 

substituted phenols in Berthelot 

reaction based 

methods.

350.130, Rev. 2.0 

(1993).

4500–NH3 G–1997 

4500–NH3 H–1997. 

.................................. I–4523–85.2


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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

Automated electrode Ion Chromatography .................................. D6919–09 ................ See footnote.7

5. Antimony—Total,4

mg/L.

Digestion,4 followed by 

any of the following: 

AA direct aspiration 36................................... 3111 B–1999.

AA furnace .............. .................................. 3113 B–2004.

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

(1994).

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

(2003) 68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 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–2009 or .......

3114 C–2009 ...........

D2972–08 (B) .......... I–3062–85.2

AA furnace .............. .................................. 3113 B–2004 ........... 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–1999 ........... D1976–07.

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4020– 

05.70

Colorimetric (SDDC) .................................. 3500–As B–1997 ..... D2972–08 (A) .......... I–3060–85.2

7. Barium–Total,4 mg/ 

L.

Digestion4, followed by 

any of the following: 

AA direct aspiration 36................................... 3111 D–1999 ........... .................................. I–3084–85.2

AA furnace .............. .................................. 3113 B–2004 ........... D4382–02(07).

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

(2003) 68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... .................................. I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 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–1999 or ......

3111 E–1999 ...........

D3645–08 (A) .......... I–3095–85.2

AA furnace .............. .................................. 3113 B–2004 ........... 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–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 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–2001 ........... .................................. 973.443, p. 17.9, I– 

1578–78,8 See 

footnote.10,63

10. Boron—Total,37

mg/L.

Colorimetric (curcumin) .. .................................. 4500–B B –2000 ..... .................................. I–3112–85.2

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

(2003) 68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4471– 

97.50

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

11. Bromide, mg/L ...... Electrode ........................ .................................. .................................. D1246–05 ................ I–1125–85.2

Ion Chromatography 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000, C– 

2000, D–2000.

D4327–03 ................ 993.30.3

CIE/UV .................... .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

12. Cadmium—Total,4

mg/L.

Digestion,4 followed by 

any of the following: 


srobinson on DSK4SPTVN1PROD with RULES2
29776 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

AA direct aspiration 36.

.................................. 3111 B–1999 ...........

or 3111 C–1999 ......

D3557–02(07) (A or 

B).

974.27,3 p. 37.9, I– 

3135–85 2 or I– 

3136–85.2

AA furnace .............. .................................. 3113 B–2004 ........... D3557–02(07) (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–1999 ........... D1976–07 ................ I–1472–85 2 or I– 

4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4471– 

97.50

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

Voltametry11 ............ .................................. .................................. D3557–02(07) (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–1999 ........... D511–08(B) ............. I–3152–85.2

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

(2003) 68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... .................................. I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14.3

DCP ......................... .................................. .................................. .................................. See footnote.34

Titrimetric (EDTA) ... .................................. 3500–Ca B–1997 .... D511–08 (A).

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

14. Carbonaceous biochemical oxygen demand (CBOD5), mg/ 

L12.

Dissolved Oxygen Depletion with nitrification inhibitor................................... 5210 B–2001 ........... .................................. See footnote.35,63

15. Chemical oxygen 

demand (COD), mg/ 

L.

Titrimetric ........................ 410.3 (Rev. 1978)1 .. 5220 B–1997 ...........

or C–1997 ................

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–1997 ........... D1252–06 (B) .......... See footnotes.13,14

I–3561–85.2

16. Chloride, mg/L ...... Titrimetric: (silver nitrate) .................................. 4500–Cl¥ B–1997 ... D512–04 (B) ............ I–1183–85.2

(Mercuric nitrate) ............ .................................. 4500–Cl¥ C–1997 ... D512–04 (A) ............ 973.51,3 I–1184–85.2

Colorimetric: manual ...... .................................. .................................. .................................. I–1187–85.2

Automated (Ferricyanide) .................................. 4500–Cl¥ E–1997 ... .................................. I–2187–85.2

Potentiometric Titration .. .................................. 4500–Cl¥ D–1997.

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

Ion Chromatography ....... 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000 or .......

4110 C–2000 ...........

D4327–03 ................ 993.303 , I–2057– 

90.51

CIE/UV ............................ .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

17. Chlorine–Total residual, mg/L.Amperometric direct ....... .................................. 4500–Cl D–2000 ...... D1253–08.

Amperometric direct (low 

level).

.................................. 4500–Cl E–2000.

Iodometric direct ............. .................................. 4500–Cl B–2000.

Back titration ether end– 

point15.

.................................. 4500–Cl C–2000.

DPD–FAS ....................... .................................. 4500–Cl F–2000.

Spectrophotometric, DPD .................................. 4500–Cl G–2000.

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

17A. Chlorine–Free 

Available, mg/L.

Amperometric direct ....... .................................. 4500–Cl D–2000 ...... D1253–08.

Amperometric direct (low 

level).

.................................. 4500–Cl E–2000.

DPD–FAS ....................... .................................. 4500–Cl F–2000.

Spectrophotometric, DPD .................................. 4500–Cl G–2000.

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

following: 

AA chelation–extraction................................... 3111 C–1999 ........... .................................. I–1232–85.2

Ion Chromatography 218.6, Rev. 3.3 

(1994).

3500–Cr C–2009 ..... D5257–03 ................ 993.23. 

Colorimetric (Diphenyl–carbazide)................................... 3500–Cr B–2009 ..... D1687–02(07) (A) .... I–1230–85.2

19. Chromium—Total,4

mg/L.

Digestion,4 followed by 

any of the following: 


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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

AA direct aspiration 36.

.................................. 3111 B–1999 ........... D1687–02(07) (B) .... 974.27,3 I–3236–85.2

AA chelation–extraction................................... 3111 C–1999.

AA furnace .............. .................................. 3113 B–2004 ........... D1687–02(07) (C) .... I–3233–93.46

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

(1994).

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

(2003),68 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4020– 

05.70

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

Colorimetric (Diphenyl–carbazide)................................... 3500–Cr B–2009.

20. Cobalt—Total,4

mg/L.

Digestion,4 followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999 or 

3111 C–1999.

D3558–08 (A or B) .. p. 37,9 I–3239–85.2

AA furnace .............. .................................. 3113 B–2004 ........... D3558–08 (C) .......... I–4243–89.51

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

(1994).

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

(2003) 68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 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) .................................. .................................. .................................. See footnote.18

(Platinum cobalt) ............ .................................. 2120 B–2001 ........... .................................. I–1250–85.2

Spectrophotometric.

22. Copper—Total,4

mg/L.

Digestion,4 followed by 

any of the following: 

AA direct aspiration 36................................... 3111 B–1999 or .......

3111 C–1999 ...........

D1688–07 (A or B) .. 974.27,3 p. 37,9 I– 

3270–85 2 or I– 

3271–85.2

AA furnace .............. .................................. 3113 B–2004 ........... D1688–07 (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–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4020– 

05.70

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

Colorimetric 

(Neocuproine).

.................................. 3500–Cu B–1999.

(Bathocuproine) ....... .................................. 3500–Cu C–1999 .... .................................. 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.

.................................. .................................. D7511–09.

Manual distillation with 

MgCl2, followed by any 

of the following: 

335.4, Rev. 1.0 

(1993) 57.

4500–CN¥ B–1999 

or C–1999.

D2036–09(A), 

D7284–08.

10–204–00–1–X.56

Flow Injection, gas 

diffusion amperometry.

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

D7284–08.

Titrimetric ................. .................................. 4500–CN¥ D–1999 D2036–09(A) ........... p. 22.9

Spectrophotometric, 

manual.

.................................. 4500–CN¥ E–1999 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).


srobinson on DSK4SPTVN1PROD with RULES2
29778 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

Ion Selective Electrode................................... 4500–CN¥ F–1999 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–1999 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–1997.

Electrode, manual ... .................................. 4500–F¥ C–1997 .... D1179–04 (B).

Electrode, automated................................... .................................. .................................. I–4327–85.2

Colorimetric, 

(SPADNS).

.................................. 4500–F¥ D–1997 .... D1179–04 (A).

Automated 

complexone.

.................................. 4500–F¥ E–1997.

Ion Chromatography 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000 or C– 

2000.

D4327–03 ................ 993.30.3

CIE/UV .................... .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

26. Gold—Total,4 mg/ 

L.

Digestion,4 followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999.

AA furnace .............. 231.2 (Issued 1978)1 3113 B–2004.

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

(1994).

3125 B–2009 ........... D5673–05 ................ 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–1997 ........... D1126–02(07) .......... 973.52B,3 I–1338– 

85.2

Ca plus Mg as their carbonates, by inductively 

coupled plasma or AA 

direct aspiration. (See 

Parameters 13 and 

33)..

.................................. 2340 B–1997.

28. Hydrogen ion (pH), 

pH units.

Electrometric measurement................................... 4500–H+ B–2000 ..... 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–1999.

AA furnace .............. 235.2 (Issued 1978)1.

ICP/MS .................... .................................. 3125 B–2009.

30. Iron—Total,4 mg/L Digestion,4 followed by 

any of the following: 

AA direct aspiration 36................................... 3111 B–1999 or .......

3111 C–1999 ...........

D1068–05 (A or B) .. 974.27,3 I–3381–85.2

AA furnace .............. .................................. 3113 B–2004 ........... D1068–05 (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–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14.3


srobinson on DSK4SPTVN1PROD with RULES2
Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29779 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

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

Colorimetric (Phenanthroline)................................... 3500–Fe-1997 ......... D1068–05 (D) .......... 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–1997 or 

C–1997 and 

4500–NH3 B–1997.

D3590–02(06) (A) .... I–4515–91.45

Titration ................... .................................. 4500–NH3 C–1997 .. .................................. 973.48.3

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

Electrode ................. .................................. 4500–NH3 D–1997 

or E–1997.

D1426–08 (B).

Semi-automated 

phenate.

350.1 Rev 2.0 1993 4500–NH3 G–1997. 

4500–NH3 H–1997.

Manual phenate, salicylate, or other 

substituted phenols in Berthelot 

reaction based 

methods.

.................................. 4500–NH3 F–1997 ... .................................. See footnote.60

Automated Methods for TKN that do not require manual distillation 

Automated phenate, salicylate, or other substituted phenols in 

Berthelot reaction 

based methods colorimetric (auto digestion 

and distillation).

351.1 (Rev. 1978)1 .. .................................. .................................. I–4551–78.8

Semi-automated block 

digestor colorimetric 

(distillation not required).

351.2, Rev. 2.0 

(1993).

4500–Norg D–1997 ... D3590–02(06) (B) .... I–4515–91.45

Block digester, followed 

by Auto distillation and 

Titration.

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

Block digester, followed 

by Auto distillation and 

Nesslerization.

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

Block Digester, followed 

by Flow injection gas 

diffusion (distillation 

not required).

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

32. Lead—Total,4 mg/ 

L.

Digestion,4 followed by 

any of the following: 

AA direct aspiration 36................................... 3111 B–1999 or .......

3111 C–1999. 

D3559–08 (A or B) .. 974.27,3 I–3399–85.2

AA furnace .............. .................................. 3113 B–2004 ........... 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–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4471– 

97.50

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

Voltametry11 ............ .................................. .................................. D3559–08 (C).

Colorimetric (Dithizone)................................... 3500–Pb B–1997.

33. Magnesium— 

Total,4 mg/L.

Digestion,4 followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999 ........... D511–08 (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–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14.3

DCP ......................... .................................. .................................. .................................. See footnote.34

Gravimetric.

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

34. Manganese— 

Total,4 mg/L.

Digestion 4 followed by 

any of the following: 


srobinson on DSK4SPTVN1PROD with RULES2
29780 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

AA direct aspiration 36.

.................................. 3111 B–1999 ........... D858–07 (A or B) .... 974.27,3 I–3454–85.2

AA furnace .............. .................................. 3113 B–2004 ........... D858–07 (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–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4471– 

97.50

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

Colorimetric 

(Persulfate).

.................................. 3500–Mn B–1999 .... .................................. 920.203.3

(Periodate) ............... .................................. .................................. .................................. See footnote.23

35. Mercury—Total,4

mg/L.

Cold vapor, Manual ........ 245.1, Rev. 3.0 

(1994).

3112 B–2009 ........... D3223–02(07) .......... 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–1999 ........... .................................. I–3490–85.2

AA furnace .............. .................................. 3113 B–2004 ........... .................................. I–3492–96.47

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

(2003) 68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 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–1999 or .......

3111 C–1999 ...........

D1886–08 (A or B) .. I–3499–85.2

AA furnace .............. .................................. 3113 B–2004 ........... 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–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14,3 I–4020– 

05.70

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

38. Nitrate (as N), mg/ 

L.

Ion Chromatography ....... 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000 or C– 

2000.

D4327–03 ................ 993.30.3

CIE/UV .................... .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

Ion Selective Electrode................................... 4500–NO3

¥ D–2000.

Colorimetric (Brucine 

sulfate).

352.1 (Issued 1971)1 .................................. .................................. 973.50,3 419D1,7, 

p. 28.9

Nitrate-nitrite N 

minus Nitrite N 

(See parameters 

39 and 40).

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

39. Nitrate-nitrite (as 

N), mg/L.

Cadmium reduction, 

Manual.

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

¥ E–2000 D3867–04 (B).

Cadmium reduction, 

Automated.

353.2, Rev. 2.0 

(1993).

4500–NO3

¥ F–2000 D3867–04 (A) .......... I–2545–90.51

Automated hydrazine................................... 4500–NO3

¥ H–2000.

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

Ion Chromatography 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000 or C– 

2000.

D4327–03 ................ 993.30.3

CIE/UV .................... .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

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

Manual.

.................................. 4500–NO2

¥ B–2000 .................................. See footnote.25

Automated 

(Diazotization).

.................................. .................................. .................................. I–4540–852, See 

footnote.62


srobinson on DSK4SPTVN1PROD with RULES2
Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29781 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

Automated (*bypass 

cadmium reduction).

353.2, Rev. 2.0 

(1993).

4500–NO3

¥ F–2000 D3867–04 (A) .......... I–4545–85.2

Manual (*bypass 

cadmium reduction).

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

¥ E–2000 D3867–04 (B).

Ion Chromatography 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000 or C– 

2000.

D4327–03 ................ 993.30.3

CIE/UV .................... .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

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–200138.

Silica gel treated 

HEM (SGT–HEM): 

Silica gel treatment and gravimetry.

1664 Rev. A; 1664 

Rev. B42.

5520 B–200138 and 

5520 F–200138.

42. Organic carbon— 

Total (TOC), mg/L.

Combustion .................... .................................. 5310 B–2000 ........... D7573–09 ................ 973.473, p. 14.24

Heated persulfate or 

UV persulfate oxidation.

.................................. 5310 C 2000 ............

5310 D 2000. 

D4839–03 ................ 973.473,, 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–1999 or 

G–1999.

.................................. 973.563, I–4601–85.2

Manual single reagent................................... 4500–P E–1999 ....... D515–88(A) ............. 973.55.3

Manual two reagent 365.3 (Issued 1978)1.

Ion Chromatography 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000 or C– 

2000.

D4327–03 ................ 993.30.3

CIE/UV .................... .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

45. Osmium—Total4, 

mg/L.

Digestion4, followed by 

any of the following: 

AA direct aspiration, .................................. 3111 D–1999.

AA furnace .............. 252.2 (Issued 1978)1.

46. Oxygen, dissolved, 

mg/L.

Winkler (Azide modification)................................... 4500–O B–2001, C– 

2001, D–2001, E– 

2001, F–2001.

D888–09 (A) ............ 973.45B3, I–1575– 

78.8

Electrode ................. .................................. 4500–O G–2001 ...... D888–09 (B) ............ I–1576–78.8

Luminescence 

Based Sensor.

.................................. .................................. D888–09 (C) ............ See footnote63

See footnote.64

47. Palladium—Total,4

mg/L.

Digestion4, followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999.

AA furnace .............. 253.21(Issued 1978).

ICP/MS .................... .................................. 3125 B–2009.

DCP ......................... .................................. .................................. .................................. See footnote.34

48. Phenols, mg/L ...... Manual distillation26, followed by any of the 

following: 

420.11(Rev. 1978) ... 5530 B–2005 ........... D1783–01.

Colorimetric (4AAP) 

manual.

420.11(Rev. 1978) ... 5530 D–200527 ........ 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.

Digestion20, followed by 

any of the following: 

.................................. 4500–P B(5)-1999 ... .................................. 973.55.3

Manual ..................... 365.31(Issued 1978) 4500–P E–1999 ....... D515–88 (A).

Automated ascorbic 

acid reduction.

365.1 Rev. 2.0 

(1993).

4500–P F–1999, G– 

1999, H–1999.

.................................. 973.563, I–4600–85.2

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

(1994).

3120 B–1999 ........... .................................. I–4471–97.50


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29782 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

Semi–automated 

block digestor 

(TKP digestion).

365.41 (Issued 1974) .................................. D515–88 (B) ............ I–4610–91.48

51. Platinum—Total,4

mg/L.

Digestion4 followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999.

AA furnace .............. 255.2 (Issued 1978)1.

ICP/MS .................... .................................. 3125 B–2009.

DCP ......................... .................................. .................................. .................................. See footnote.34

52. Potassium— 

Total,4 mg/L.

Digestion4, followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999 ........... .................................. 973.533, I–3630–85.2

ICP/AES .................. 200.7, Rev. 4.4 

(1994).

3120 B–1999.

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14.3

Flame photometric .. .................................. 3500–K B–1997.

Electrode ................. .................................. 3500–K C–1997.

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

53. Residue—Total, 

mg/L.

Gravimetric, 103–105° .... .................................. 2540 B–1997 ........... .................................. I–3750–85.2

54. Residue—filterable, mg/L.Gravimetric, 180° ........... .................................. 2540 C–1997 ........... D5907–03 ................ I–1750–85.2

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

post washing of residue.

.................................. 2540 D–1997 ........... D5907–03 ................ I–3765–85.2

56. Residue—settleable, mg/L.Volumetric, (Imhoff 

cone), or gravimetric.

.................................. 2540 F–1997.

57. Residue—Volatile, 

mg/L.

Gravimetric, 550° ........... 160.4 (Issued 1971)1 2540–E–1997 .......... .................................. I–3753–85.2

58. Rhodium—Total,4

mg/L.

Digestion4 followed by 

any of the following: 

AA direct aspiration, 

or.

.................................. 3111 B–1999.

AA furnace .............. 265.2 (Issued 1978)1.

ICP/MS .................... .................................. 3125 B–2009.

59. Ruthenium— 

Total,4 mg/L.

Digestion4 followed by 

any of the following: 

AA direct aspiration, 

or.

.................................. 3111 B–1999.

AA furnace .............. 267.21.

ICP/MS .................... .................................. 3125 B–2009.

60. Selenium—Total,4

mg/L.

Digestion4, followed by 

any of the following: 

AA furnace .............. .................................. 3113 B–2004 ........... 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–1999 ........... D1976–07.

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.143, I–4020– 

05.70

AA gaseous hydride .................................. 3114 B–2009, or 

3111 C–2009. 

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–1997 .. D859–05 .................. I–1700–85.2

Automated 

(Molybdosilicate).

.................................. 4500–SiO2 E–1997 

or F–1997.

.................................. I–2700–85.2

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

(2003)68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... .................................. I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14.3

62. Silver—Total,4, 31

mg/L.

Digestion4, 29, followed 

by any of the following: 

AA direct aspiration .................................. 3111 B–1999 or 

3111 C–1999 ...........

.................................. 974.273, p. 379, I– 

3720–85.2

AA furnace .............. .................................. 3113 B–2004 ........... .................................. I–4724–89.51

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

(1994).


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TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

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

(2003)68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.143, I–4471– 

97.50

DCP ......................... .................................. .................................. .................................. See footnote.34

63. Sodium—Total,4

mg/L.

Digestion4,, followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999 ........... .................................. 973.543, I–3735–85.2

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

(2003)68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... .................................. I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14.3

DCP ......................... .................................. .................................. .................................. See footnote.34

Flame photometric .. .................................. 3500–Na B–1997.

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

64. Specific conductance, micromhos/cm 

at 25°C.

Wheatstone bridge ......... 120.11(Rev. 1982) ... 2510 B–1997 ........... D1125–95(99) (A) .... 973.403, I–2781–85.2

65. Sulfate (as SO4), 

mg/L.

Automated colorimetric ... 375.2, Rev. 2.0 

(1993).

4500–SO4

2 F– 

1997 or G–1997.

Gravimetric .............. .................................. 4500–SO4

2 C– 

1997 or D–1997.

.................................. 925.54.3

Turbidimetric ............ .................................. 4500–SO4

2 E– 

1997.

D516–07.

Ion Chromatography 300.0, Rev 2.1 

(1993) and 300.1– 

1, Rev 1.0 (1997).

4110 B–2000 or C– 

2000.

D4327–03 ................ 993.303, I–4020– 

05.70

CIE/UV .................... .................................. 4140 B–1997 ........... D6508–00(05) .......... D6508, Rev. 2.54

66. Sulfide (as S), mg/ 

L.

Sample Pretreatment ..... .................................. 4500–S2¥ B, C– 

2000.

Titrimetric (iodine) ... .................................. 4500–S2¥F–2000 .... .................................. I–3840–85.2

Colorimetric (methylene blue)................................... 4500–S2¥D–2000.

Ion Selective Electrode................................... 4500–S2¥G–2000 ... D4658–08.

67. Sulfite (as SO3), 

mg/L.

Titrimetric (iodine-iodate) .................................. 4500–SO3

2¥B–2000.

68. Surfactants, mg/L Colorimetric (methylene 

blue).

.................................. 5540 C–2000 ........... D2330–02.

69. Temperature, °C .. Thermometric ................. .................................. 2550 B–2000 ........... .................................. See footnote.32

70. Thallium–Total,4

mg/L.

Digestion4, followed by 

any of the following: 

AA direct aspiration .................................. 3111 B–1999.

AA furnace .............. 279.21(Issued 1978) 3113 B–2004.

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

(1994).

ICP/AES .................. 200.7, Rev. 4.4 

(1994); 200.5 Rev. 

4.2 (2003)68.

3120 B–1999 ........... D1976–07.

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.143, I–4471– 

97.50

71. Tin–Total,4 mg/L .. Digestion4, followed by 

any of the following:.

AA direct aspiration .................................. 3111 B–1999 ........... .................................. I–3850–78.8

AA furnace .............. .................................. 3113 B–2004.

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–2009 ........... D5673–05 ................ 993.14.3

72. Titanium–Total,4

mg/L.

Digestion4 followed by 

any of the following: 

AA direct aspiration .................................. 3111 D–1999.

AA furnace .............. 283.21(Issued 1978).

ICP/AES .................. 200.7, Rev. 4.4 

(1994).

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.14.3


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29784 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

TABLE IB—LIST OF APPROVED INORGANIC TEST PROCEDURES—Continued 

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

DCP ......................... .................................. .................................. .................................. See footnote.34

73. Turbidity, NTU53 ... Nephelometric ................ 180.1, Rev. 2.0 

(1993).

2130 B–2001 ........... D1889–00 ................ I–3860–85.2

See footnote.65

See footnote.66

See footnote.67

74. Vanadium–Total,4

mg/L.

Digestion4, followed by 

any of the following: 

AA direct aspiration .................................. 3111 D–1999.

AA furnace .............. .................................. 3113 B–2004 ........... D3373–03(07).

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

(2003)68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.143, I–4020– 

05.70

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

Colorimetric (Gallic 

Acid).

.................................. 3500–V B–1997.

75. Zinc–Total4, mg/L Digestion4, followed by 

any of the following: 

AA direct aspiration36.

.................................. 3111 B–1999 or 

3111 C–1999.

D1691–02(07) (A or 

B).

974.273, p. 379, I– 

3900–85.2

AA furnace .............. 289.21(Issued 1978).

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

(2003)68; 200.7, 

Rev. 4.4 (1994).

3120 B–1999 ........... D1976–07 ................ I–4471–97.50

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

(1994).

3125 B–2009 ........... D5673–05 ................ 993.143, I–4020– 

05.70

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

Colorimetric (Zincon) .................................. 3500 Zn B–1997 ...... .................................. See footnote.33

76. Acid Mine Drainage.......................................... 162769.

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 the EPA 

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

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

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

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

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

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

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

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

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

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

Luebbe Analyzing Technologies Inc. 8The approved method is that cited in Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, Techniques of 

Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1979. USGS. 9American National Standard on Photographic Processing Effluents. April 2, 1975. American National Standards Institute. 

10 In-Situ Method 1003–8–2009, Biochemical Oxygen Demand (BOD) Measurement by Optical Probe. 2009. In-Situ Incorporated. 11The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable. 12 Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test method which measures ‘‘total 

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

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

discharger’s permit specifically states CBOD5 is required can the permittee report data using a nitrification inhibitor. 13OIC Chemical Oxygen Demand Method. 1978. Oceanography International Corporation. 14 Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company. 15The back titration method will be used to resolve controversy. 


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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, December 1971. 19 Method 8506, Biocinchoninate Method for Copper, Hach Handbook of Water Analysis. 1979. Hach Company. 20When using a method with block digestion, this treatment is not required. 21 Industrial Method Number 378–75WA, Hydrogen ion (pH) Automated Electrode Method, Bran & Luebbe (Technicon) Autoanalyzer II. October 1976. Bran & Luebbe Analyzing Technologies. 22 Method 8008, 1,10–Phenanthroline Method using FerroVer Iron Reagent for Water. 1980. Hach Company. 23 Method 8034, Periodate Oxidation Method for Manganese, Hach Handbook of Wastewater Analysis. 1979. Hach Company. 24 Methods for Analysis of Organic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A3, (1972 Revised 1987) p. 14. 1987. USGS. 25 Method 8507, Nitrogen, Nitrite-Low Range, Diazotization Method for Water and Wastewater. 1979. Hach Company. 26 Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH. 27The colorimetric reaction must be conducted at a pH of 10.0 ± 0.2. 28Addison, R.F., and R.G. Ackman. 1970. Direct Determination of Elemental Phosphorus by Gas–Liquid Chromatography, Journal of Chromatography, 47(3):421–426. 29Approved methods for the analysis of silver in industrial wastewaters at concentrations of 1 mg/L and above are inadequate where silver exists as an inorganic halide. Silver halides such as the bromide and chloride are relatively insoluble in reagents such as nitric acid but are readily 

soluble in an aqueous buffer of sodium thiosulfate and sodium hydroxide to pH of 12. Therefore, for levels of silver above 1 mg/L, 20 mL of sample should be diluted to 100 mL by adding 40 mL each of 2 M Na2S2O3 and NaOH. Standards should be prepared in the same manner. For levels of silver below 1 mg/L the approved method is satisfactory. 30The use of EDTA decreases method sensitivity. Analysts may omit EDTA or replace with another suitable complexing reagent provided that 

all method specified quality control acceptance criteria are met. 31For samples known or suspected to contain high levels of silver (e.g., in excess of 4 mg/L), cyanogen iodide should be used to keep the silver in solution for analysis. Prepare a cyanogen iodide solution by adding 4.0 mL of concentrated NH4OH, 6.5 g of KCN, and 5.0 mL of a 1.0 N 

solution of I2 to 50 mL of reagent water in a volumetric flask and dilute to 100.0 mL. After digestion of the sample, adjust the pH of the digestate 

to >7 to prevent the formation of HCN under acidic conditions. Add 1 mL of the cyanogen iodide solution to the sample digestate and adjust the 

volume to 100 mL with reagent water (NOT acid). If cyanogen iodide is added to sample digestates, then silver standards must be prepared that 

contain cyanogen iodide as well. Prepare working standards by diluting a small volume of a silver stock solution with water and adjusting the 

pH≤7 with NH4OH. Add 1 mL of the cyanogen iodide solution and let stand 1 hour. Transfer to a 100-mL volumetric flask and dilute to volume 

with water. 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, Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry, EPA–821–R–02–019. 

Revision E. August 2002, U.S. EPA. The application of clean techniques described in EPA’s Method 1669: Sampling Ambient Water for Trace 

Metals at EPA Water Quality Criteria Levels, EPA–821–R–96–011, are recommended to preclude contamination at low-level, trace metal determinations. 44 Method OIA–1677–09, Available Cyanide by Ligand Exchange and Flow Injection Analysis (FIA). 2010. OI Analytical. 45Open File Report 00–170, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Ammonium Plus Organic Nitrogen by a Kjeldahl Digestion Method and an Automated Photometric Finish that Includes Digest Cleanup by Gas Diffusion. 2000. USGS. 46Open File Report 93–449, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Chromium in Water by Graphite Furnace Atomic Absorption Spectrophotometry. 1993. USGS. 47Open File Report 97–198, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Molybdenum by Graphite Furnace Atomic Absorption Spectrophotometry. 1997.. USGS. 48Open File Report 92–146, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Total 

Phosphorus by Kjeldahl Digestion Method and an Automated Colorimetric Finish That Includes Dialysis. 1992. USGS. 49Open File Report 98–639, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Arsenic 

and Selenium in Water and Sediment by Graphite Furnace-Atomic Absorption Spectrometry. 1999. USGS. 50Open File Report 98–165, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Elements in Whole-water Digests Using Inductively Coupled Plasma-Optical Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry. 1998. USGS. 51Open File Report 93–125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993.. USGS. 52 Unless otherwise indicated, all EPA methods, excluding EPA Method 300.1–1, are published in U.S. EPA. May 1994. Methods for the Determination of Metals in Environmental Samples, Supplement I, EPA/600/R–94/111; or U.S. EPA. August 1993. Methods for the Determination of 

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

sheet April 27, 1999. Determination of Inorganic Ions in Drinking Water by Ion Chromatography. 53Styrene divinyl benzene beads (e.g., AMCO–AEPA–1 or equivalent) and stabilized formazin (e.g., Hach StablCalTM or equivalent) are acceptable substitutes for formazin. 54 Method D6508, Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and 

Chromate Electrolyte. December 2000. Waters Corp. 


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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. 

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, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98)

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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

GC/MS ............. 624 4, 1624B. 

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

GC/MS ............. 624 4, 1624B. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440B–2000 ..... D4657–92 (98). 

6. Benzene ............................................................ GC .................... 602 .................... 6200 C–1997.

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

p.1. 

GC/MS ............. 625 5, 1625B ..... 6410 B–2000. 

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

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29787 

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, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... 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, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

18. Bromodichloromethane ................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

19. Bromoform ....................................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

20. Bromomethane ................................................ GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

22. Carbon tetrachloride ........................................ GC .................... 601 .................... 6200 C–1997 ... .......................... See footnote 3, 

p. 130. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000. See footnote 9, 

p. 27. 

24. Chlorobenzene ................................................ GC .................... 601, 602 ............ 6200 C–1997 ... .......................... See footnote 3, 

p. 130. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

25. Chloroethane ................................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

GC/MS ............. 624, 1624B. 

27. Chloroform ....................................................... GC .................... 601 .................... 6200 C–1997 ... .......................... See footnote 3, 

p. 130. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

28. Chloromethane ................................................ GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

34. Dibromochloromethane ................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

35. 1,2-Dichlorobenzene ....................................... GC .................... 601, 602 ............ 6200 C–1997. 


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29788 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

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

Parameter 1 Method EPA2,7 Standard 

methods ASTM Other 

GC/MS ............. 624, 1625B ....... 6200 B–1997 .... .......................... See footnote 9, 

p. 27. 

36. 1,3-Dichlorobenzene ....................................... GC .................... 601, 602 ............ 6200 C–1997. 

GC/MS ............. 624, 1625B ....... 6200 B–1997 .... .......................... See footnote 9, 

p. 27. 

37. 1,4-Dichlorobenzene ....................................... GC .................... 601, 602 ............ 6200 C–1997. 

GC/MS ............. 624, 1625B ....... 6200 B–1997 .... .......................... See footnote 9, 

p. 27. 

38. 3,3’-Dichlorobenzidine ..................................... GC/MS ............. 625, 1625B ....... 6410 B–2000. 

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

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

GC/MS ............. ........................... 6200 C–1997. 

40. 1,1-Dichloroethane .......................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

41. 1,2-Dichloroethane .......................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

42. 1,1-Dichloroethene .......................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

43. trans-1,2-Dichloroethene ................................. GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

45. 1,2-Dichloropropane ........................................ GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

46. cis-1,3-Dichloropropene ................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

47. trans-1,3-Dichloropropene ............................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 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, 1625B ....... 6410 B–2000. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

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

p. 130. 

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

p. S102. 

57. Ethylbenzene ................................................... GC .................... 602 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

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

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

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

63. Hexachlorobenzene ......................................... GC .................... 612. 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29789 

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, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

64. Hexachlorobutadiene ....................................... GC .................... 612. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

65. Hexachlorocyclopentadiene ............................ GC .................... 612. 

GC/MS ............. 625 5, 1625B ..... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

66. 1,2,3,4,7,8-Hexachloro-dibenzofuran .............. GC/MS ............. 1613B. 

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

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

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

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

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

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

73. Hexachloroethane ........................................... GC .................... 612. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

74. Indeno(1,2,3-c,d) pyrene ................................. GC .................... 610. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

75. Isophorone ....................................................... GC .................... 609. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

76. Methylene chloride .......................................... GC .................... 601 .................... 6200 C–1997. .......................... See footnote 3, 

p. 130. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

77. 2-Methyl-4,6-dinitrophenol ............................... GC .................... 604 .................... 6420 B–2000. 

GC/MS ............. 625, 1625B ....... 6410 B–2000. .......................... See footnote 9, 

p. 27. 

78. Naphthalene .................................................... GC .................... 610. 

GC/MS ............. 625, 1625B ....... 6410 B–2000. ... .......................... See footnote 9, 

p. 27 

HPLC ................ 610 .................... 6440 B–2000. 

79. Nitrobenzene ................................................... GC .................... 609. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ ........................... .......................... D4657–92 (98). 

80. 2-Nitrophenol ................................................... GC .................... 604 .................... 6420 B–2000. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

81. 4-Nitrophenol ................................................... GC .................... 604 .................... 6420 B–2000. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

82. N-Nitrosodimethylamine .................................. GC .................... 607. 

GC/MS ............. 625 5, 1625B ..... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

83. N-Nitrosodi-n-propylamine ............................... GC .................... 607. 

GC/MS ............. 625 5, 1625B ..... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

84. N-Nitrosodiphenylamine .................................. GC .................... 607. 

GC/MS ............. 625 5, 1625B ..... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

85. Octachlorodibenzofuran .................................. GC/MS ............. 1613B.10

86. Octachlorodibenzo-p-dioxin ............................. GC/MS ............. 1613B.10

87. 2,2’-Oxybis(2-chloro-propane) [also known as 

bis(2-Chloroisopropyl) ether].

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

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

88. PCB–1016 ....................................................... GC .................... 608 .................... .......................... .......................... See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625 .................... 6410 B–2000. 

89. PCB–1221 ....................................................... GC .................... 608 .................... .......................... .......................... See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625 .................... 6410 B–2000. 

90. PCB–1232 ....................................................... GC .................... 608 .................... .......................... .......................... See footnote 3, 

p. 43; See 

footnote. 8


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29790 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

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 .................... 6410 B–2000. 

91. PCB–1242 ....................................................... GC .................... 608 .................... .......................... .......................... See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625 .................... 6410 B–2000. 

92. PCB–1248 ....................................................... GC .................... 608. 

GC/MS ............. 625 .................... 6410 B–2000. 

93. PCB–1254 ....................................................... GC .................... 608 .................... .......................... .......................... See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625 .................... 6410 B–2000. 

94. PCB–1260 ....................................................... GC .................... 608 .................... .......................... .......................... See footnote 3, 

p. 43; See 

footnote. 8

GC/MS ............. 625 .................... 6410 B–2000. 

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

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

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

98. Pentachlorophenol ........................................... GC .................... 604 .................... 6420 B–2000 .... .......................... See footnote 3, 

p. 140. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

99. Phenanthrene .................................................. GC .................... 610. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

100. Phenol ........................................................... GC .................... 604 .................... 6420 B–2000.

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

101. Pyrene ........................................................... GC .................... 610. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

HPLC ................ 610 .................... 6440 B–2000 .... D4657–92 (98). 

102. 2,3,7,8-Tetrachloro-dibenzofuran .................. GC/MS ............. 1613B.10

103. 2,3,7,8-Tetrachloro-dibenzo-p-dioxin ............. GC/MS ............. 613, 625 5a, 

1613B.

104. 1,1,2,2-Tetrachloroethane ............................. GC .................... 601 .................... 6200 C–1997 ... .......................... See footnote 3, 

p. 130. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

105. Tetrachloroethene ......................................... GC .................... 601 .................... 6200 C–1997 ... .......................... See footnote 3, 

p. 130. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

106. Toluene .......................................................... GC .................... 602 .................... 6200 C–1997.

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

107. 1,2,4-Trichlorobenzene .................................. GC .................... 612 .................... .......................... .......................... See footnote 3, 

p. 130. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

108. 1,1,1-Trichloroethane .................................... GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

109. 1,1,2-Trichloroethane .................................... GC .................... 601 .................... 6200 C–1997. .. .......................... See footnote 3, 

p. 130. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

110. Trichloroethene .............................................. GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

111. Trichlorofluoromethane .................................. GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624 .................... 6200 B–1997. 

112. 2,4,6-Trichlorophenol ..................................... GC .................... 604 .................... 6420 B–2000. 

GC/MS ............. 625, 1625B ....... 6410 B–2000 .... .......................... See footnote 9, 

p. 27. 

113. Vinyl chloride ................................................. GC .................... 601 .................... 6200 C–1997. 

GC/MS ............. 624, 1624B ....... 6200 B–1997. 

114. Nonylphenol ................................................... GC/MS ............. ........................... .......................... D7065–06. 

115. Bisphenol A (BPA) ........................................ GC/MS ............. ........................... .......................... D7065–06. 

116. p-tert-Octylphenol (OP) ................................. GC/MS ............. ........................... .......................... D7065–06. 

117. Nonylphenol Monoethoxylate (NP1EO) ........ GC/MS ............. ........................... .......................... D7065–06.

118. Nonylphenol Diethoxylate (NP2EO) .............. GC/MS ............. ........................... .......................... D7065–06. 

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

Coulometric 

Titration.

1650.11


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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 

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

Acetylation 

and GC/MS.

1653.11

Table IC notes: 

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

per liter (pg/L). 2The full text of Methods 601–613, 624, 625, 1613B, 1624B, and 1625B are provided at Appendix A, Test Procedures for Analysis of Organic 

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

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

EPA. 4 Method 624 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. 5 Method 625 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, screening only. 6Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency, Supplement to the 15th Edition of 

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

603, 624, 625, 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 and 625 and 100% for methods 1624B and 1625B) of all samples to monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls 

outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect. The results should be reported, but cannot be used to demonstrate regulatory compliance. These quality control requirements also apply to the Standard Methods, ASTM Methods, and 

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

Phenolics in Wastewater by In Situ Acetylation and GCMS. Revision A, 1997. U.S. EPA. The full text for both of these methods is provided at 

Appendix A in Part 430, The Pulp, Paper, and Paperboard Point Source Category. 

TABLE ID—LIST OF APPROVED TEST PROCEDURES FOR PESTICIDES 1

Parameter Method EPA2,7,10 Standard 

methods ASTM Other 

1. Aldrin ....................... GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812–96 

(02).

See footnote 3, p. 7; See footnote 4, O–3104–83; See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 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 ............................... .......................... .......................... 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. 

5. Atrazine ................... GC .................... 507, 619 ......................... .......................... .......................... 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 ................... .......................... .......................... 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 .............. ......................................... .......................... .......................... See footnote 11, O–1126–95. 

7. Barban ..................... TLC ................... ......................................... .......................... .......................... See footnote 3, p. 104; See footnote 6, p. S64. 

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

8. a-BHC ...................... GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 8, 3M0222. 

GC/MS .............. 625 5 ............................... 6410 B–2000 ... .......................... 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 

9. b–BHC ..................... GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 6410 B–2000. 

10. d-BHC .................... GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 6410 B–2000. 

11. g-BHC (Lindane) .... GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3104–83; See footnote 8, 3M0222. 

GC/MS .............. 625 5 ............................... 6410 B–2000 ... .......................... See footnote 11, O–1126–95. 

12. Captan ................... GC .................... 617 .................................. 6630 B–2000 ... 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 .............. ......................................... .......................... .......................... See footnote 11, O–1126–95. 

14. Carbophenothion ... GC .................... 617 .................................. 6630 B–2000 ... .......................... See footnote 4, page 27; See footnote 6, p. S73. 

15. Chlordane .............. GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3104–83; See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 6410 B–2000. 

16. Chloropropham ...... TLC ................... ......................................... .......................... .......................... See footnote 3, p. 104; See footnote 6, p. S64. 

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

17. 2,4-D ...................... GC .................... 615 .................................. 6640 B–2001 ... .......................... See footnote 3, p. 115; See footnote 4, O–3105 –83. 

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

18. 4,4’-DDD ................ GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3105–83; See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 6410 B–2000. 

19. 4,4’-DDE ................ GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3104–83; See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 6410 B–2000 ... .......................... See footnote 11, O–1126–95. 

20. 4,4’-DDT ................ GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3104–83; See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 6410 B–2000. 

21. Demeton-O ............ GC .................... 614, 622 ......................... .......................... .......................... See footnote 3, p. 25; See footnote 6, p. S51. 

22. Demeton-S ............ GC .................... 614, 622 ......................... .......................... .......................... See footnote 3, p. 25; See footnote 6, p. S51. 

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 ............................... .......................... .......................... 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 ...................... 6630 B–2000 ... .......................... See footnote 3, p. 7; 

27. Dicofol .................... GC .................... 617 .................................. .......................... .......................... See footnote 4, O–3104–83. 

28. Dieldrin .................. GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3104–83; See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 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 ............................... .......................... .......................... 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. 


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

Parameter Method EPA2,7,10 Standard methods ASTM Other 

32. Endosulfan I .......... GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3104–83; See footnote 8, 3M022). 

GC/MS .............. 625 5 ............................... 6410 B–2000 ... .......................... See footnote 13, O–2002–01. 

33. Endosulfan II ......... GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 8, 3M0222. 

GC/MS .............. 625 5 ............................... 6410 B–2000 ... .......................... See footnote 13, O–2002–01. 

34. Endosulfan Sulfate GC .................... 608, 617 ......................... 6630 C–2000 ... .......................... See footnote 8, 3M0222. 

GC/MS .............. 625 .................................. 6410 B–2000 ... ..........................

35. Endrin .................... GC .................... 505, 508, 608, 617, 1656 6630 B–2000 & 

C–2000.

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 5 ......... 6410 B–2000. 

36. Endrin aldehyde .... GC .................... 608, 617 ......................... 6630 C–2000 ... .......................... See footnote 8, 3M0222. 

GC/MS .............. 625. 

37. Ethion .................... GC .................... 614, 614.1,1657 ............. .......................... .......................... See footnote 4, page 27; See footnote 6, p. S73. 

GC/MS .............. ......................................... .......................... .......................... 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, 608, 617, 1656 6630 B–2000 & 

C–2000.

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 ........... 6410 B–2000. 

41. Heptachlor epoxide GC .................... 608, 617 ......................... 6630 B–2000 & 

C–2000.

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 .................................. 6410 B–2000. 

42. Isodrin .................... GC .................... 617 .................................. 6630 B–2000 & 

C–2000.

.......................... See footnote 4, O–3104–83; See 

footnote 6, p. S73. 

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–2000 ... .......................... See footnote 3, p. 25; See footnote 6, p. S51. 

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

6630 B–2000 & 

C–2000.

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

47. Mexacarbate .......... TLC ................... ......................................... .......................... .......................... See footnote 3, p. 94; See footnote 6, p.S60. 

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

48. Mirex ...................... GC .................... 617 .................................. 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7; See footnote 4, O–3104–83. 

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–2000 ... .......................... See footnote 4, page 27; See footnote 3, p. 25. 


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

Parameter Method EPA2,7,10 Standard methods ASTM Other 

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

53. Parathion ethyl ...... GC .................... 614 .................................. 6630 B–2000 ... .......................... See footnote 4, page 27; See footnote 3, p. 25. 

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

54. PCNB ..................... GC .................... 608.1, 617 ...................... 6630 B–2000 & 

C–2000.

D3086–90, 

D5812– 

96(02).

See footnote 3, p. 7. 

55. Perthane ................ GC .................... 617 .................................. .......................... 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 ............................... .......................... .......................... 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 ................... .......................... .......................... See footnote 13, O–2002–01. 

58. Propazine .............. GC .................... 507, 619, 1656 ............... .......................... .......................... See footnote 3, p. 83; See footnote 6, p. S68; See footnote 9, 

O–3106–93. 

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

59. Propham ................ TLC ................... ......................................... .......................... .......................... See footnote 3, p. 104; See footnote 6, p. S64. 

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

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

60. Propoxur ................ TLC ................... ......................................... .......................... .......................... See footnote 3, p. 94; See footnote 6, p. S60. 

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

61. Secbumeton .......... TLC ................... ......................................... .......................... .......................... See footnote 3, p. 83; See footnote 6, p. S68. 

GC .................... 619. 

62. Siduron .................. TLC ................... ......................................... .......................... .......................... See footnote 3, p. 104; See footnote 6, p. S64. 

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

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

63. Simazine ................ GC .................... 505, 507, 619, 1656 ....... .......................... .......................... See footnote 3, p. 83; See footnote 6, p. S68; See footnote 9, 

O–3106–93. 

GC/MS .............. 525.1, 525.2 ................... .......................... .......................... See footnote 11, O–1126–95. 

64. Strobane ................ GC .................... 617 .................................. 6630 B–2000 & 

C–2000.

.......................... 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–2001 ... .......................... See footnote 3, p. 115; See footnote 4, O–3105–83. 

67. 2,4,5-TP (Silvex) .... GC .................... 615 .................................. 6640 B–2001 ... .......................... See footnote 3, p. 115; See footnote 4, O–3105–83. 

68. Terbuthylazine ....... GC .................... 619, 1656 ....................... .......................... .......................... See footnote 3, p. 83; See footnote 6, p. S68. 

GC/MS .............. ......................................... .......................... .......................... See footnote 13, O–2002–01. 

69. Toxaphene ............. GC .................... 505, 508, 608, 617, 1656 6630 B–2000 & 

C–2000.

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 ........... 6410 B–2000. 

70. Trifluralin ................ GC .................... 508, 617, 627, 1656 ....... 6630 B–2000 ... .......................... See footnote 3, p. 7; See footnote 9, O–3106–93. 

GC/MS .............. 525.2 ............................... .......................... .......................... See footnote 11, O–1126–95. 

Table ID notes: 

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

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

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

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

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

Method 608 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). 


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7Each analyst must make an initial, one-time, demonstration of their ability to generate acceptable precision and accuracy with Methods 608 

and 625 in accordance with procedures given in Section 8.2 of each of these methods. Additionally, each laboratory, on an on-going basis, must 

spike and analyze 10% of all samples analyzed with Method 608 or 5% of all samples analyzed with Method 625 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 Empore TM Disk. Revised October 28, 1994. 3M Corporation. 9 Method O–3106–93 is in Open File Report 94–37, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory— 

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

USGS. 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. The full text of Methods 608 and 625 are 

provided at Appendix A, Test Procedures for Analysis of Organic Pollutants, of this Part 136. 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. 11 Method O–1126–95 is in Open-File Report 95–181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory— 

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

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

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

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

selected-ion monitoring. 1992. USGS. 

* * * * * 

TABLE 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 

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

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 

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

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

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 

41 ................... Propanil ......................................................................... 709–98–8 632.1/1656 

45 ................... Metribuzin ..................................................................... 21087–64–9 507/633/525.1/525.2/1656 

52 ................... Acephate ....................................................................... 30560–19–1 1656/1657 

53 ................... Acifluorfen ..................................................................... 50594–66–6 515.1/515.2/555

54 ................... Alachlor ......................................................................... 15972–60–8 505/507/645/525.1/525.2/1656 

55 ................... Aldicarb ......................................................................... 116–06–3 531.1 

58 ................... Ametryn ........................................................................ 834–12–8 507/619/525.2 

60 ................... Atrazine ......................................................................... 1912–24–9 505/507/619/525.1/525.2/1656 

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

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

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

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

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

73 ................... Captafol ........................................................................ 2425–06–1 1656 

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

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

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

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

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

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

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

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

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

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 


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

EPA survey 

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

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

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 1656/505/508/608/617/525.1/525.2 

125 ................. Ethalfluralin ................................................................... 55283–68–6 1656/627 See footnote 1 

126 ................. Ethion ............................................................................ 563–12–2 1657/614/614.1 

127 ................. Ethoprop ....................................................................... 13194–48–4 1657/507/622/525.1/525.2 

132 ................. Fenarimol ...................................................................... 60168–88–9 507/633.1/525.1/525.2/1656 

133 ................. Fenthion ........................................................................ 55–38–9 1657/622 

138 ................. Glyphosate [N-(Phosphonomethyl) glycine] ................. 1071–83–6 547 

140 ................. Heptachlor .................................................................... 76–44–8 1656/505/508/608/617/525.1/525.2 

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

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

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

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 

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

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

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

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

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

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

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

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

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

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

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

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

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

206 ................. Pentachlorophenol ........................................................ 87–86–5 625/1625/515.2/555/515.1/525.1/525.2 

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

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

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 

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

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

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 

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 

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

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

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

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

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

262 ................. Toxaphene .................................................................... 8001–35–2 1656/505/508/608/617/525.1/525.2 

263 ................. Merphos [Tributyl phosphorotrithioate] ......................... 150–50–5 1657/507/525.1/525.2/622 

264 ................. Trifluralin 1 ..................................................................... 1582–09–8 1656/508/617/627/525.2 

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

Table 1G notes: 

1 Monitor and report as total Trifluralin. 

2Applicable to the analysis of DCPA degradates. 

3EPA Methods 608.1 through 645, 1645 through 1661, and Ind-01 are available in Methods For The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume I, EPA 821–R–93–010A, Revision I, August 1993, U.S. EPA. EPA Methods 200.9 and 

505 through 555 are available in Methods For The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume 

II, EPA 821–R–93–010B, August 1993, U.S. EPA. The full text of Methods 608, 625 and 1625 are provided at Appendix A of this Part 136. The 

full text of Method 200.7 is provided at Appendix C of this Part 136. 


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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–1997 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–1997. 

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–1997 ................ 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+B.5c)–1997. 

5. E. coli, number 

per 100 mL.

MPN 6,8,14, multiple 

tube, or.

................... 9221 B.1–2006/9221 

F–2006 11,13.

Multiple tube/multiple 

well, or.

................... 9223 B–2004 12 ............ 991.15 10 ...................... Colilert®12,16, Colilert18®12,15,16. 

MF 2,5,6,7,8, two step, or 1103.1 19 ... 9222 B–1997/9222 G– 

1997 18, 9213 D– 

2007.

D5392–93 9. 

Single step ................... 1603 20, 

1604 21.

...................................... ...................................... mColiBlue-24®17. 

6. Fecal 

streptococci, number per 100 mL.

MPN, 5 tube, 3 dilution, 

or.

p. 139 3 ..... 9230 B–2007. 

MF 2, or ........................ p. 136 3 ..... 9230 C–2007 ............... B–0055–85 4. 

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

7. Enterococci, number per 100 mL.MPN 6,8, multiple tube/ 

multiple well, or.

................... ...................................... D6503–99 9 .................. Enterolert®12,22. 

MF 2,5,6,7,8 two step, or 1106.1 23 ... 9230 C–2007 ............... D5259–92 9. 

Single step, or .............. 1600 24 ...... 9230 C–2007. 

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

Protozoa: 

8. Cryptosporidium .. Filtration/IMS/FA .......... 1622 25, 

1623 26.

9. Giardia ................ Filtration/IMS/FA .......... 1623 26

Table 1H notes: 

1The method must be specified when results are reported. 

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

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

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

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

required to resolve any controversies. 6Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes to account for the quality, character, consistency, and anticipated organism density of the water sample. 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.1–2006. Lactose broth may be used in lieu of lauryl tryptose broth (LTB), if at least 25 

parallel tests are conducted between this broth and LTB using the water samples normally tested, and this comparison demonstrates that the 

false-positive rate and false-negative rate for total coliform using lactose broth is less than 10 percent. No requirement exists to run the completed phase on 10 percent of all total coliform-positive tubes on a seasonal basis. 12These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is used to detect the enzyme b-glucuronidase produced by E. coli. 13After prior enrichment in a presumptive medium for total coliform using 9221B.1–2006, 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. 


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29798 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

14Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube 

and dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert® may be enumerated with the multiple-well procedures, Quanti-Tray® or Quanti-Tray®/2000, and the MPN calculated from the table provided by the manufacturer. 15 Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms and E. coli that provides results within 18 h of 

incubation at 35 °C, rather than the 24 h required for the Colilert® test, and is recommended for marine water samples. 16 Descriptions of the Colilert®, Colilert-18®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories Inc. 17A description of the mColiBlue24® test may be obtained from Hach Company. 18Subject total coliform positive samples determined by 9222B–1997 or other membrane filter procedure to 9222G–1997 using NA–MUG 

media. 19 Method 1103.1: Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC), 

EPA–821–R–10–002. March 2010. US EPA. 20 Method 1603: Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane-Thermotolerant Escherichia coli Agar 

(Modified mTEC), EPA–821–R–09–007. December 2009. US EPA. 21Preparation and use of MI agar with a standard membrane filter procedure is set forth in the article, Brenner et al. 1993. New Medium for 

the Simultaneous Detection of Total Coliform and Escherichia coli in Water. Appl. Environ. Microbiol. 59:3534–3544 and in Method 1604: Total 

Coliforms and Escherichia coli (E. coli) in Water by Membrane Filtration by Using a Simultaneous Detection Technique (MI Medium), EPA 821– 

R–02–024, September 2002, US EPA. 22A description of the Enterolert® test may be obtained from IDEXX Laboratories Inc. 23 Method 1106.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE–EIA), EPA–821–R–09– 

015. December 2009. US EPA. 24 Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-b-D-Glucoside Agar (mEI), EPA–821–R– 

09–016. December 2009. US EPA. 25 Method 1622 uses a filtration, concentration, immunomagnetic separation of oocysts from captured material, immunofluorescence assay to 

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

Cryptosporidium. Method 1622: Cryptosporidium in Water by Filtration/IMS/FA, EPA–821–R–05–001. December 2005. US EPA. 26 Method 1623 uses a filtration, concentration, immunomagnetic separation of oocysts and cysts from captured material, immunofluorescence 

assay to determine concentrations, and confirmation through vital dye staining and differential interference contrast microscopy for the simultaneous detection of Cryptosporidium and Giardia oocysts and cysts. Method 1623. Cryptosporidium and Giardia in Water by Filtration/IMS/FA. 

EPA–821–R–05–002. December 2005. US EPA. 

(b) The documents required in this 

section are incorporated by reference 

into this section with approval of the 

Director of the Federal Register in 

accordance with 5 U.S.C. 552(a) and 1 

CFR part 51. Copies of the documents 

may be obtained from the sources listed 

in paragraph (b) of this section. 

Documents may be inspected at EPA’s 

Water Docket, EPA West, 1301 

Constitution Avenue NW., Room B102, 

Washington, DC (Telephone: 202–566– 

2426); or at the National Archives and 

Records Administration (NARA). For 

information on the availability of this 

material at NARA, call 202–741–6030, 

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

federal_register/code_of_federal_

regulations/ibr_locations.html. These 

test procedures are incorporated as they 

exist on the day of approval and a notice 

of any change in these test procedures 

will be published in the Federal 

Register. The full texts of the methods 

from the following references which are 

cited in Tables IA, IB, IC, ID, IE, IF, IG 

and IH are incorporated by reference 

into this regulation and may be obtained 

from the source identified. All costs 

cited are subject to change and must be 

verified from the indicated source. 

(1) Environmental Monitoring and 

Support Laboratory, U.S. Environmental 

Protection Agency, Cincinnati OH (US 

EPA). Available at http://water.epa.gov/ 

scitech/methods/cwa/index.cfm or from: 

National Technical Information Service, 

5285 Port Royal Road, Springfield, 

Virginia 22161 

(i) Microbiological Methods for 

Monitoring the Environment, Water, 

and Wastes. 1978. EPA/600/8–78/017, 

Pub. No. PB–290329/A.S. 

(A) Part III Analytical Methodology, 

Section B Total Coliform Methods, page 

108. Table IA, Note 3; Table IH, Note 3. 

(B) Part III Analytical Methodology, 

Section B Total Coliform Methods, 2.6.2 

Two-Step Enrichment Procedure, page 

111. Table IA, Note 3; Table IH, Note 3. 

(C) Part III Analytical Methodology, 

Section B Total Coliform Methods, 4 

Most Probable Number (MPN) Method, 

page 114. Table IA, Note 3; Table IH, 

Note 3. 

(D) Part III Analytical Methodology, 

Section C Fecal Coliform Methods, 2 

Direct Membrane Filter (MF) Method, 

page 124. Table IA, Note 3; Table IH, 

Note 3. 

(E) Part III, Analytical Methodology, 

Section C Fecal Coliform Methods, 5 

Most Probable Number (MPN) Method, 

page 132. Table IA, Note 3; Table IH, 

Note 3. 

(F) Part III Analytical Methodology, 

Section D Fecal Streptococci, 2 

Membrane Filter (MF) Method, page 

136. Table IA, Note 3; Table IH, Note 3. 

(G) Part III Analytical Methodology, 

Section D Fecal Streptococci, 4 Most 

Probable Number Method, page 139. 

Table IA, Note 3; Table IH, Note 3. 

(H) Part III Analytical Methodology, 

Section D Fecal Streptococci, 5 Pour 

Plate Method, page 143. Table IA, Note 

3; Table IH, Note 3. 

(ii) [Reserved] 

(2) Environmental Monitoring and 

Support Laboratory, U.S. Environmental 

Protection Agency, Cincinnati OH (US 

EPA). Available at http://water.epa.gov/ 

scitech/methods/cwa/index.cfm. 

(i) Method 300.1 (including Errata 

Cover Sheet, April 27, 1999), 

Determination of Inorganic Ions in 

Drinking Water by Ion Chromatography, 

Revision 1.0, 1997. Table IB, Note 52. 

(ii) Method 551, Determination of 

Chlorination Disinfection Byproducts 

and Chlorinated Solvents in Drinking 

Water by Liquid-Liquid Extraction and 

Gas Chromatography With ElectronCapture Detection. 1990. Table IF. 

(3) National Exposure Risk 

Laboratory-Cincinnati, U.S. 

Environmental Protection Agency, 

Cincinnati OH (US EPA). Available from 

http://water.epa.gov/scitech/methods/ 

cwa/index.cfm or from the National 

Technical Information Service (NTIS), 

5285 Port Royal Road, Springfield, VA 

22161. Telephone: 800–553–6847. 

(i) Methods for the Determination of 

Inorganic Substances in Environmental 

Samples. August 1993. EPA/600/R–93/ 

100, Pub. No. PB 94120821. Table IB, 

Note 52. 

(A) Method 180.1, Determination of 

Turbidity by Nephelometry. Revision 

2.0. Table IB, Note 52. 

(B) Method 300.0, Determination of 

Inorganic Anions by Ion 

Chromatography. Revision 2.1. Table IB, 

Note 52. 

(C) Method 335.4, Determination of 

Total Cyanide by Semi-Automated 

Colorimetry. Revision 1.0. Table IB, 

Notes 52 and 57. 

(D) Method 350.1, Determination of 

Ammonium Nitrogen by SemiAutomated Colorimetry. Revision 2.0. 

Table IB, Notes 30 and 52. 

(E) Method 351.2, Determination of 

Total Kjeldahl Nitrogen by SemiAutomated Colorimetry. Revision 2.0. 

Table IB, Note 52. 

(F) Method 353.2, Determination of 

Nitrate-Nitrite Automated Colorimetry. 

Revision 2.0. Table IB, Note 52. 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29799 

(G) Method 365.1, Determination of 

Phosphorus by Automated Colorimetry. 

Revision 2.0. Table IB, Note 52. 

(H) Method 375.2, Determination of 

Sulfate by Automated Colorimetry. 

Revision 2.0. Table IB, Note 52. 

(I) Method 410.4, Determination of 

Chemical Oxygen Demand by SemiAutomated Colorimetry. Revision 2.0. 

Table IB, Note 52. 

(ii) Methods for the Determination of 

Metals in Environmental Samples, 

Supplement I. May 1994. EPA/600/R– 

94/111, Pub. No. PB 95125472. Table IB, 

Note 52. 

(A) Method 200.7, Determination of 

Metals and Trace Elements in Water and 

Wastes by Inductively Coupled PlasmaAtomic Emission Spectrometry. 

Revision 4.4. Table IB, Note 52. 

(B) Method 200.8, Determination of 

Trace Elements in Water and Wastes by 

Inductively Coupled Plasma Mass 

Spectrometry. Revision 5.3. Table IB, 

Note 52. 

(C) Method 200.9, Determination of 

Trace Elements by Stabilized 

Temperature Graphite Furnace Atomic 

Absorption Spectrometry. Revision 2.2. 

Table IB, Note 52. 

(D) Method 218.6, Determination of 

Dissolved Hexavalent Chromium in 

Drinking Water, Groundwater, and 

Industrial Wastewater Effluents by Ion 

Chromatography. Revision 3.3. Table IB, 

Note 52. 

(E) Method 245.1, Determination of 

Mercury in Water by Cold Vapor Atomic 

Absorption Spectrometry. Revision 3.0. 

Table IB, Note 52. 

(4) National Exposure Risk 

Laboratory-Cincinnati, U.S. 

Environmental Protection Agency, 

Cincinnati OH (US EPA). Available at 

http://water.epa.gov/scitech/methods/ 

cwa/index.cfm. 

(i) EPA Method 200.5, Determination 

of Trace Elements in Drinking Water by 

Axially Viewed Inductively Coupled 

Plasma-Atomic Emission Spectrometry. 

Revision 4.2, October 2003. EPA/600/R– 

06/115. Table IB, Note 68. 

(ii) EPA Method 525.2, Determination 

of Organic Compounds in Drinking 

Water by Liquid-Solid Extraction and 

Capillary Column Gas Chromatography/ 

Mass Spectrometry. Revision 2.0, 1995. 

Table ID, Note 10. 

(5) Office of Research and 

Development, Cincinnati OH. U.S. 

Environmental Protection Agency, 

Cincinnati OH (US EPA). Available at 

http://water.epa.gov/scitech/methods/ 

cwa/index.cfm or from ORD 

Publications, CERI, U.S. Environmental 

Protection Agency, Cincinnati OH 

45268. 

(i) Methods for Benzidine, 

Chlorinated Organic Compounds, 

Pentachlorophenol, and Pesticides in 

Water and Wastewater. 1978. Table IC, 

Note 3; Table ID, Note 3. 

(ii) Methods for Chemical Analysis of 

Water and Wastes. March 1979. EPA– 

600/4–79–020. Table IB, Note 1. 

(iii) Methods for Chemical Analysis of 

Water and Wastes. Revised March 1983. 

EPA–600/4–79–020. Table IB, Note 1. 

(A) Method 120.1, Conductance, 

Specific Conductance, mmhos at 25 °C. 

Revision 1982. Table IB, Note 1. 

(B) Method 130.1, Hardness, Total 

(mg/L as CaCO3), Colorimetric, 

Automated EDTA. Issued 1971. Table 

IB, Note 1. 

(C) Method 150.2, pH, Continuous 

Monitoring (Electrometric). December 

1982. Table IB, Note 1. 

(D) Method 160.4, Residue, Volatile, 

Gravimetric, Ignition at 550 °C. Issued 

1971. Table IB, Note 1. 

(E) Method 206.5, Arsenic, Sample 

Digestion Prior to Total Arsenic 

Analysis by Silver 

Diethyldithiocarbamate or Hydride 

Procedures. Issued 1978. Table IB, Note 

1. 

(F) Method 231.2, Gold, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(G) Method 245.2, Mercury, 

Automated Cold Vapor Technique. 

Issued 1974. Table IB, Note 1. 

(H) Method 252.2, Osmium, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(I) Method 253.2, Palladium, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(J) Method 255.2, Platinum, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(K) Method 265.2, Rhodium, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(L) Method 279.2, Thallium, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(M) Method 283.2, Titanium, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(N) Method 289.2, Zinc, Atomic 

Absorption, Furnace Technique. Issued 

1978. Table IB, Note 1. 

(O) Method 310.2, Alkalinity, 

Colorimetric, Automated, Methyl 

Orange. Revision 1974. Table IB, Note 1. 

(P) Method 351.1, Nitrogen, Kjeldahl, 

Total, Colorimetric, Automated Phenate. 

Revision 1978. Table IB, Note 1. 

(Q) Method 352.1, Nitrogen, Nitrate, 

Colorimetric, Brucine. Issued 1971. 

Table IB, Note 1. 

(R) Method 365.3, Phosphorus, All 

Forms, Colorimetric, Ascorbic Acid, 

Two Reagent. Issued 1978. Table IB, 

Note 1. 

(S) Method 365.4, Phosphorus, Total, 

Colorimetric, Automated, Block Digestor 

AA II. Issued 1974. Table IB, Note 1. 

(T) Method 410.3, Chemical Oxygen 

Demand, Titrimetric, High Level for 

Saline Waters. Revision 1978. Table IB, 

Note 1. 

(U) Method 420.1, Phenolics, Total 

Recoverable, Spectrophotometric, 

Manual 4–AAP With Distillation. 

Revision 1978. Table IB, Note 1. 

(iv) Prescribed Procedures for 

Measurement of Radioactivity in 

Drinking Water. 1980. EPA–600/4–80– 

032. Table IE. 

(A) Method 900.0, Gross Alpha and 

Gross Beta Radioactivity. Table IE. 

(B) Method 903.0, Alpha-Emitting 

iRadio Isotopes. Table IE. 

(C) Method 903.1, Radium-226, Radon 

Emanation Technique. Table IE. 

(D) Appendix B, Error and Statistical 

Calculations. Table IE. 

(6) Office of Science and Technology, 

U.S. Environmental Protection Agency, 

Washington DC (US EPA). Available at 

http://water.epa.gov/scitech/methods/ 

cwa/index.cfm. 

(i) Method 1625C, Semivolatile 

Organic Compounds by Isotope Dilution 

GCMS. 1989. Table IF. 

(ii) [Reserved] 

(7) Office of Water, U.S. 

Environmental Protection Agency, 

Washington DC (US EPA). Available at 

http://water.epa.gov/scitech/methods/ 

cwa/index.cfm or from National 

Technical Information Service, 5285 

Port Royal Road, Springfield, Virginia 

22161. 

(i) Method 1631, Mercury in Water by 

Oxidation, Purge and Trap, and Cold 

Vapor Atomic Fluorescence 

Spectrometry. Revision E, August 2002. 

EPA–821–R–02–019, Pub. No. PB2002– 

108220. Table IB, Note 43. 

(ii) Kelada-01, Kelada Automated Test 

Methods for Total Cyanide, Acid 

Dissociable Cyanide, and Thiocyanate. 

Revision 1.2, August 2001. EPA 821–B– 

01–009, Pub. No. PB 2001–108275. 

Table IB, Note 55. 

(iii) In the compendium Analytical 

Methods for the Determination of 

Pollutants in Pharmaceutical 

Manufacturing Industry Wastewaters. 

July 1998. EPA 821–B–98–016, Pub. No. 

PB95201679. Table IF, Note 1. 

(A) EPA Method 1666, Volatile 

Organic Compounds Specific to the 

Pharmaceutical Industry by Isotope 

Dilution GC/MS. Table IF, Note 1. 

(B) EPA Method 1667, Formaldehyde, 

Isobutyraldehyde, and Furfural by 

Derivatization Followed by High 

Performance Liquid Chromatography. 

Table IF. 

(C) Method 1671, Volatile Organic 

Compounds Specific to the 


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Pharmaceutical Manufacturing Industry 

by GC/FID. Table IF. 

(iv) Methods For The Determination 

of Nonconventional Pesticides In 

Municipal and Industrial Wastewater, 

Volume I. Revision I, August 1993. EPA 

821–R–93–010A, Pub. No. PB 94121654. 

Tables ID, IG. 

(A) Method 608.1, Organochlorine 

Pesticides. Table ID, Note 10; Table IG, 

Note 3. 

(B) Method 608.2, Certain 

Organochlorine Pesticides. Table ID, 

Note 10; Table IG, Note 3. 

(C) Method 614, Organophosphorus 

Pesticides. Table ID, Note 10; Table IG, 

Note 3. 

(D) Method 614.1, Organophosphorus 

Pesticides. Table ID, Note 10; Table IG, 

Note 3. 

(E) Method 615, Chlorinated 

Herbicides. Table ID, Note 10; Table IG, 

Note 3. 

(F) Method 617, Organohalide 

Pesticides and PCBs. Table ID, Note 10; 

Table IG, Note 3. 

(G) Method 619, Triazine Pesticides. 

Table ID, Note 10; Table IG, Note 3. 

(H) Method 622, Organophosphorus 

Pesticides. Table ID, Note 10; Table IG, 

Note 3. 

(I) Method 622.1, Thiophosphate 

Pesticides. Table ID, Note 10; Table IG, 

Note 3. 

(J) Method 627, Dinitroaniline 

Pesticides. Table ID, Note 10; Table IG, 

Notes 1 and 3. 

(K) Method 629, Cyanazine. Table IG, 

Note 3. 

(L) Method 630, Dithiocarbamate 

Pesticides. Table IG, Note 3. 

(M) Method 630.1, Dithiocarbamate 

Pesticides. Table IG, Note 3. 

(N) Method 631, Benomyl and 

Carbendazim. Table IG, Note 3. 

(O) Method 632, Carbamate and Urea 

Pesticides. Table ID, Note 10; Table IG, 

Note 3. 

(P) Method 632.1, Carbamate and 

Amide Pesticides. Table IG, Note 3. 

(Q) Method 633, Organonitrogen 

Pesticides. Table IG, Note 3. 

(R) Method 633.1, Neutral NitrogenContaining Pesticides. Table IG, Note 3. 

(S) Method 637, MBTS and TCMTB. 

Table IG, Note 3. 

(T) Method 644, Picloram. Table IG, 

Note 3. 

(U) Method 645, Certain Amine 

Pesticides and Lethane. Table IG, Note 

3. 

(V) Method 1656, Organohalide 

Pesticides. Table ID, Note 10; Table IG, 

Notes 1 and 3. 

(W) Method 1657, Organophosphorus 

Pesticides. Table ID, Note 10; Table IG, 

Note 3. 

(X) Method 1658, Phenoxy-Acid 

Herbicides. Table IG, Note 3. 

(Y) Method 1659, Dazomet. Table IG, 

Note 3. 

(Z) Method 1660, Pyrethrins and 

Pyrethroids. Table IG, Note 3. 

(AA) Method 1661, Bromoxynil. Table 

IG, Note 3. 

(BB) Ind-01. Methods EV–024 and 

EV–025, Analytical Procedures for 

Determining Total Tin and Triorganotin 

in Wastewater. Table IG, Note 3. 

(v) Methods For The Determination of 

Nonconventional Pesticides In 

Municipal and Industrial Wastewater, 

Volume II. August 1993. EPA 821–R– 

93–010B, Pub. No. PB 94166311. Table 

IG. 

(A) Method 200.9, Determination of 

Trace Elements by Stabilized 

Temperature Graphite Furnace Atomic 

Absorption Spectrometry. Table IG, 

Note 3. 

(B) Method 505, Analysis of 

Organohalide Pesticides and 

Commercial Polychlorinated Biphenyl 

(PCB) Products in Water by 

Microextraction and Gas 

Chromatography. Table ID, Note 10; 

Table IG, Note 3. 

(C) Method 507, The Determination of 

Nitrogen- and Phosphorus-Containing 

Pesticides in Water by Gas 

Chromatography with a NitrogenPhosphorus Detector. Table ID, Note 10; 

Table IG, Note 3. 

(D) Method 508, Determination of 

Chlorinated Pesticides in Water by Gas 

Chromatography with an Electron 

Capture Detector. Table ID, Note 10; 

Table IG, Note 3. 

(E) Method 515.1, Determination of 

Chlorinated Acids in Water by Gas 

Chromatography with an Electron 

Capture Detector. Table IG, Notes 2 and 

3. 

(F) Method 515.2, Determination of 

Chlorinated Acids in Water Using 

Liquid-Solid Extraction and Gas 

Chromatography with an Electron 

Capture Detector. Table IG, Notes 2 and 

3. 

(G) Method 525.1, Determination of 

Organic Compounds in Drinking Water 

by Liquids-Solid Extraction and 

Capillary Column Gas Chromatography/ 

Mass Spectrometry. Table ID, Note 10; 

Table IG, Note 3. 

(H) Method 531.1, Measurement of NMethylcarbamoyloximes and NMethylcarbamates in Water by Direct 

Aqueous Injection HPLC with PostColumn Derivatization. Table ID, Note 

10; Table IG, Note 3. 

(I) Method 547, Determination of 

Glyphosate in Drinking Water by DirectAqueous-Injection HPLC, Post-Column 

Derivatization, and Fluorescence 

Detection. Table IG, Note 3. 

(J) Method 548, Determination of 

Endothall in Drinking Water by 

Aqueous Derivatization, Liquid-Solid 

Extraction, and Gas Chromatography 

with Electron-Capture Detector. Table 

IG, Note 3. 

(K) Method 548.1, Determination of 

Endothall in Drinking Water by IonExchange Extraction, Acidic Methanol 

Methylation and Gas Chromatography/ 

Mass Spectrometry. Table IG, Note 3. 

(L) Method 553, Determination of 

Benzidines and Nitrogen-Containing 

Pesticides in Water by Liquid-Liquid 

Extraction or Liquid-Solid Extraction 

and Reverse Phase High Performance 

Liquid Chromatography/Particle Beam/ 

Mass Spectrometry Table ID, Note 10; 

Table IG, Note 3. 

(M) Method 555, Determination of 

Chlorinated Acids in Water by High 

Performance Liquid Chromatography 

With a Photodiode Array Ultraviolet 

Detector. Table IG, Note 3. 

(vi) In the compendium Methods for 

the Determination of Organic 

Compounds in Drinking Water. Revised 

July 1991, December 1998. EPA–600/4– 

88–039, Pub. No. PB92–207703. Table 

IF. 

(A) EPA Method 502.2, Volatile 

Organic Compounds in Water by Purge 

and Trap Capillary Column Gas 

Chromatography with Photoionization 

and Electrolytic Conductivity Detectors 

in Series. Table IF. 

(B) [Reserved] 

(vii) In the compendium Methods for 

the Determination of Organic 

Compounds in Drinking WaterSupplement II. August 1992. EPA–600/ 

R–92–129, Pub. No. PB92–207703. 

Table IF. 

(A) EPA Method 524.2, Measurement 

of Purgeable Organic Compounds in 

Water by Capillary Column Gas 

Chromatography/Mass Spectrometry. 

Table IF. 

(B) [Reserved] 

(viii) Methods for Measuring the 

Acute Toxicity of Effluents and 

Receiving Waters to Freshwater and 

Marine Organisms, Fifth Edition. 

October 2002. EPA 821–R–02–012, Pub. 

No. PB2002–108488. Table IA, Note 26. 

(ix) Short-Term Methods for 

Measuring the Chronic Toxicity of 

Effluents and Receiving Waters to 

Freshwater Organisms, Fourth Edition. 

October 2002. EPA 821–R–02–013, Pub. 

No. PB2002–108489. Table IA, Note 27. 

(x) Short-Term Methods for 

Measuring the Chronic Toxicity of 

Effluents and Receiving Waters to 

Marine and Estuarine Organisms, Third 

Edition. October 2002. EPA 821–R–02– 

014, Pub. No. PB2002–108490. Table IA, 

Note 28. 

(8) Office of Water, U.S. 

Environmental Protection Agency, 

Washington DC (US EPA). Available at 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29801 

http://water.epa.gov/scitech/methods/ 

cwa/index.cfm. 

(i) Method 245.7, Mercury in Water by 

Cold Vapor Atomic Fluorescence 

Spectrometry. Revision 2.0, February 

2005. EPA–821–R–05–001. Table IB, 

Note 17. 

(ii) Method 1103.1: Escherichia coli 

(E. coli) in Water by Membrane 

Filtration Using membraneThermotolerant Escherichia coli Agar 

(mTEC). March 2010. EPA–621–R–10– 

002. Table IH, Note 19. 

(iii) Method 1106.1: Enterococci in 

Water by Membrane Filtration Using 

membrane-Enterococcus-Esculin Iron 

Agar (mE–EIA). December 2009. EPA– 

621–R–09–015. Table IH, Note 23. 

(iv) Method 1600: Enterococci in 

Water by Membrane Filtration Using 

membrane-Enterococcus Indoxyl-b-DGlucoside Agar (mEI). December 2009. 

EPA–821–R–09–016. 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). December 2009. 

EPA–821–R–09–007. Table IA, Note 22; 

Table IH, Note 20. 

(vi) Method 1604: Total Coliforms and 

Escherichia coli (E. coli) in Water by 

Membrane Filtration Using a 

Simultaneous Detection Technique (MI 

Medium). September 2002. EPA–821– 

R–02–024. Table IH, Note 21. 

(vii) Method 1622: Cryptosporidium 

in Water by Filtration/IMS/FA. 

December 2005. EPA–821–R–05–001. 

Table IH, Note 25. 

(viii) Method 1623: Cryptosporidium 

and Giardia in Water by Filtration/IMS/ 

FA. December 2005. EPA–821–R–05– 

002. Table IH, Note 26. 

(ix) Method 1627, Kinetic Test 

Method for the Prediction of Mine 

Drainage Quality. December 2011. EPA– 

821–R–09–002. Table IB, Note 69. 

(x) Method 1664, n-Hexane 

Extractable Material (HEM; Oil and 

Grease) and Silica Gel Treated n-Hexane 

Extractable Material (SGT-HEM; Nonpolar Material) by Extraction and 

Gravimetry. Revision A, February 1999. 

EPA–821–R–98–002. Table IB, Notes 38 

and 42. 

(xi) Method 1664, n-Hexane 

Extractable Material (HEM; Oil and 

Grease) and Silica Gel Treated n-Hexane 

Extractable Material (SGT-HEM; Nonpolar Material) by Extraction and 

Gravimetry. Revision B, February 2010. 

EPA–821–R–10–001. Table IB, Notes 38 

and 42. 

(xii) Method 1669, Sampling Ambient 

Water for Trace Metals at EPA Water 

Quality Criteria Levels. July 1996. Table 

IB, Note 43. 

(xiii) Method 1680: Fecal Coliforms in 

Sewage Sludge (Biosolids) by MultipleTube Fermentation using Lauryl 

Tryptose Broth (LTB) and EC Medium. 

April 2010. EPA–821–R–10–003. Table 

IA, Note 15. 

(xiv) Method 1681: Fecal Coliforms in 

Sewage Sludge (Biosolids) by MultipleTube Fermentation using A–1 Medium. 

July 2006. EPA 821–R–06–013. Table 

IA, Note 20. 

(xv) Method 1682: Salmonella in 

Sewage Sludge (Biosolids) by Modified 

Semisolid Rappaport-Vassiliadis 

(MSRV) Medium. July 2006. EPA 821– 

R–06–014. Table IA, Note 23. 

(9) American National Standards 

Institute, 1430 Broadway, New York NY 

10018. 

(i) ANSI. American National Standard 

on Photographic Processing Effluents. 

April 2, 1975. Table IB, Note 9. 

(ii) [Reserved] 

(10) American Public Health 

Association, 1015 15th Street NW., 

Washington, DC 20005. Standard 

Methods Online is available through the 

Standard Methods Web site (http:// 

www.standardmethods.org). 

(i) Standard Methods for the 

Examination of Water and Wastewater. 

14th Edition, 1975. Table IB, Notes 17 

and 27. 

(ii) Standard Methods for the 

Examination of Water and Wastewater. 

15th Edition, 1980, Table IB, Note 30; 

Table ID. 

(iii) Selected Analytical Methods 

Approved and Cited by the United 

States Environmental Protection 

Agency, Supplement to the 15th Edition 

of Standard Methods for the 

Examination of Water and Wastewater. 

1981. Table IC, Note 6; Table ID, Note 

6. 

(iv) Standard Methods for the 

Examination of Water and Wastewater. 

18th Edition, 1992. Tables IA, IB, IC, ID, 

IE, and IH. 

(v) Standard Methods for the 

Examination of Water and Wastewater. 

19th Edition, 1995. Tables IA, IB, IC, ID, 

IE, and IH. 

(vi) Standard Methods for the 

Examination of Water and Wastewater. 

20th Edition, 1998. Tables IA, IB, IC, ID, 

IE, and IH. 

(vii) Standard Methods for the 

Examination of Water and Wastewater. 

21st Edition, 2005. Table IB, Notes 17 

and 27. 

(viii) 2120, Color. 2001. Table IB. 

(ix) 2130, Turbidity. 2001. Table IB. 

(x) 2310, Acidity. 1997. Table IB. 

(xi) 2320, Alkalinity. 1997. Table IB. 

(xii) 2340, Hardness. 1997. Table IB. 

(xiii) 2510, Conductivity. 1997. Table 

IB. 

(xiv) 2540, Solids. 1997. Table IB. 

(xv) 2550, Temperature. 2000. Table 

IB. 

(xvi) 3111, Metals by Flame Atomic 

Absorption Spectrometry. 1999. Table 

IB. 

(xvii) 3112, Metals by Cold-Vapor 

Atomic Absorption Spectrometry. 2009. 

Table IB. 

(xviii) 3113, Metals by Electrothermal 

Atomic Absorption Spectrometry. 2004. 

Table IB. 

(xix) 3114, Arsenic and Selenium by 

Hydride Generation/Atomic Absorption 

Spectrometry. 2009. Table IB. 

(xx) 3120, Metals by Plasma Emission. 

1999. Table IB. 

(xxi) 3125, Metals by Inductively 

Coupled Plasma-Mass Spectrometry. 

2009. Table IB. 

(xxii) 3500-Al, Aluminum. 2001. 

Table IB. 

(xxiii) 3500-As, Arsenic. 1997. Table 

IB. 

(xxiv) 3500-Ca, Calcium. 1997. Table 

IB. 

(xxv) 3500-Cr, Chromium. 2009. Table 

IB. 

(xxvi) 3500-Cu, Copper. 1999. Table 

IB. 

(xxvii) 3500-Fe, Iron. 1997. Table IB. 

(xxviii) 3500-Pb, Lead. 1997. Table IB. 

(xxix) 3500-Mn, Manganese. 1999. 

Table IB. 

(xxx) 3500-K, Potassium. 1997. Table 

IB. 

(xxxi) 3500-Na, Sodium. 1997. Table 

IB. 

(xxxii) 3500-V, Vanadium. 1997. 

Table IB. 

(xxxiii) 3500-Zn, Zinc. 1997. Table IB. 

(xxxiv) 4110, Determination of Anions 

by Ion Chromatography. 2000. Table IB. 

(xxxv) 4140, Inorganic Anions by 

Capillary Ion Electrophoresis. 1997. 

Table IB. 

(xxxvi) 4500-B, Boron. 2000. Table IB. 

(xxxvii) 4500-Cl¥, Chloride. 1997. 

Table IB. 

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

2000. Table IB. 

(xxxix) 4500-CN¥, Cyanide. 1999. 

Table IB. 

(xl) 4500-F¥, Fluoride. 1997. Table 

IB. 

(xli) 4500-H+, pH Value. 2000. Table 

IB. 

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

1997. Table IB. 

(xliii) 4500-NO2

¥, Nitrogen (Nitrite). 

2000. Table IB. 

(xliv) 4500-NO3

¥, Nitrogen (Nitrate). 

2000. Table IB. 

(xlv) 4500-Norg, Nitrogen (Organic). 

1997. Table IB. 

(xlvi) 4500-O, Oxygen (Dissolved). 

2001. Table IB. 

(xlvii) 4500-P, Phosphorus. 1999. 

Table IB. 

(xlviii) 4500-SiO2, Silica. 1997. Table 

IB. 


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(xlix) 4500-S2¥, Sulfide. 2000. Table 

IB. 

(l) 4500-SO3

2¥, Sulfite. 2000. Table 

IB. 

(li) 4500-SO4

2¥, Sulfate. 1997. Table 

IB. 

(lii) 5210, Biochemical Oxygen 

Demand (BOD). 2001. Table IB. 

(liii) 5220, Chemical Oxygen Demand 

(COD). 1997. Table IB. 

(liv) 5310, Total Organic Carbon 

(TOC). 2000. Table IB. 

(lv) 5520, Oil and Grease. 2001. Table 

IB. 

(lvi) 5530, Phenols. 2005. Table IB. 

(lvii) 5540, Surfactants. 2000. Table 

IB. 

(lviii) 6200, Volatile Organic 

Compounds. 1997. Table IC. 

(lix) 6410, Extractable Base/Neutrals 

and Acids. 2000. Tables IC, ID. 

(lx) 6420, Phenols. 2000. Table IC. 

(lxi) 6440, Polynuclear Aromatic 

Hydrocarbons. 2000. Table IC. 

(lxii) 6630, Organochlorine Pesticides. 

2000. Table ID. 

(lxiii) 6640, Acidic Herbicide 

Compounds. 2001. Table ID. 

(lxiv) 7110, Gross Alpha and Gross 

Beta Radioactivity (Total, Suspended, 

and Dissolved). 2000. Table IE. 

(lxv) 7500, Radium. 2001. Table IE. 

(lxvi) 9213, Recreational Waters. 

2007. Table IH. 

(lxvii) 9221, Multiple-Tube 

Fermentation Technique for Members of 

the Coliform Group. 2006. Table IA, 

Notes 12 and 14; Table IH, Notes 11 and 

13. 

(lxviii) 9222, Membrane Filter 

Technique for Members of the Coliform 

Group. 1997. Table IA; Table IH, Note 

18. 

(lxix) 9223, Enzyme Substrate 

Coliform Test. 2004. Table IA; Table IH. 

(lxx) 9230, Fecal Enterococcus/ 

Streptococcus Groups. 2007. Table IA; 

Table IH. 

(11) The Analyst, The Royal Society 

of Chemistry, RSC Publishing, Royal 

Society of Chemistry, Thomas Graham 

House, Science Park, Milton Road, 

Cambridge CB4 0WF, United Kingdom. 

(Also available from most public 

libraries.) 

(i) Spectrophotometric Determination 

of Ammonia: A Study of a Modified 

Berthelot Reaction Using Salicylate and 

Dichloroisocyanurate. Krom, M.D. 

105:305–316, April 1980. Table IB, Note 

60. 

(ii) [Reserved] 

(12) Analytical Chemistry, ACS 

Publications, 1155 Sixteenth St. NW., 

Washington DC 20036. (Also available 

from most public libraries.) 

(i) Spectrophotometric and Kinetics 

Investigation of the Berthelot Reaction 

for the Determination of Ammonia. 

Patton, C.J. and S.R. Crouch. 49(3):464– 

469, March 1977. Table IB, Note 60. 

(ii) [Reserved] 

(13) AOAC International, 481 North 

Frederick Avenue, Suite 500, 

Gaithersburg, MD 20877–2417. 

(i) Official Methods of Analysis of 

AOAC International. 16th Edition, 4th 

Revision, 1998. 

(A) 920.203, Manganese in Water, 

Persulfate Method. Table IB, Note 3. 

(B) 925.54, Sulfate in Water, 

Gravimetric Method. Table IB, Note 3. 

(C) 973.40, Specific Conductance of 

Water. Table IB, Note 3. 

(D) 973.41, pH of Water. Table IB, 

Note 3. 

(E) 973.43, Alkalinity of Water, 

Titrimetric Method. Table IB, Note 3. 

(F) 973.44, Biochemical Oxygen 

Demand (BOD) of Water, Incubation 

Method. Table IB, Note 3. 

(G) 973.45, Oxygen (Dissolved) in 

Water, Titrimetric Methods. Table IB, 

Note 3. 

(H) 973.46, Chemical Oxygen Demand 

(COD) of Water, Titrimetric Methods. 

Table IB, Note 3. 

(I) 973.47, Organic Carbon in Water, 

Infrared Analyzer Method. Table IB, 

Note 3. 

(J) 973.48, Nitrogen (Total) in Water, 

Kjeldahl Method. Table IB, Note 3. 

(K) 973.49, Nitrogen (Ammonia) in 

Water, Colorimetric Method. Table IB, 

Note 3. 

(L) 973.50, Nitrogen (Nitrate) in 

Water, Brucine Colorimetric Method. 

Table IB, Note 3. 

(M) 973.51, Chloride in Water, 

Mercuric Nitrate Method. Table IB, Note 

3. 

(N) 973.52, Hardness of Water. Table 

IB, Note 3. 

(O) 973.53, Potassium in Water, 

Atomic Absorption Spectrophotometric 

Method. Table IB, Note 3. 

(P) 973.54, Sodium in Water, Atomic 

Absorption Spectrophotometric Method. 

Table IB, Note 3. 

(Q) 973.55, Phosphorus in Water, 

Photometric Method. Table IB, Note 3. 

(R) 973.56, Phosphorus in Water, 

Automated Method. Table IB, Note 3. 

(S) 974.27, Cadmium, Chromium, 

Copper, Iron, Lead, Magnesium, 

Manganese, Silver, Zinc in Water, 

Atomic Absorption Spectrophotometric 

Method. Table IB, Note 3. 

(T) 977.22, Mercury in Water, 

Flameless Atomic Absorption 

Spectrophotometric Method. Table IB, 

Note 3. 

(U) 991.15. Total Coliforms and 

Escherichia coli in Water Defined 

Substrate Technology (Colilert) Method. 

Table IA, Note 10; Table IH, Note 10. 

(V) 993.14, Trace Elements in Waters 

and Wastewaters, Inductively Coupled 

Plasma-Mass Spectrometric Method. 

Table IB, Note 3. 

(W) 993.23, Dissolved Hexavalent 

Chromium in Drinking Water, Ground 

Water, and Industrial Wastewater 

Effluents, Ion Chromatographic Method. 

Table IB, Note 3. 

(X) 993.30, Inorganic Anions in 

Water, Ion Chromatographic Method. 

Table IB, Note 3. 

(ii) [Reserved] 

(14) Applied and Environmental 

Microbiology, American Society for 

Microbiology, 1752 N Street NW., 

Washington DC 20036. (Also available 

from most public libraries.) 

(i) New Medium for the Simultaneous 

Detection of Total Coliforms and 

Escherichia coli in Water. Brenner, K.P., 

C.C. Rankin, Y.R. Roybal, G.N. Stelma, 

Jr., P.V. Scarpino, and A.P. Dufour. 

59:3534–3544, November 1993. Table 

IH, Note 21. 

(ii) [Reserved] 

(15) ASTM International, 100 Barr 

Harbor Drive, P.O. Box C700, West 

Conshohocken, PA 19428–2959, or 

online at http://www.astm.org. 

(i) Annual Book of ASTM Standards, 

Water, and Environmental Technology, 

Section 11, Volumes 11.01 and 11.02. 

1994. Tables IA, IB, IC, ID, IE, and IH. 

(ii) Annual Book of ASTM Standards, 

Water, and Environmental Technology, 

Section 11, Volumes 11.01 and 11.02. 

1996. Tables IA, IB, IC, ID, IE, and IH. 

(iii) Annual Book of ASTM Standards, 

Water, and Environmental Technology, 

Section 11, Volumes 11.01 and 11.02. 

1999. Tables IA, IB, IC, ID, IE, and IH. 

(iv) Annual Book of ASTM Standards, 

Water, and Environmental Technology, 

Section 11, Volumes 11.01 and 11.02. 

2000. Tables IA, IB, IC, ID, IE, and IH. 

(v) ASTM D511–08, Standard Test 

Methods for Calcium and Magnesium in 

Water. November 2008. Table IB. 

(vi) ASTM D512–04, Standard Test 

Methods for Chloride Ion in Water. July 

2004. Table IB. 

(vii) ASTM D515–88, Test Methods 

for Phosphorus in Water, March 1989. 

Table IB. 

(viii) ASTM D516–07, Standard Test 

Method for Sulfate Ion in Water, 

September 2007. Table IB. 

(ix) ASTM D858–07, Standard Test 

Methods for Manganese in Water. 

August 2007. Table IB. 

(x) ASTM D859–05, Standard Test 

Method for Silica in Water. February 

2005. Table IB. 

(xi) ASTM D888–09, Standard Test 

Methods for Dissolved Oxygen in Water. 

December 2009. Table IB. 

(xii) ASTM D1067–06, Standard Test 

Methods for Acidity or Alkalinity of 

Water. January 2007. Table IB. 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29803 

(xiii) ASTM D1068–05E1, Standard 

Test Methods for Iron in Water. July 

2005. Table IB. 

(xiv) ASTM D1125–95 (Reapproved 

1999), Standard Test Methods for 

Electrical Conductivity and Resistivity 

of Water. December 1995. Table IB. 

(xv) ASTM D1126–02 (Reapproved 

2007)E1, Standard Test Method for 

Hardness in Water. August 2007. Table 

IB. 

(xvi) ASTM D1179–04, Standard Test 

Methods for Fluoride Ion in Water. July 

2004. Table IB. 

(xvii) ASTM D1246–05, Standard Test 

Method for Bromide Ion in Water. 

February 2005. Table IB. 

(xviii) ASTM D1252–06, Standard 

Test Methods for Chemical Oxygen 

Demand (Dichromate Oxygen Demand) 

of Water. February 2006. Table IB. 

(xix) ASTM D1253–08, Standard Test 

Method for Residual Chlorine in Water. 

October 2008. Table IB. 

(xx) ASTM D1293–99, Standard Test 

Methods for pH of Water. March 2000. 

Table IB. 

(xxi) ASTM D1426–08, Standard Test 

Methods for Ammonia Nitrogen in 

Water. September 2008. Table IB. 

(xxii) ASTM D1687–02 (Reapproved 

2007)E1, Standard Test Methods for 

Chromium in Water. August 2007. Table 

IB. 

(xxiii) ASTM D1688–07, Standard 

Test Methods for Copper in Water. 

August 2007. Table IB. 

(xxiv) ASTM D1691–02 (Reapproved 

2007)E1, Standard Test Methods for Zinc 

in Water. August 2007. Table IB. 

(xxv) ASTM D1783–01 (Reapproved 

2007), Standard Test Methods for 

Phenolic Compounds in Water. January 

2008). Table IB. 

(xxvi) ASTM D1886–08, Standard 

Test Methods for Nickel in Water. 

October 2008. Table IB. 

(xxvii) ASTM D1889–00, Standard 

Test Method for Turbidity of Water. 

October 2000. Table IB. 

(xxviii) ASTM D1890–96, Standard 

Test Method for Beta Particle 

Radioactivity of Water. April 1996. 

Table IE. 

(xxix) ASTM D1943–96, Standard 

Test Method for Alpha Particle 

Radioactivity of Water. April 1996. 

Table IE. 

(xxx) ASTM D1976–07, Standard Test 

Method for Elements in Water by 

Inductively-Coupled Argon Plasma 

Atomic Emission Spectroscopy. August 

2007. Table IB. 

(xxxi) ASTM D2036–09, Standard 

Test Methods for Cyanides in Water. 

October 2009. Table IB. 

(xxxii) ASTM D2330–02, Standard 

Test Method for Methylene Blue Active 

Substances. August 2002. Table IB. 

(xxxiii) ASTM D2460–97, Standard 

Test Method for Alpha-Particle-Emitting 

Isotopes of Radium in Water. October 

1997. Table IE. 

(xxxiv) ASTM D2972–08, Standard 

Tests Method for Arsenic in Water. 

October 2008. Table IB. 

(xxxv) ASTM D3223–02 (Reapproved 

2007)E1, Standard Test Method for Total 

Mercury in Water. August 2007. Table 

IB. 

(xxxvi) ASTM D3371–95, Standard 

Test Method for Nitriles in Aqueous 

Solution by Gas-Liquid 

Chromatography, February 1996. Table 

IF. 

(xxxvii) ASTM D3373–03 

(Reapproved 2007)E1, Standard Test 

Method for Vanadium in Water. 

September 2007. Table IB. 

(xxxviii) ASTM D3454–97, Standard 

Test Method for Radium-226 in Water. 

February 1998. Table IE. 

(xxxix) ASTM D3557–02 (Reapproved 

2007)E1, Standard Test Method for 

Cadmium in Water. September 2007. 

Table IB. 

(xl) ASTM D3558–08, Standard Test 

Method for Cobalt in Water. November 

2008. Table IB. 

(xli) ASTM D3559–08, Standard Test 

Methods for Lead in Water. October 

2008. Table IB. 

(xlii) ASTM D3590–02 (Reapproved 

2006), Standard Test Methods for Total 

Kjeldahl Nitrogen in Water. February 

2007. Table IB. 

(xliii) ASTM D3645–08, Standard Test 

Methods for Beryllium in Water. 

October 2008. Table IB. 

(xliv) ASTM D3695–95, Standard Test 

Method for Volatile Alcohols in Water 

by Direct Aqueous-Injection Gas 

Chromatography. April 1995. Table IF. 

(xlv) ASTM D3859–08, Standard Test 

Methods for Selenium in Water. October 

2008. Table IB. 

(xlvi) ASTM D3867–04, Standard Test 

Method for Nitrite-Nitrate in Water. July 

2004. Table IB. 

(xlvii) ASTM D4190–08, Standard 

Test Method for Elements in Water by 

Direct-Current Plasma Atomic Emission 

Spectroscopy. October 2008. Table IB. 

(xlviii) ASTM D4282–02, Standard 

Test Method for Determination of Free 

Cyanide in Water and Wastewater by 

Microdiffusion. August 2002. Table IB. 

(xlix) ASTM D4327–03, Standard Test 

Method for Anions in Water by 

Chemically Suppressed Ion 

Chromatography. January 2003. Table 

IB. 

(l) ASTM D4382–02 (Reapproved 

2007)E1, Standard Test Method for 

Barium in Water, Atomic Absorption 

Spectrophotometry, Graphite Furnace. 

September 2007. Table IB. 

(li) ASTM D4657–92 (Reapproved 

1998), Standard Test Method for 

Polynuclear Aromatic Hydrocarbons in 

Water. January 1993. Table IC. 

(lii) ASTM D4658–08, Standard Test 

Method for Sulfide Ion in Water. August 

2008. Table IB. 

(liii) ASTM D4763–88 (Reapproved 

2001), Standard Practice for 

Identification of Chemicals in Water by 

Fluorescence Spectroscopy. September 

1988. Table IF. 

(liv) ASTM D4839–03, Standard Test 

Method for Total Carbon and Organic 

Carbon in Water by Ultraviolet, or 

Persulfate Oxidation, or Both, and 

Infrared Detection. January 2003. Table 

IB. 

(lv) ASTM D5257–03, Standard Test 

Method for Dissolved Hexavalent 

Chromium in Water by Ion 

Chromatography. January 2003. Table 

IB. 

(lvi) ASTM D5259–92, Standard Test 

Method for Isolation and Enumeration 

of Enterococci from Water by the 

Membrane Filter Procedure. October 

1992. Table IH, Note 9. 

(lvii) ASTM D5392–93, Standard Test 

Method for Isolation and Enumeration 

of Escherichia coli in Water by the TwoStep Membrane Filter Procedure. 

September 1993. Table IH, Note 9. 

(lviii) ASTM D5673–05, Standard Test 

Method for Elements in Water by 

Inductively Coupled Plasma—Mass 

Spectrometry. July 2005. Table IB. 

(lix) ASTM D5907–03, Standard Test 

Method for Filterable and Nonfilterable 

Matter in Water. July 2003. Table IB. 

(lx) ASTM D6503–99, Standard Test 

Method for Enterococci in Water Using 

Enterolert. April 2000. Table IA Note 9, 

Table IH, Note 9. 

(lxi) ASTM. D6508–00 (Reapproved 

2005)E2, Standard Test Method for 

Determination of Dissolved Inorganic 

Anions in Aqueous Matrices Using 

Capillary Ion Electrophoresis and 

Chromate Electrolyte. April 2005. Table 

IB. 

(lxii) ASTM. D6888–09, Standard Test 

Method for Available Cyanide with 

Ligand Displacement and Flow Injection 

Analysis (FIA) Utilizing Gas Diffusion 

Separation and Amperometric 

Detection. October 2009. Table IB, Note 

59. 

(lxiii) ASTM. D6919–09, Standard 

Test Method for Determination of 

Dissolved Alkali and Alkaline Earth 

Cations and Ammonium in Water and 

Wastewater by Ion Chromatography. 

May 2009. Table IB. 

(lxiv) ASTM. D7065–06, Standard 

Test Method for Determination of 

Nonylphenol, Bisphenol A, p-tertOctylphenol, Nonylphenol 

Monoethoxylate and Nonylphenol 

Diethoxylate in Environmental Waters 


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29804 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

by Gas Chromatography Mass 

Spectrometry. January 2007. Table IC. 

(lxv) ASTM. D7237–10, Standard Test 

Method for Free Cyanide with Flow 

Injection Analysis (FIA) Utilizing Gas 

Diffusion Separation and Amperometric 

Detection. June 2010. Table IB. 

(lxvi) ASTM. D7284–08, Standard 

Test Method for Total Cyanide in Water 

by Micro Distillation followed by Flow 

Injection Analysis with Gas Diffusion 

Separation and Amperometric 

Detection. April 2008). Table IB. 

(lxvii) ASTM. D7365–09a, Standard 

Practice for Sampling, Preservation, and 

Mitigating Interferences in Water 

Samples for Analysis of Cyanide. 

October 2009. Table II, Notes 5 and 6. 

(lxviii) ASTM. D7511–09E2, Standard 

Test Method for Total Cyanide by 

Segmented Flow Injection Analysis, InLine Ultraviolet Digestion and 

Amperometric Detection. March 2009. 

Table IB. 

(lxix) ASTM. D7573–09, Standard 

Test Method for Total Carbon and 

Organic Carbon in Water by High 

Temperature Catalytic Combustion and 

Infrared Detection. November 2009. 

Table IB. 

(16) Bran & Luebbe Analyzing 

Technologies, Inc., Elmsford NY 10523. 

(i) Industrial Method Number 378– 

75WA, Hydrogen Ion (pH) Automated 

Electrode Method, Bran & Luebbe 

(Technicon) Auto Analyzer II. October 

1976. Table IB, Note 21. 

(ii) [Reserved] 

(17) CEM Corporation, P.O. Box 200, 

Matthews NC 28106–0200. 

(i) Closed Vessel Microwave Digestion 

of Wastewater Samples for 

Determination of Metals. April 16, 1992. 

Table IB, Note 36. 

(ii) [Reserved] 

(18) Craig R. Chinchilla, 900 Jorie 

Blvd., Suite 35, Oak Brook IL 60523. 

Telephone: 630–645–0600. 

(i) Nitrate by Discrete Analysis Easy 

(1-Reagent) Nitrate Method, 

(Colorimetric, Automated, 1 Reagent). 

Revision 1, November 12, 2011. Table 

IB, Note 62. 

(ii) [Reserved] 

(19) Hach Company, P.O. Box 389, 

Loveland CO 80537. 

(i) Method 8000, Chemical Oxygen 

Demand. Hach Handbook of Water 

Analysis. 1979. Table IB, Note 14. 

(ii) Method 8008, 1,10-Phenanthroline 

Method using FerroVer Iron Reagent for 

Water. 1980. Table IB, Note 22. 

(iii) Method 8009, Zincon Method for 

Zinc. Hach Handbook for Water 

Analysis. 1979. Table IB, Note 33. 

(iv) Method 8034, Periodate Oxidation 

Method for Manganese. Hach Handbook 

for Water Analysis. 1979. Table IB, Note 

23. 

(v) Method 8506, Bicinchoninate 

Method for Copper. Hach Handbook of 

Water Analysis. 1979. Table IB, Note 19. 

(vi) Method 8507, Nitrogen, Nitrite— 

Low Range, Diazotization Method for 

Water and Wastewater. 1979. Table IB, 

Note 25. 

(vii) 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. Table IB, 

Note 63. 

(viii) m-ColiBlue24® Method, for total 

Coliforms and E. coli. Revision 2, 1999. 

Table IA, Note 18; Table IH, Note 17. 

(20) IDEXX Laboratories Inc., One 

Idexx Drive, Westbrook ME 04092. 

(i) Colilert® Method. 2002. Table IA, 

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

and 16. 

(ii) Colilert-18® Method. 2002. Table 

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

15 and 16. 

(iii) Enterolert® Method. 2002. Table 

IA, Note 24; Table IH, Note 12. 

(iv) Quanti-Tray® Method. 2002. 

Table IA, Note 18; Table IH, Notes 14 

and 16. 

(v) Quanti-Tray®/2000 Method. 2002. 

Table IA, Note 18; Table IH, Notes 14 

and 16. 

(21) In-Situ Incorporated, 221 E. 

Lincoln Ave., Ft. Collins CO 80524. 

Telephone: 970–498–1500. 

(i) In-Situ Inc. Method 1002–8–2009, 

Dissolved Oxygen Measurement by 

Optical Probe. 2009. Table IB, Note 64. 

(ii) In-Situ Inc. Method 1003–8–2009, 

Biochemical Oxygen Demand (BOD) 

Measurement by Optical Probe. 2009. 

Table IB, Note 10. 

(iii) In-Situ Inc. Method 1004–8–2009, 

Carbonaceous Biochemical Oxygen 

Demand (CBOD) Measurement by 

Optical Probe. 2009. Table IB, Note 35. 

(22) Journal of Chromatography, 

Elsevier/North-Holland, Inc., Journal 

Information Centre, 52 Vanderbilt 

Avenue, New York NY 10164. (Also 

available from most public libraries. 

(i) Direct Determination of Elemental 

Phosphorus by Gas-Liquid 

Chromatography. Addison, R.F. and 

R.G. Ackman. 47(3): 421–426, 1970. 

Table IB, Note 28. 

(ii) [Reserved] 

(23) Lachat Instruments, 6645 W. Mill 

Road, Milwaukee WI 53218, Telephone: 

414–358–4200. 

(i) QuikChem Method 10–204–00–1– 

X, Digestion and Distillation of Total 

Cyanide in Drinking and Wastewaters 

using MICRO DIST and Determination 

of Cyanide by Flow Injection Analysis. 

Revision 2.2, March 2005. Table IB, 

Note 56. 

(ii) [Reserved] 

(24) Leck Mitchell, Ph.D., P.E., 656 

Independence Valley Dr., Grand 

Junction CO 81507. Telephone: 970– 

244–8661. 

(i) Mitchell Method M5271, 

Determination of Turbidity by 

Nephelometry. Revision 1.0, July 31, 

2008. Table IB, Note 66. 

(ii) Mitchell Method M5331, 

Determination of Turbidity by 

Nephelometry. Revision 1.0, July 31, 

2008. Table IB, Note 65. 

(25) National Council of the Paper 

Industry for Air and Stream 

Improvements, Inc. (NCASI), 260 

Madison Avenue, New York NY 10016. 

(i) 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. 

(ii) [Reserved] 

(26) Oceanography International 

Corporation, 512 West Loop, P.O. Box 

2980, College Station TX 77840. 

(i) OIC Chemical Oxygen Demand 

Method. 1978. Table IB, Note 13. 

(ii) [Reserved] 

(27) OI Analytical, Box 9010, College 

Station TX 77820–9010. 

(i) Method OIA–1677–09, Available 

Cyanide by Ligand Exchange and Flow 

Injection Analysis (FIA). Copyright 

2010. Table IB, Note 59. 

(ii) Method PAI–DK01, Nitrogen, 

Total Kjeldahl, Block Digestion, Steam 

Distillation, Titrimetric Detection. 

Revised December 22, 1994. Table IB, 

Note 39. 

(iii) Method PAI–DK02, Nitrogen, 

Total Kjeldahl, Block Digestion, Steam 

Distillation, Colorimetric Detection. 

Revised December 22, 1994. Table IB, 

Note 40. 

(iv) Method PAI–DK03, Nitrogen, 

Total Kjeldahl, Block Digestion, 

Automated FIA Gas Diffusion. Revised 

December 22, 1994. Table IB, Note 41. 

(28) ORION Research Corporation, 

840 Memorial Drive, Cambridge, 

Massachusetts 02138. 

(i) ORION Research Instruction 

Manual, Residual Chlorine Electrode 

Model 97–70. 1977. Table IB, Note 16. 

(ii) [Reserved] 

(29) Technicon Industrial Systems, 

Tarrytown NY 10591. 

(i) Industrial Method Number 379– 

75WE Ammonia, Automated Electrode 

Method, Technicon Auto Analyzer II. 

February 19, 1976. Table IB, Note 7. 

(ii) [Reserved] 

(30) Thermo Jarrell Ash Corporation, 

27 Forge Parkway, Franklin MA 02038. 

(i) Method AES0029. Direct Current 

Plasma (DCP) Optical Emission 

Spectrometric Method for Trace 

Elemental Analysis of Water and 

Wastes. 1986, Revised 1991. Table IB, 

Note 34. 


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(ii) [Reserved] 

(31) Thermo Scientific, 166 

Cummings Center, Beverly MA 01915. 

Telephone: 1–800–225–1480. 

www.thermoscientific.com. 

(i) Thermo Scientific Orion Method 

AQ4500, Determination of Turbidity by 

Nephelometry. Revision 5, March 12, 

2009. Table IB, Note 67. 

(ii) [Reserved] 

(32) 3M Corporation, 3M Center 

Building 220–9E–10, St. Paul MN 

55144–1000. 

(i) Organochlorine Pesticides and 

PCBs in Wastewater Using EmporeTM

Disk’’ Test Method 3M 0222. Revised 

October 28, 1994. Table IC, Note 8; 

Table ID, Note 8. 

(ii) [Reserved] 

(33) 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) OFR 76–177, Selected Methods of 

the U.S. Geological Survey of Analysis 

of Wastewaters. 1976. Table IE, Note 2. 

(ii) 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. 

(iii) 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. 

(iv) 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. 

(v) 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. 

(vi) 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. 

(vii) 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. 

(viii) 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. 

(ix) 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. 

(x) OFR 98–639, Methods of Analysis 

by the U.S. Geological Survey National 

Water Quality Laboratory— 

Determination of Arsenic and Selenium 

in Water and Sediment by Graphite 

Furnace—Atomic Absorption 

Spectrometry. 1999. Table IB, Note 49. 

(xi) 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. 

(xii) 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. 

(xiii) 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. 

(xiv) 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. 

(xv) 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. 

(xvi) 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. 

(xvii) 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. 

(xviii) 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. 

(xix) 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. 

(xx) 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. 

(34) Waters Corporation, 34 Maple 

Street, Milford MA 01757, Telephone: 

508–482–2131, Fax: 508–482–3625. 

(i) Method D6508, Test Method for 

Determination of Dissolved Inorganic 

Anions in Aqueous Matrices Using 

Capillary Ion Electrophoresis and 

Chromate Electrolyte. Revision 2, 

December 2000. Table IB, Note 54. 

(ii) [Reserved] 

* * * * * 

(e) Sample preservation procedures, 

container materials, and maximum 

allowable holding times for parameters 

are cited in Tables IA, IB, IC, ID, IE, IF, 

IG, and IH are prescribed in Table II. 

Information in the table takes 

precedence over information in specific 

methods or elsewhere. Any person may 

apply for a change from the prescribed 

preservation techniques, container 

materials, and maximum holding times 

applicable to samples taken from a 

specific discharge. Applications for 

such limited use changes may be made 

by letters to the Regional Alternative 

Test Procedure (ATP) Program 

Coordinator or the permitting authority 

in the Region in which the discharge 

will occur. Sufficient data should be 


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provided to assure such changes in 

sample preservation, containers or 

holding times do not adversely affect 

the integrity of the sample. The Regional 

ATP Coordinator or permitting authority 

will review the application and then 

notify the applicant and the appropriate 

State agency of approval or rejection of 

the use of the alternate test procedure. 

A decision to approve or deny any 

request on deviations from the 

prescribed Table II requirements will be 

made within 90 days of receipt of the 

application by the Regional 

Administrator. An analyst may not 

modify any sample preservation and/or 

holding time requirements of an 

approved method unless the 

requirements of this section are met. 

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, 0.0008% 

Na2S2O3 5.

8 hours.22,23

6. Fecal streptococci ................................................ PA, G ................................. Cool, <10 °C, 0.0008% 

Na2S2O3 5.

8 hours.22

7. Enterococci ........................................................... PA, G ................................. Cool, <10 °C, 0.0008% 

Na2S2O3 5.

8 hours.22

8. Salmonella ............................................................ PA, G ................................. Cool, <10 °C, 0.0008% 

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 °C18, H2SO4 to 

pH <2.

28 days. 

Table IB—Metals: 7

18. Chromium VI ...................................................... P, FP, G ............................ Cool, ≤6 °C18, pH = 9.3– 

9.7 20.

28 days. 

35. Mercury (CVAA) ................................................. P, FP, G ............................ HNO3 to pH <2 .................. 28 days. 

35. Mercury (CVAFS) ............................................... FP, G; and FP-lined cap 17 5 mL/L 12N HCl or 5 mL/L 

BrCl 17.

90 days.17

3, 5–8, 12, 13, 19, 20, 22, 26, 29, 30, 32–34, 36, 

37, 45, 47, 51, 52, 58–60, 62, 63, 70–72, 74, 75. 

Metals, except boron, chromium VI, and mercury.

P, FP, G ............................ HNO3 to pH <2, or at least 

24 hours prior to analysis 19.

6 months. 

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

39. Nitrate-nitrite ....................................................... P, FP, G ............................ Cool, ≤6 °C18, H2SO4 to 

pH <2.

28 days. 

40. Nitrite .................................................................. P, FP, G ............................ Cool, ≤6 °C 18 .................... 48 hours. 

41. Oil and grease .................................................... G ........................................ Cool to ≤6 °C18, 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 °C18, 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. 


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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

55. Residue, Nonfilterable (TSS) ............................. P, FP, G ............................ Cool, ≤6 °C 18 .................... 7 days. 

56. Residue, Settleable ............................................ P, FP, G ............................ Cool, ≤6 °C 18 .................... 48 hours. 

57. Residue, Volatile ................................................ P, FP, G ............................ Cool, ≤6 °C 18 .................... 7 days. 

61. Silica ................................................................... P or Quartz ........................ Cool, ≤6 °C 18 .................... 28 days. 

64. Specific conductance ......................................... P, FP, G ............................ Cool, ≤6 °C 18 .................... 28 days. 

65. Sulfate ................................................................ P, FP, G ............................ Cool, ≤6 °C 18 .................... 28 days. 

66. Sulfide ................................................................ P, FP, G ............................ Cool, ≤6 °C 18, add zinc 

acetate plus sodium hydroxide to pH >9.

7 days. 

67. Sulfite ................................................................. P, FP, G ............................ None required .................... Analyze within 15 minutes. 

68. Surfactants ......................................................... P, FP, G ............................ Cool, ≤6 °C 18 .................... 48 hours. 

69. Temperature ....................................................... P, FP, G ............................ None required .................... Analyze. 

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

Table IC—Organic Tests: 8 .

13, 18–20, 22, 24–28, 34–37, 39–43, 45–47, 56, 

76, 104, 105, 108–111, 113. Purgeable 

Halocarbons.

G, FP-lined septum ........... Cool, ≤6 °C 18, 0.008% 

Na2S2O3

5.

14 days. 

6, 57, 106. Purgeable aromatic hydrocarbons ......... G, FP-lined septum ........... Cool, ≤6 °C18, 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 4–510.

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 °C18, 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.

.

Aqueous Samples: Field and Lab Preservation ...... G ........................................ Cool, ≤6 °C 18, 0.008% 

Na2S2O3

5, pH <9.

1 year. 

Solids and Mixed-Phase Samples: Field Preservation.G ........................................ Cool, ≤6 °C 18 .................... 7 days. 

Tissue Samples: Field Preservation ........................ G ........................................ Cool, ≤6 °C 18 .................... 24 hours. 

Solids, Mixed-Phase, and Tissue Samples: Lab 

Preservation.

G ........................................ Freeze, ≤ ¥10 °C ............. 1 year. 

114–118. Alkylated phenols ..................................... G ........................................ Cool, <6 °C, H2SO4 to pH 

<2.

28 days until extraction, 40 

days after extraction. 

119. Adsorbable Organic Halides (AOX) ................. G ........................................ Cool, <6 °C, 0.008% 

Na2S2O3 HNO3 to pH <2.

Hold at least 3 days, but 

not more than 6 months. 

120. Chlorinated Phenolics ...................................... ............................................ 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 °C18, 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. E. coli ................................................................... PA, G ................................. Cool, <10 °C, 0.0008% 

Na2S2O3

5.

8 hours.22

2. Enterococci ........................................................... PA, G ................................. Cool, <10 °C, 0.0008% 

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. 


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29808 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

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 

141.34(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 has 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 Administrator under Sec. 136.3(e). For a grab sample, the holding time begins at the time of collection. For a composite sample 

collected with an automated sampler (e.g., using a 24-hour composite sampler; see 40 CFR 122.21(g)(7)(i) or 40 CFR part 403, Appendix E), the 

holding time begins at the time of the end of collection of the composite sample. For a set of grab samples composited in the field or laboratory, 

the holding time begins at the time of collection of the last grab sample in the set. Some samples may not be stable for the maximum time period 

given in the table. A permittee or monitoring laboratory is obligated to hold the sample for a shorter time if it knows that a shorter time is necessary to maintain sample stability. See 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). Also, Section 9060A of Standard Methods for 

the Examination of Water and Wastewater (20th and 21st editions) addresses dechlorination procedures. 6Sampling, preservation and mitigating interferences in water samples for analysis of cyanide are described in ASTM D7365–09a. There may 

be interferences that are not mitigated by the analytical test methods or D7365–09a. Any technique for removal or suppression of interference 

may be employed, provided the laboratory demonstrates that it more accurately measures cyanide through quality control measures described in 

the analytical test method. Any removal or suppression technique not described in D7365–09a or the analytical test method must be documented 

along with supporting data. 7For dissolved metals, filter grab samples within 15 minutes of collection and before adding preservatives. For a composite sample collected 

with an automated sampler (e.g., using a 24-hour composite sampler; see 40 CFR 122.21(g)(7)(i) or 40 CFR Part 403, Appendix E), filter the 

sample within 15 minutes after completion of collection and before adding preservatives. If it is known or suspected that dissolved sample integrity will be compromised during collection of a composite sample collected automatically over time (e.g., by interchange of a metal between dissolved and suspended forms), collect and filter grab samples to be composited (footnote 2) in place of a composite sample collected automatically. 8Guidance applies to samples to be analyzed by GC, LC, or GC/MS for specific compounds. 

9 If the sample is not adjusted to pH 2, then the sample must be analyzed within seven days of sampling. 

10The pH adjustment is not required if acrolein will not be measured. Samples for acrolein receiving no pH adjustment must be analyzed within 3 days of sampling. 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). 


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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). 

■ 4. Section 136.4 is revised 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 

alternate test procedure (ATP) under 

this paragraph (a) shall: 

(1) Provide the name and address of 

the responsible person or firm making 

the application. 

(2) Identify the pollutant(s) or 

parameter(s) for which nationwide 

approval of an alternate test procedure 

is being requested. 

(3) Provide a detailed description of 

the proposed alternate test procedure, 

together with references to published or 

other studies confirming the general 

applicability of the alternate test 

procedure for the analysis of the 

pollutant(s) or parameter(s) in 

wastewater discharges from 

representative and specified industrial 

or other categories. 

(4) Provide comparability data for the 

performance of the proposed alternative 

test procedure compared to the 

performance of the reference method. 

(b) The National Coordinator may 

request additional information and 

analyses from the applicant in order to 

determine 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 

acceptance or rejection of the alternate 

test procedure for nationwide use in 

CWA programs. If the application is not 

approved, the National Coordinator will 

specify what additional information 

might lead to a reconsideration of the 

application, and notify the Regional 

Alternate Test Procedure Coordinators 

of such rejection. Based on the National 

Coordinator’s rejection of a proposed 

alternate test procedure and an 

assessment of any approvals for limited 

uses for the unapproved method, the 

Regional ATP Coordinator or permitting 

authority may decide to withdraw 

approval of the method for limited use 

in the Region. 

(2) Where the National Coordinator 

approved an applicant’s request for 

nationwide use of an alternate test 

procedure, the National Coordinator 

will notify the applicant that the 

National Coordinator will recommend 

rulemaking to approve the alternate test 

procedure. The National Coordinator 

will notify the Regional ATP 

Coordinator or permitting authorities 

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 

applicant’s application. The Regional 

ATP Coordinator or permitting authority 

will grant approval on a case-by-case 

basis prior to use of the alternate test 

procedure for compliance analyses until 

the alternate test procedure is approved 

by publication in a final rule in the 

Federal Register. 

(3) EPA will propose to amend 40 

CFR Part 136 to include the alternate 

test procedure in § 136.3. EPA shall 

make available for review all the factual 

bases for its proposal, including any 

performance data submitted by the 

applicant and any available EPA 

analysis of those data. 

(4) Following public comment, EPA 

shall publish in the Federal Register a 

final decision on whether to amend 40 

CFR Part 136 to include the alternate 

test procedure as an approved analytical 

method. 

(5) Whenever the National 

Coordinator has approved an applicant’s 

request for nationwide use of an 

alternate test procedure, any person may 

request an approval of the method for 

limited use under § 136.5 from the EPA 

Region. 

■ 5. Section 136.5 is revised to read as 

follows: 

§ 136.5 Approval of alternate test 

procedures for limited use. 

(a) Any person may request the 

Regional Alternate Test Procedure 

(ATP) Coordinator or permitting 

authority 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 or permitting authority 

with a recommendation for or against 

approval. 

(c) Any application for approval of an 

alternate test procedure for limited use 

may be made by letter, email or by hard 

copy. The application shall include the 

following: 

(1) Provide the name and address of 

the applicant and the applicable ID 

number of the existing or pending 

permit and issuing agency for which use 

of the alternate test procedure is 

requested, and the discharge serial 

number. 

(2) Identify the pollutant or parameter 

for which approval of an alternate test 

procedure is being requested. 

(3) Provide justification for using 

testing procedures other than those 

specified in Tables IA through IH of 

§ 136.3, or in the NPDES permit. 

(4) Provide a detailed description of 

the proposed alternate test procedure, 

together with references to published 

studies of the applicability of the 

alternate test procedure to the effluents 

in question. 


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29810 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

(5) Provide comparability data for the 

performance of the proposed alternate 

test procedure compared to the 

performance of the reference method. 

(d) Approval for limited use. (1) 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. 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 or permitting 

authority, to all discharger or facilities 

(and their associated laboratories) 

specified in the approval for the Region. 

If the application is not approved, the 

Regional ATP Coordinator or permitting 

authority shall specify what additional 

information might lead to a 

reconsideration of the application. 

(2) The Regional ATP Coordinator or 

permitting authority will forward a copy 

of every approval and rejection 

notification to the National Alternate 

Test Procedure Coordinator. 

■ 6. Section 136.6 is revised to read as 

follows: 

§ 136.6 Method modifications and 

analytical requirements. 

(a) Definitions of terms used in this 

section—(1) Analyst means the person 

or laboratory using a test procedure 

(analytical method) in this Part. 

(2) Chemistry of the method means 

the reagents and reactions used in a test 

procedure that allow determination of 

the analyte(s) of interest in an 

environmental sample. 

(3) Determinative technique means 

the way in which an analyte is 

identified and quantified (e.g., 

colorimetry, mass spectrometry). 

(4) Equivalent performance means 

that the modified method produces 

results that meet or exceed the QC 

acceptance criteria of the approved 

method. 

(5) Method-defined analyte means an 

analyte defined solely by the method 

used to determine the analyte. Such an 

analyte may be a physical parameter, a 

parameter that is not a specific 

chemical, or a parameter that may be 

comprised of a number of substances. 

Examples of such analytes include 

temperature, oil and grease, total 

suspended solids, total phenolics, 

turbidity, chemical oxygen demand, and 

biochemical oxygen demand. 

(6) QC means ‘‘quality control.’’ 

(b) Method modifications. (1) If the 

underlying chemistry and determinative 

technique in a modified method are 

essentially the same as an approved Part 

136 method, then the modified method 

is an equivalent and acceptable 

alternative to the approved method 

provided the requirements of this 

section are met. However, those who 

develop or use a modification to an 

approved (Part 136) method must 

document that the performance of the 

modified method, in the matrix to 

which the modified method will be 

applied, is equivalent to the 

performance of the approved method. If 

such a demonstration cannot be made 

and documented, then the modified 

method is not an acceptable alternative 

to the approved method. Supporting 

documentation must, if applicable, 

include the routine initial 

demonstration of capability and ongoing 

QC including determination of precision 

and accuracy, detection limits, and 

matrix spike recoveries. Initial 

demonstration of capability typically 

includes analysis of four replicates of a 

mid-level standard and a method 

detection limit study. Ongoing quality 

control typically includes method 

blanks, mid-level laboratory control 

samples, and matrix spikes (QC is as 

specified in the method). The method is 

considered equivalent if the quality 

control requirements in the reference 

method are achieved. The method user’s 

Standard Operating Procedure (SOP) 

must clearly document the 

modifications made to the reference 

method. Examples of allowed method 

modifications are listed in this section. 

The user 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 user may indicate 

the specific paragraph of § 136.6 

allowing the method modification. 

However, specific details of the 

modification need not be provided, but 

must be documented in the Standard 

Operating Procedure (SOP). If the 

method user is uncertain whether a 

method modification is allowed, the 

Regional ATP Coordinator or permitting 

authority 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 be sufficiently sensitive 

and meet or exceed performance of the 

approved method(s) for the analyte(s) of 

interest, as documented by meeting the 

initial and ongoing quality control 

requirements in the method. 

(i) Requirements for establishing 

equivalent performance. If the approved 

method contains QC tests and QC 

acceptance criteria, the modified 

method must use these QC tests and the 

modified method must meet the QC 

acceptance criteria with the following 

conditions: 

(A) The analyst may only rely on QC 

tests and QC acceptance criteria in a 

method if it includes wastewater matrix 

QC tests and QC acceptance criteria 

(e.g., matrix spikes) and both initial 

(start-up) and ongoing QC tests and QC 

acceptance criteria. 

(B) If the approved method does not 

contain QC tests and QC acceptance 

criteria or if the QC tests and QC 

acceptance criteria in the method do not 

meet the requirements of this section, 

then the analyst must employ QC tests 

published in the ‘‘equivalent’’ of a Part 

136 method that has such QC, or the 

essential QC requirements specified at 

136.7, as applicable. If the approved 

method is from a compendium or VCSB 

and the QA/QC requirements are 

published in other parts of that 

organization’s compendium rather than 

within the Part 136 method then that 

part of the organization’s compendium 

must be used for the QC tests. 

(C) In addition, the analyst must 

perform ongoing QC tests, including 

assessment of performance of the 

modified method on the sample matrix 

(e.g., analysis of a matrix spike/matrix 

spike duplicate pair for every twenty 

samples), and analysis of an ongoing 

precision and recovery sample (e.g., 

laboratory fortified blank or blank spike) 

and a blank with each batch of 20 or 

fewer samples. 

(D) If the performance of the modified 

method in the wastewater matrix or 

reagent water does not meet or exceed 

the QC acceptance criteria, the method 

modification may not be used. 

(ii) Requirements for documentation. 

The modified method must be 

documented in a method write-up or an 

addendum that describes the 

modification(s) to the approved method 

prior to the use of the method for 

compliance purposes. The write-up or 

addendum must include a reference 

number (e.g., method number), revision 

number, and revision date so that it may 

be referenced accurately. In addition, 

the organization that uses the modified 

method must document the results of 

QC tests and keep these records, along 

with a copy of the method write-up or 

addendum, for review by an auditor. 

(3) Restrictions. An analyst may not 

modify an approved Clean Water Act 

analytical method for a method-defined 


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analyte. In addition, an analyst may not 

modify an approved method if the 

modification would result in 

measurement of a different form or 

species of an analyte. Changes in 

method procedures are not allowed if 

such changes would alter the defined 

chemistry (i.e., method principle) of the 

unmodified method. For example, 

phenol method 420.1 or 420.4 defines 

phenolics as ferric iron oxidized 

compounds that react with 4- 

aminoantipyrine (4-AAP) at pH 10 after 

being distilled from acid solution. 

Because total phenolics represents a 

group of compounds that all react at 

different efficiencies with 4-AAP, 

changing test conditions likely would 

change the behavior of these different 

phenolic compounds. An analyst may 

not modify any sample collection, 

preservation, or holding time 

requirements of an approved method. 

Such modifications to sample 

collection, preservation, and holding 

time requirements do not fall within the 

scope of the flexibility allowed at 

§ 136.6. Method flexibility refers to 

modifications of the analytical 

procedures used for identification and 

measurement of the analyte only and 

does not apply to sample collection, 

preservation, or holding time 

procedures, which may only be 

modified as specified in § 136.3(e). 

(4) Allowable changes. Except as 

noted under paragraph (b)(3) of this 

section, an analyst may modify an 

approved test procedure (analytical 

method) provided that the underlying 

reactions and principles used in the 

approved method remain essentially the 

same, and provided that the 

requirements of this section are met. If 

equal or better performance can be 

obtained with an alternative reagent, 

then it is allowed. A laboratory wishing 

to use these modifications must 

demonstrate acceptable method 

performance by performing and 

documenting all applicable initial 

demonstration of capability and ongoing 

QC tests and meeting all applicable QC 

acceptance criteria as described in 

§ 136.7. Some examples of the allowed 

types of changes, provided the 

requirements of this section are met 

include: 

(i) Changes between manual method, 

flow analyzer, and discrete 

instrumentation. 

(ii) Changes in chromatographic 

columns or temperature programs. 

(iii) Changes between automated and 

manual sample preparation, such as 

digestions, distillations, and extractions; 

in-line sample preparation is an 

acceptable form of automated sample 

preparation for CWA methods. 

(iv) In general, ICP–MS is a sensitive 

and selective detector for metal analysis; 

however isobaric interference can cause 

problems for quantitative determination, 

as well as identification based on the 

isotope pattern. Interference reduction 

technologies, such as collision cells or 

reaction cells, are designed to reduce 

the effect of spectroscopic interferences 

that may bias results for the element of 

interest. The use of interference 

reduction technologies is allowed, 

provided the method performance 

specifications relevant to ICP–MS 

measurements are met. 

(v) The use of EPA Method 200.2 or 

the sample preparation steps from EPA 

Method 1638, including the use of 

closed-vessel digestion, is allowed for 

EPA Method 200.8, provided the 

method performance specifications 

relevant to the ICP–MS are met. 

(vi) Changes in pH adjustment 

reagents. Changes in compounds used to 

adjust pH are acceptable as long as they 

do not produce interference. For 

example, using a different acid to adjust 

pH in colorimetric methods. 

(vii) Changes in buffer reagents are 

acceptable provided that the changes do 

not produce interferences. 

(viii) Changes in the order of reagent 

addition are acceptable provided that 

the change does not alter the chemistry 

and does not produce an interference. 

For example, using the same reagents, 

but adding them in different order, or 

preparing them in combined or separate 

solutions (so they can be added 

separately), is allowed, provided reagent 

stability or method performance is 

equivalent or improved. 

(ix) Changes in calibration range 

(provided that the modified range 

covers any relevant regulatory limit and 

the method performance specifications 

for calibration are met). 

(x) Changes in calibration model. (A) 

Linear calibration models do not 

adequately fit calibration data with one 

or two inflection points. For example, 

vendor-supplied data acquisition and 

processing software on some 

instruments may provide quadratic 

fitting functions to handle such 

situations. If the calibration data for a 

particular analytical method routinely 

display quadratic character, using 

quadratic fitting functions may be 

acceptable. In such cases, the minimum 

number of calibrators for second order 

fits should be six, and in no case should 

concentrations be extrapolated for 

instrument responses that exceed that of 

the most concentrated calibrator. 

Examples of methods with nonlinear 

calibration functions include chloride 

by SM4500–Cl–E–1997, hardness by 

EPA Method 130.1, cyanide by ASTM 

D6888 or OIA1677, Kjeldahl nitrogen by 

PAI–DK03, and anions by EPA Method 

300.0. 

(B) As an alternative to using the 

average response factor, the quality of 

the calibration may be evaluated using 

the Relative Standard Error (RSE). The 

acceptance criterion for the RSE is the 

same as the acceptance criterion for 

Relative Standard Deviation (RSD), in 

the method. RSE is calculated as: 

Where: 

x′i = Calculated concentration at level i 

xi = Actual concentration of the calibration 

level i 

n = Number of calibration points 

p = Number of terms in the fitting equation 

(average = 1, linear = 2, quadratic = 3) 

(C) Using the RSE as a metric has the 

added advantage of allowing the same 

numerical standard to be applied to the 

calibration model, regardless of the form 

of the model. Thus, if a method states 

that the RSD should be ≤20% for the 

traditional linear model through the 

origin, then the RSE acceptance limit 

can remain ≤20% as well. Similarly, if 

a method provides an RSD acceptance 

limit of ≤15%, then that same figure can 

be used as the acceptance limit for the 

RSE. The RSE may be used as an 

alternative to correlation coefficients 

and coefficients of determination for 

evaluating calibration curves for any of 


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the methods at Part 136. If the method 

includes a numerical criterion for the 

RSD, then the same numerical value is 

used for the RSE. Some older methods 

do not include any criterion for the 

calibration curve—for these methods, if 

RSE is used the value should be ≤20%. 

Note that the use of the RSE is included 

as an alternative to the use of the 

correlation coefficient as a measure of 

the suitability of a calibration curve. It 

is not necessary to evaluate both the 

RSE and the correlation coefficient. 

(xi) Changes in equipment such as 

equipment from a vendor different from 

the one specified in the method. 

(xii) The use of micro or midi 

distillation apparatus in place of macro 

distillation apparatus. 

(xiii) The use of prepackaged reagents. 

(xiv) The use of digital titrators and 

methods where the underlying 

chemistry used for the determination is 

similar to that used in the approved 

method. 

(xv) Use of selected ion monitoring 

(SIM) mode for analytes that cannot be 

effectively analyzed in full-scan mode 

and reach the required sensitivity. False 

positives are more of a concern when 

using SIM analysis, so at a minimum, 

one quantitation and two qualifying 

ions must be monitored for each analyte 

(unless fewer than three ions with 

intensity greater than 15% of the base 

peak are available). The ratio of each of 

the two qualifying ions to the 

quantitation ion must be evaluated and 

should agree with the ratio observed in 

an authentic standard within ±20 

percent. Analyst judgment must be 

applied to the evaluation of ion ratios 

because the ratios can be affected by coeluting compounds present in the 

sample matrix. The signal-to-noise ratio 

of the least sensitive ion should be at 

least 3:1. Retention time in the sample 

should match within 0.05 minute of an 

authentic standard analyzed under 

identical conditions. Matrix 

interferences can cause minor shifts in 

retention time and may be evident as 

shifts in the retention times of the 

internal standards. The total scan time 

should be such that a minimum of eight 

scans are obtained per chromatographic 

peak. 

(xvi) Changes are allowed in purgeand-trap sample volumes or operating 

conditions. Some examples are: 

(A) Changes in purge time and purgegas flow rate. A change in purge time 

and purge-gas flow rate is allowed 

provided that sufficient total purge 

volume is used to achieve the required 

minimum detectible concentration and 

calibration range for all compounds. In 

general, a purge rate in the range 20–200 

mL/min and a total purge volume in the 

range 240–880 mL are recommended. 

(B) Use of nitrogen or helium as a 

purge gas, provided that the required 

sensitivities for all compounds are met. 

(C) Sample temperature during the 

purge state. Gentle heating of the sample 

during purging (e.g., 40 °C) increases 

purging efficiency of hydrophilic 

compounds and may improve sampleto-sample repeatability because all 

samples are purged under precisely the 

same conditions. 

(D) Trap sorbent. Any trap design is 

acceptable, provided that the data 

acquired meet all QC criteria. 

(E) Changes to the desorb time. 

Shortening the desorb time (e.g., from 

4 minutes to 1 minute) may not affect 

compound recoveries, and can shorten 

overall cycle time and significantly 

reduce the amount of water introduced 

to the analytical system, thus improving 

the precision of analysis, especially for 

water-soluble analytes. A desorb time of 

four minutes is recommended, however 

a shorter desorb time may be used, 

provided that all QC specifications in 

the method are met. 

(F) Use of water management 

techniques is allowed. Water is always 

collected on the trap along with the 

analytes and is a significant interference 

for analytical systems (GC and GC/MS). 

Modern water management techniques 

(e.g., dry purge or condensation points) 

can remove moisture from the sample 

stream and improve analytical 

performance. 

(xvii) The following modifications are 

allowable when performing EPA 

Method 625: The base/neutral and acid 

fractions may be added together and 

analyzed as one extract, provided that 

the analytes can be reliably identified 

and quantified in the combined extracts; 

the pH extraction sequence may be 

reversed to better separate acid and 

neutral components; neutral 

components may be extracted with 

either acid or base components; a 

smaller sample volume may be used to 

minimize matrix interferences provided 

matrix interferences are demonstrated 

and documented; alternative surrogate 

and internal standard concentrations 

other than those specified in the method 

are acceptable, provided that method 

performance is not degraded; an 

alternative concentration range may be 

used for the calibration other than the 

range specified in the method; the 

solvent for the calibration standards 

may be changed to match the solvent of 

the final sample extract. 

(xviii) If the characteristics of a 

wastewater matrix prevent efficient 

recovery of organic pollutants and 

prevent the method from meeting QC 

requirements, the analyst may attempt 

to resolve the issue by adding salts to 

the sample, provided that such salts do 

not react with or introduce the target 

pollutant into the sample (as evidenced 

by the analysis of method blanks, 

laboratory control samples, and spiked 

samples that also contain such salts), 

and that all requirements of paragraph 

(b)(2) of this section are met. Samples 

having residual chlorine or other 

halogen must be dechlorinated prior to 

the addition of such salts. 

(xix) If the characteristics of a 

wastewater matrix result in poor sample 

dispersion or reagent deposition on 

equipment and prevent the analyst from 

meeting QC requirements, the analyst 

may attempt to resolve the issue by 

adding a inert surfactant that does not 

affect the chemistry of the method, such 

as Brij-35 or sodium dodecyl sulfate 

(SDS), provided that such surfactant 

does not react with or introduce the 

target pollutant into the sample (as 

evidenced by the analysis of method 

blanks, laboratory control samples, and 

spiked samples that also contain such 

surfactant) and that all requirements of 

paragraph (b)(1) and (b)(2) of this 

section are met. Samples having 

residual chlorine or other halogen must 

be dechlorinated prior to the addition of 

such surfactant. 

(xx) The use of gas diffusion (using 

pH change to convert the analyte to 

gaseous form and/or heat to separate an 

analyte contained in steam from the 

sample matrix) across a hydrophobic 

semi-permeable membrane to separate 

the analyte of interest from the sample 

matrix may be used in place of manual 

or automated distillation in methods for 

analysis such as ammonia, total 

cyanide, total Kjeldahl nitrogen, and 

total phenols. These procedures do not 

replace the digestion procedures 

specified in the approved methods and 

must be used in conjunction with those 

procedures. 

(xxi) Changes in equipment operating 

parameters such as the monitoring 

wavelength of a colorimeter or the 

reaction time and temperature as 

needed to achieve the chemical 

reactions defined in the unmodified 

CWA method. For example, 

molybdenum blue phosphate methods 

have two absorbance maxima, one at 

about 660 nm and another at about 880 

nm. The former is about 2.5 times less 

sensitive than the latter. Wavelength 

choice provides a cost-effective, 

dilution-free means to increase 

sensitivity of molybdenum blue 

phosphate methods. 

(xxii) Interchange of oxidants, such as 

the use of titanium oxide in UV-assisted 

automated digestion of TOC and total 


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phosphorus, as long as complete 

oxidation can be demonstrated. 

(xxii) Use of an axially viewed torch 

with Method 200.7. 

■ 7. Add new § 136.7 to read as follows: 

§ 136.7 Quality assurance and quality 

control. 

The permittee/laboratory shall use 

suitable QA/QC procedures when 

conducting compliance analyses with 

any Part 136 chemical method or an 

alternative method specified by the 

permitting authority. These QA/QC 

procedures are generally included in the 

analytical method or may be part of the 

methods compendium for approved Part 

136 methods from a consensus 

organization. For example, Standard 

Methods contains QA/QC procedures in 

the Part 1000 section of the Standard 

Methods Compendium. The permittee/ 

laboratory shall follow these QA/QC 

procedures, as described in the method 

or methods compendium. If the method 

lacks QA/QC procedures, the permittee/ 

laboratory has the following options to 

comply with the QA/QC requirements: 

(a) Refer to and follow the QA/QC 

published in the ‘‘equivalent’’ EPA 

method for that parameter that has such 

QA/QC procedures; 

(b) Refer to the appropriate QA/QC 

section(s) of an approved Part 136 

method from a consensus organization 

compendium; 

(c)(1) Incorporate the following twelve 

quality control elements, where 

applicable, into the laboratory’s 

documented standard operating 

procedure (SOP) for performing 

compliance analyses when using an 

approved Part 136 method when the 

method lacks such QA/QC procedures. 

One or more of the twelve QC elements 

may not apply to a given method and 

may be omitted if a written rationale is 

provided indicating why the element(s) 

is/are inappropriate for a specific 

method. 

(i) Demonstration of Capability (DOC); 

(ii) Method Detection Limit (MDL); 

(iii) Laboratory reagent blank (LRB), 

also referred to as method blank (MB); 

(iv) Laboratory fortified blank (LFB), 

also referred to as a spiked blank, or 

laboratory control sample (LCS); 

(v) Matrix spike (MS) and matrix 

spike duplicate (MSD), or laboratory 

fortified matrix (LFM) and LFM 

duplicate, may be used for suspected 

matrix interference problems to assess 

precision; 

(vi) Internal standards (for GC/MS 

analyses), surrogate standards (for 

organic analysis) or tracers (for 

radiochemistry); 

(vii) Calibration (initial and 

continuing), also referred to as initial 

calibration verification (ICV) and 

continuing calibration verification 

(CCV); 

(viii) Control charts (or other trend 

analyses of quality control results); 

(ix) Corrective action (root cause 

analysis); 

(x) QC acceptance criteria; 

(xi) Definitions of preparation and 

analytical batches that may drive QC 

frequencies; and 

(xii) Minimum frequency for 

conducting all QC elements. 

(2) These twelve quality control 

elements must be clearly documented in 

the written standard operating 

procedure for each analytical method 

not containing QA/QC procedures, 

where applicable. 

■ 8. Revise Appendix C to Part 136 to 

read as follows. 

APPENDIX C TO PART 136— 

DETERMINATION OF METALS AND 

TRACE ELEMENTS IN WATER AND 

WASTES BY INDUCTIVELY COUPLED 

PLASMA–ATOMIC EMISSION 

SPECTROMETRY METHOD 200.7 

1.0 Scope and Application 

1.1 Inductively coupled plasma-atomic 

emission spectrometry (ICP–AES) is used to 

determine metals and some nonmetals in 

solution. This method is a consolidation of 

existing methods for water, wastewater, and 

solid wastes.1–4 (For analysis of petroleum 

products see References 5 and 6, Section 

16.0). This method is applicable to the 

following analytes: 

Analyte 

Chemical abstract 

services registry 

number (CASRN) 

Aluminum (Al) ........... 7429–90–5 

Antimony (Sb) ........... 7440–36–0 

Arsenic (As) .............. 7440–38–2 

Barium (Ba) .............. 7440–39–3 

Beryllium (Be) ........... 7440–41–7 

Boron (B) .................. 7440–42–8 

Cadmium (Cd) .......... 7440–43–9 

Calcium (Ca) ............. 7440–70–2 

Cerium a (Cr) ............. 7440–45–1 

Chromium (Cr) .......... 7440–47–3 

Cobalt (Co) ............... 7440–48–4 

Copper (Cu) .............. 7440–50–8 

Iron (Fe) .................... 7439–89–6 

Lead (Pb) .................. 7439–92–1 

Lithium (Li) ................ 7439–93–2 

Magnesium (Mg) ....... 7439–95–4 

Manganese (Mn) ...... 7439–96–5 

Mercury (Hg) ............. 7439–97–6 

Molybdenum (Mo) ..... 7439–98–7 

Nickel (Ni) ................. 7440–02–0 

Phosphorus (P) ......... 7723–14–0 

Potassium (K) ........... 7440–09–7 

Selenium (Se) ........... 7782–49–2 

Silica b (Si02) ............. 7631–86–9 

Silver (Ag) ................. 7440–22–4 

Sodium (Na) ............. 7440–23–5 

Strontium (Sr) ........... 7440–24–6 

Thallium (Tl) .............. 7440–28–0 

Tin (Sn) ..................... 7440–31–5 

Titanium (Ti) ............. 7440–32–6 

Analyte 

Chemical abstract 

services registry 

number (CASRN) 

Vanadium (V) ............ 7440–62–2 

Zinc (Zn) ................... 7440–66–6 

a Cerium has been included as method 

analyte for correction of potential interelement 

spectral interference. bThis method is not suitable for the determination of silica in solids. 

1.2 For reference where this method is 

approved for use in compliance monitoring 

programs [e.g., Clean Water Act (NPDES) or 

Safe Drinking Water Act (SDWA)] consult 

both the appropriate sections of the Code of 

Federal Regulation (40 CFR Part 136 Table 1B 

for NPDES, and Part 141 § 141.23 for 

drinking water), and the latest Federal 

Register announcements. 

1.3 ICP–AES can be used to determine 

dissolved analytes in aqueous samples after 

suitable filtration and acid preservation. To 

reduce potential interferences, dissolved 

solids should be <0.2% (w/v) (Section 4.2). 

1.4 With the exception of silver, where 

this method is approved for the 

determination of certain metal and metalloid 

contaminants in drinking water, samples may 

be analyzed directly by pneumatic 

nebulization without acid digestion if the 

sample has been properly preserved with 

acid and has turbidity of <1 NTU at the time 

of analysis. This total recoverable 

determination procedure is referred to as 

‘‘direct analysis’’. However, in the 

determination of some primary drinking 

water metal contaminants, preconcentration 

of the sample may be required prior to 

analysis in order to meet drinking water 

acceptance performance criteria (Sections 

11.2.2 through 11.2.7). 

1.5 For the determination of total 

recoverable analytes in aqueous and solid 

samples a digestion/extraction is required 

prior to analysis when the elements are not 

in solution (e.g., soils, sludges, sediments 

and aqueous samples that may contain 

particulate and suspended solids). Aqueous 

samples containing suspended or particulate 

material 1% (w/v) should be extracted as a 

solid type sample. 

1.6 When determining boron and silica in 

aqueous samples, only plastic, PTFE or 

quartz labware should be used from time of 

sample collection to completion of analysis. 

For accurate determination of boron in solid 

samples only quartz or PTFE beakers should 

be used during acid extraction with 

immediate transfer of an extract aliquot to a 

plastic centrifuge tube following dilution of 

the extract to volume. When possible, 

borosilicate glass should be avoided to 

prevent contamination of these analytes. 

1.7 Silver is only slightly soluble in the 

presence of chloride unless there is a 

sufficient chloride concentration to form the 

soluble chloride complex. Therefore, low 

recoveries of silver may occur in samples, 

fortified sample matrices and even fortified 

blanks if determined as a dissolved analyte 

or by ‘‘direct analysis’’ where the sample has 

not been processed using the total 

recoverable mixed acid digestion. For this 

reason it is recommended that samples be 

digested prior to the determination of silver. 


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The total recoverable sample digestion 

procedure given in this method is suitable for 

the determination of silver in aqueous 

samples containing concentrations up to 0.1 

mg/L. For the analysis of wastewater samples 

containing higher concentrations of silver, 

succeeding smaller volume, well mixed 

aliquots should be prepared until the 

analysis solution contains <0.1 mg/L silver. 

The extraction of solid samples containing 

concentrations of silver >50 mg/kg should be 

treated in a similar manner. Also, the 

extraction of tin from solid samples should 

be prepared again using aliquots <1 g when 

determined sample concentrations exceed 

1%. 

1.8 The total recoverable sample 

digestion procedure given in this method 

will solubilize and hold in solution only 

minimal concentrations of barium in the 

presence of free sulfate. For the analysis of 

barium in samples having varying and 

unknown concentrations of sulfate, analysis 

should be completed as soon as possible after 

sample preparation. 

1.9 The total recoverable sample 

digestion procedure given in this method is 

not suitable for the determination of volatile 

organo-mercury compounds. However, if 

digestion is not required (turbidity <1 NTU), 

the combined concentrations of inorganic 

and organo-mercury in solution can be 

determined by ‘‘direct analysis’’ pneumatic 

nebulization provided the sample solution is 

adjusted to contain the same mixed acid 

(HNO3 + HCl) matrix as the total recoverable 

calibration standards and blank solutions. 

1.10 Detection limits and linear ranges for 

the elements will vary with the wavelength 

selected, the spectrometer, and the matrices. 

Table 1 provides estimated instrument 

detection limits for the listed wavelengths.7

However, actual method detection limits and 

linear working ranges will be dependent on 

the sample matrix, instrumentation, and 

selected operating conditions. 

1.11 Users of the method data should 

state the data-quality objectives prior to 

analysis. Users of the method must document 

and have on file the required initial 

demonstration performance data described in 

Section 9.2 prior to using the method for 

analysis. 

2.0 Summary of Method 

2.1 An aliquot of a well mixed, 

homogeneous aqueous or solid sample is 

accurately weighed or measured for sample 

processing. For total recoverable analysis of 

a solid or an aqueous sample containing 

undissolved material, analytes are first 

solubilized by gentle refluxing with nitric 

and hydrochloric acids. After cooling, the 

sample is made up to volume, is mixed and 

centrifuged or allowed to settle overnight 

prior to analysis. For the determination of 

dissolved analytes in a filtered aqueous 

sample aliquot, or for the ‘‘direct analysis’’ 

total recoverable determination of analytes in 

drinking water where sample turbidity is <1 

NTU, the sample is made ready for analysis 

by the appropriate addition of nitric acid, 

and then diluted to a predetermined volume 

and mixed before analysis. 

2.2 The analysis described in this method 

involves multielemental determinations by 

ICP–AES using sequential or simultaneous 

instruments. The instruments measure 

characteristic atomic-line emission spectra by 

optical spectrometry. Samples are nebulized 

and the resulting aerosol is transported to the 

plasma torch. Element specific emission 

spectra are produced by a radio-frequency 

inductively coupled plasma. The spectra are 

dispersed by a grating spectrometer, and the 

intensities of the line spectra are monitored 

at specific wavelengths by a photosensitive 

device. Photocurrents from the 

photosensitive device are processed and 

controlled by a computer system. A 

background correction technique is required 

to compensate for variable background 

contribution to the determination of the 

analytes. Background must be measured 

adjacent to the analyte wavelength during 

analysis. Various interferences must be 

considered and addressed appropriately as 

discussed in Sections 4.0, 7.0, 9.0, 10.0, and 

11.0. 

3.0 Definitions 

3.1 Calibration Blank—A volume of 

reagent water acidified with the same acid 

matrix as in the calibration standards. The 

calibration blank is a zero standard and is 

used to calibrate the ICP instrument (Section 

7.10.1). 

3.2 Calibration Standard (CAL)—A 

solution prepared from the dilution of stock 

standard solutions. The CAL solutions are 

used to calibrate the instrument response 

with respect to analyte concentration 

(Section 7.9). 

3.3 Dissolved Analyte—The 

concentration of analyte in an aqueous 

sample that will pass through a 0.45 mm 

membrane filter assembly prior to sample 

acidification (Section 11.1). 

3.4 Field Reagent Blank (FRB)—An 

aliquot of reagent water or other blank matrix 

that is placed in a sample container in the 

laboratory and treated as a sample in all 

respects, including shipment to the sampling 

site, exposure to the sampling site 

conditions, storage, preservation, and all 

analytical procedures. The purpose of the 

FRB is to determine if method analytes or 

other interferences are present in the field 

environment (Section 8.5). 

3.5 Instrument Detection Limit (IDL)— 

The concentration equivalent to the analyte 

signal which is equal to three times the 

standard deviation of a series of 10 replicate 

measurements of the calibration blank signal 

at the same wavelength (Table 1.). 

3.6 Instrument Performance Check (IPC) 

Solution—A solution of method analytes, 

used to evaluate the performance of the 

instrument system with respect to a defined 

set of method criteria (Sections 7.11 and 

9.3.4). 

3.7 Internal Standard—Pure analyte(s) 

added to a sample, extract, or standard 

solution in known amount(s) and used to 

measure the relative responses of other 

method analytes that are components of the 

same sample or solution. The internal 

standard must be an analyte that is not a 

sample component (Section 11.5). 

3.8 Laboratory Duplicates (LD1 and 

LD2)—Two aliquots of the same sample 

taken in the laboratory and analyzed 

separately with identical procedures. 

Analyses of LD1 and LD2 indicate precision 

associated with laboratory procedures, but 

not with sample collection, preservation, or 

storage procedures. 

3.9 Laboratory Fortified Blank (LFB)—An 

aliquot of LRB to which known quantities of 

the method analytes are added in the 

laboratory. The LFB is analyzed exactly like 

a sample, and its purpose is to determine 

whether the methodology is in control and 

whether the laboratory is capable of making 

accurate and precise measurements (Sections 

7.10.3 and 9.3.2). 

3.10 Laboratory Fortified Sample Matrix 

(LFM)—An aliquot of an environmental 

sample to which known quantities of the 

method analytes are added in the laboratory. 

The LFM is analyzed exactly like a sample, 

and its purpose is to determine whether the 

sample matrix contributes bias to the 

analytical results. The background 

concentrations of the analytes in the sample 

matrix must be determined in a separate 

aliquot and the measured values in the LFM 

corrected for background concentrations 

(Section 9.4). 

3.11 Laboratory Reagent Blank (LRB)—An 

aliquot of reagent water or other blank 

matrices that are treated exactly as a sample 

including exposure to all glassware, 

equipment, solvents, reagents, and internal 

standards that are used with other samples. 

The LRB is used to determine if method 

analytes or other interferences are present in 

the laboratory environment, reagents, or 

apparatus (Sections 7.10.2 and 9.3.1). 

3.12 Linear Dynamic Range (LDR)—The 

concentration range over which the 

instrument response to an analyte is linear 

(Section 9.2.2). 

3.13 Method Detection Limit (MDL)—The 

minimum concentration of an analyte that 

can be identified, measured, and reported 

with 99% confidence that the analyte 

concentration is greater than zero (Section 

9.2.4 and Table 4.). 

3.14 Plasma Solution—A solution that is 

used to determine the optimum height above 

the work coil for viewing the plasma 

(Sections 7.15 and 10.2.3). 

3.15 Quality Control Sample (QCS)—A 

solution of method analytes of known 

concentrations which is used to fortify an 

aliquot of LRB or sample matrix. The QCS is 

obtained from a source external to the 

laboratory and different from the source of 

calibration standards. It is used to check 

either laboratory or instrument performance 

(Sections 7.12 and 9.2.3). 

3.16 Solid Sample—For the purpose of 

this method, a sample taken from material 

classified as soil, sediment or sludge. 

3.17 Spectral Interference Check (SIC) 

Solution—A solution of selected method 

analytes of higher concentrations which is 

used to evaluate the procedural routine for 

correcting known interelement spectral 

interferences with respect to a defined set of 

method criteria (Sections 7.13, 7.14 and 

9.3.5). 

3.18 Standard Addition—The addition of 

a known amount of analyte to the sample in 

order to determine the relative response of 

the detector to an analyte within the sample 

matrix. The relative response is then used to 


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assess either an operative matrix effect or the 

sample analyte concentration (Sections 9.5.1 

and 11.5). 

3.19 Stock Standard Solution—A 

concentrated solution containing one or more 

method analytes prepared in the laboratory 

using assayed reference materials or 

purchased from a reputable commercial 

source (Section 7.8). 

3.20 Total Recoverable Analyte—The 

concentration of analyte determined either by 

‘‘direct analysis’’ of an unfiltered acid 

preserved drinking water sample with 

turbidity of <1 NTU (Section 11.2.1), or by 

analysis of the solution extract of a solid 

sample or an unfiltered aqueous sample 

following digestion by refluxing with hot 

dilute mineral acid(s) as specified in the 

method (Sections 11.2 and 11.3). 

3.21 Water Sample—For the purpose of 

this method, a sample taken from one of the 

following sources: drinking, surface, ground, 

storm runoff, industrial or domestic 

wastewater. 

4.0 Interferences 

4.1 Spectral interferences are caused by 

background emission from continuous or 

recombination phenomena, stray light from 

the line emission of high concentration 

elements, overlap of a spectral line from 

another element, or unresolved overlap of 

molecular band spectra. 

4.1.1 Background emission and stray light 

can usually be compensated for by 

subtracting the background emission 

determined by measurement(s) adjacent to 

the analyte wavelength peak. Spectral scans 

of samples or single element solutions in the 

analyte regions may indicate not only when 

alternate wavelengths are desirable because 

of severe spectral interference, but also will 

show whether the most appropriate estimate 

of the background emission is provided by an 

interpolation from measurements on both 

sides of the wavelength peak or by the 

measured emission on one side or the other. 

The location(s) selected for the measurement 

of background intensity will be determined 

by the complexity of the spectrum adjacent 

to the wavelength peak. The location(s) used 

for routine measurement must be free of offline spectral interference (interelement or 

molecular) or adequately corrected to reflect 

the same change in background intensity as 

occurs at the wavelength peak. 

4.1.2 Spectral overlaps may be avoided 

by using an alternate wavelength or can be 

compensated for by equations that correct for 

interelement contributions, which involves 

measuring the interfering elements. Some 

potential on-line spectral interferences 

observed for the recommended wavelengths 

are given in Table 2. When operative and 

uncorrected, these interferences will produce 

false-positive determinations and be reported 

as analyte concentrations. The interferences 

listed are only those that occur between 

method analytes. Only interferences of a 

direct overlap nature that were observed with 

a single instrument having a working 

resolution of 0.035 nm are listed. More 

extensive information on interferant effects at 

various wavelengths and resolutions is 

available in Boumans’ Tables.8 Users may 

apply interelement correction factors 

determined on their instruments within 

tested concentration ranges to compensate 

(off-line or on-line) for the effects of 

interfering elements. 

4.1.3 When interelement corrections are 

applied, there is a need to verify their 

accuracy by analyzing spectral interference 

check solutions as described in Section 7.13. 

Interelement corrections will vary for the 

same emission line among instruments 

because of differences in resolution, as 

determined by the grating plus the entrance 

and exit slit widths, and by the order of 

dispersion. Interelement corrections will also 

vary depending upon the choice of 

background correction points. Selecting a 

background correction point where an 

interfering emission line may appear should 

be avoided when practical. Interelement 

corrections that constitute a major portion of 

an emission signal may not yield accurate 

data. Users should not forget that some 

samples may contain uncommon elements 

that could contribute spectral 

interferences.7,8

4.1.4 The interference effects must be 

evaluated for each individual instrument 

whether configured as a sequential or 

simultaneous instrument. For each 

instrument, intensities will vary not only 

with optical resolution but also with 

operating conditions (such as power, viewing 

height and argon flow rate). When using the 

recommended wavelengths given in Table 1, 

the analyst is required to determine and 

document for each wavelength the effect 

from the known interferences given in Table 

2, and to utilize a computer routine for their 

automatic correction on all analyses. To 

determine the appropriate location for offline background correction, the user must 

scan the area on either side adjacent to the 

wavelength and record the apparent emission 

intensity from all other method analytes. 

This spectral information must be 

documented and kept on file. The location 

selected for background correction must be 

either free of off-line interelement spectral 

interference or a computer routine must be 

used for their automatic correction on all 

determinations. If a wavelength other than 

the recommended wavelength is used, the 

user must determine and document both the 

on-line and off-line spectral interference 

effect from all method analytes and provide 

for their automatic correction on all analyses. 

Tests to determine the spectral interference 

must be done using analyte concentrations 

that will adequately describe the 

interference. Normally, 100 mg/L single 

element solutions are sufficient, however, for 

analytes such as iron that may be found at 

high concentration a more appropriate test 

would be to use a concentration near the 

upper LDR limit. See Section 10.4 for 

required spectral interference test criteria. 

4.1.5 When interelement corrections are 

not used, either on-going SIC solutions 

(Section 7.14) must be analyzed to verify the 

absence of interelement spectral interference 

or a computer software routine must be 

employed for comparing the determinative 

data to limits files for notifying the analyst 

when an interfering element is detected in 

the sample at a concentration that will 

produce either an apparent false positive 

concentration, greater than the analyte IDL, 

or false negative analyte concentration, less 

than the 99% lower control limit of the 

calibration blank. When the interference 

accounts for 10% or more of the analyte 

concentration, either an alternate wavelength 

free of interference or another approved test 

procedure must be used to complete the 

analysis. For example, the copper peak at 

213.853 nm could be mistaken for the zinc 

peak at 213.856 nm in solutions with high 

copper and low zinc concentrations. For this 

example, a spectral scan in the 213.8 nm 

region would not reveal the misidentification 

because a single peak near the zinc location 

would be observed. The possibility of this 

misidentification of copper for the zinc peak 

at 213.856 nm can be identified by measuring 

the copper at another emission line, e.g., 

324.754 nm. Users should be aware that, 

depending upon the instrumental resolution, 

alternate wavelengths with adequate 

sensitivity and freedom from interference 

may not be available for all matrices. In these 

circumstances the analyte must be 

determined using another approved test 

procedure. 

4.2 Physical interferences are effects 

associated with the sample nebulization and 

transport processes. Changes in viscosity and 

surface tension can cause significant 

inaccuracies, especially in samples 

containing high dissolved solids or high acid 

concentrations. If physical interferences are 

present, they must be reduced by such means 

as a high-solids nebulizer, diluting the 

sample, using a peristaltic pump, or using an 

appropriate internal standard element. 

Another problem that can occur with high 

dissolved solids is salt buildup at the tip of 

the nebulizer, which affects aerosol flow rate 

and causes instrumental drift. This problem 

can be controlled by a high-solids nebulizer, 

wetting the argon prior to nebulization, using 

a tip washer, or diluting the sample. Also, it 

has been reported that better control of the 

argon flow rates, especially for the nebulizer, 

improves instrument stability and precision; 

this is accomplished with the use of mass 

flow controllers. 

4.3 Chemical interferences include 

molecular-compound formation, ionization 

effects, and solute-vaporization effects. 

Normally, these effects are not significant 

with the ICP–AES technique. If observed, 

they can be minimized by careful selection 

of operating conditions (such as incident 

power and observation height), by buffering 

of the sample, by matrix matching, and by 

standard-addition procedures. Chemical 

interferences are highly dependent on matrix 

type and the specific analyte element. 

4.4 Memory interferences result when 

analytes in a previous sample contribute to 

the signals measured in a new sample. 

Memory effects can result from sample 

deposition on the uptake tubing to the 

nebulizer, and from the buildup of sample 

material in the plasma torch and spray 

chamber. The site where these effects occur 

is dependent on the element and can be 

minimized by flushing the system with a 

rinse blank between samples (Section 7.10.4). 

The possibility of memory interferences 

should be recognized within an analytical 

run and suitable rinse times should be used 


srobinson on DSK4SPTVN1PROD with RULES2
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to reduce them. The rinse times necessary for 

a particular element must be estimated prior 

to analysis. This may be achieved by 

aspirating a standard containing elements 

corresponding to either their LDR or a 

concentration ten times those usually 

encountered. The aspiration time should be 

the same as a normal sample analysis period, 

followed by analysis of the rinse blank at 

designated intervals. The length of time 

required to reduce analyte signals to within 

a factor of two of the method detection limit, 

should be noted. Until the required rinse 

time is established, this method requires a 

rinse period of at least 60 seconds between 

samples and standards. If a memory 

interference is suspected, the sample must be 

re-analyzed after a long rinse period. 

5.0 Safety 

5.1 The toxicity or carcinogenicity of 

each reagent used in this method have not 

been fully established. Each chemical should 

be regarded as a potential health hazard and 

exposure to these compounds should be as 

low as reasonably achievable. Each 

laboratory is responsible for maintaining a 

current awareness file of OSHA regulations 

regarding the safe handling of the chemicals 

specified in this method.9–12 A reference file 

of material data handling sheets should also 

be made available to all personnel involved 

in the chemical analysis. Specifically, 

concentrated nitric and hydrochloric acids 

present various hazards and are moderately 

toxic and extremely irritating to skin and 

mucus membranes. Use these reagents in a 

fume hood whenever possible and if eye or 

skin contact occurs, flush with large volumes 

of water. Always wear safety glasses or a 

shield for eye protection, protective clothing 

and observe proper mixing when working 

with these reagents. 

5.2 The acidification of samples 

containing reactive materials may result in 

the release of toxic gases, such as cyanides 

or sulfides. Acidification of samples should 

be done in a fume hood. 

5.3 All personnel handling 

environmental samples known to contain or 

to have been in contact with human waste 

should be immunized against known disease 

causative agents. 

5.4 The inductively coupled plasma 

should only be viewed with proper eye 

protection from the ultraviolet emissions. 

5.5 It is the responsibility of the user of 

this method to comply with relevant disposal 

and waste regulations. For guidance see 

Sections 14.0 and 15.0. 

6.0 Equipment and Supplies 

6.1 Inductively coupled plasma emission 

spectrometer: 

6.1.1 Computer-controlled emission 

spectrometer with background-correction 

capability. 

The spectrometer must be capable of meeting 

and complying with the requirements 

described and referenced in Section 2.2. 

6.1.2 Radio-frequency generator 

compliant with FCC regulations. 

6.1.3 Argon gas supply—High purity 

grade (99.99%). When analyses are 

conducted frequently, liquid argon is more 

economical and requires less frequent 

replacement of tanks than compressed argon 

in conventional cylinders. 

6.1.4 A variable speed peristaltic pump is 

required to deliver both standard and sample 

solutions to the nebulizer. 

6.1.5 (Optional) Mass flow controllers to 

regulate the argon flow rates, especially the 

aerosol transport gas, are highly 

recommended. Their use will provide more 

exacting control of reproducible plasma 

conditions. 

6.2 Analytical balance, with capability to 

measure to 0.1 mg, for use in weighing solids, 

for preparing standards, and for determining 

dissolved solids in digests or extracts. 

6.3 A temperature adjustable hot plate 

capable of maintaining a temperature of 95 

°C. 

6.4 (Optional) A temperature adjustable 

block digester capable of maintaining a 

temperature of 95 °C and equipped with 250 

mL constricted digestion tubes. 

6.5 (Optional) A steel cabinet centrifuge 

with guard bowl, electric timer and brake. 

6.6 A gravity convection drying oven 

with thermostatic control capable of 

maintaining 180 °C ± 5 °C. 

6.7 (Optional) An air displacement 

pipetter capable of delivering volumes 

ranging from 0.1–2500 mL with an assortment 

of high quality disposable pipet tips. 

6.8 Mortar and pestle, ceramic or 

nonmetallic material. 

6.9 Polypropylene sieve, 5-mesh (4 mm 

opening). 

6.10 Labware—For determination of trace 

levels of elements, contamination and loss 

are of prime consideration. Potential 

contamination sources include improperly 

cleaned laboratory apparatus and general 

contamination within the laboratory 

environment from dust, etc. A clean 

laboratory work area designated for trace 

element sample handling must be used. 

Sample containers can introduce positive 

and negative errors in the determination of 

trace elements by contributing contaminants 

through surface desorption or leaching, or 

depleting element concentrations through 

adsorption processes. All reusable labware 

(glass, quartz, polyethylene, PTFE, FEP, etc.) 

should be sufficiently clean for the task 

objectives. Several procedures found to 

provide clean labware include washing with 

a detergent solution, rinsing with tap water, 

soaking for four hours or more in 20% (v/v) 

nitric acid or a mixture of HNO3 and HCl 

(1+2+9), rinsing with reagent water and 

storing clean.2 3 Chromic acid cleaning 

solutions must be avoided because chromium 

is an analyte. 

6.10.1 Glassware—Volumetric flasks, 

graduated cylinders, funnels and centrifuge 

tubes (glass and/or metal-free plastic). 

6.10.2 Assorted calibrated pipettes. 

6.10.3 Conical Phillips beakers (Corning 

1080–250 or equivalent), 250 mL with 50 mm 

watch glasses. 

6.10.4 Griffin beakers, 250 mL with 75 

mm watch glasses and (optional) 75 mm 

ribbed watch glasses. 

6.10.5 (Optional) PTFE and/or quartz 

Griffin beakers, 250 mL with PTFE covers. 

6.10.6 Evaporating dishes or high-form 

crucibles, porcelain, 100 mL capacity. 

6.10.7 Narrow-mouth storage bottles, FEP 

(fluorinated ethylene propylene) with screw 

closure, 125 mL to 1 L capacities. 

6.10.8 One-piece stem FEP wash bottle 

with screw closure, 125 mL capacity. 

7.0 Reagents and Standards 

7.1 Reagents may contain elemental 

impurities which might affect analytical data. 

Only high-purity reagents that conform to the 

American Chemical Society specifications 13

should be used whenever possible. If the 

purity of a reagent is in question, analyze for 

contamination. All acids used for this 

method must be of ultra high-purity grade or 

equivalent. Suitable acids are available from 

a number of manufacturers. Redistilled acids 

prepared by sub-boiling distillation are 

acceptable. 

7.2 Hydrochloric acid, concentrated 

(sp.gr. 1.19)—HCl. 

7.2.1 Hydrochloric acid (1+1)—Add 500 

mL concentrated HCl to 400 mL reagent 

water and dilute to 1 L. 

7.2.2 Hydrochloric acid (1+4)—Add 200 

mL concentrated HCl to 400 mL reagent 

water and dilute to 1 L. 

7.2.3 Hydrochloric acid (1+20)—Add 10 

mL concentrated HCl to 200 mL reagent 

water. 

7.3 Nitric acid, concentrated (sp.gr. 

1.41)—HNO3. 

7.3.1 Nitric acid (1+1)—Add 500 mL 

concentrated HNO3 to 400 mL reagent water 

and dilute to 1 L. 

7.3.2 Nitric acid (1+2)—Add 100 mL 

concentrated HNO3 to 200 mL reagent water. 

7.3.3 Nitric acid (1+5)—Add 50 mL 

concentrated HNO3 to 250 mL reagent water. 

7.3.4 Nitric acid (1+9)—Add 10 mL 

concentrated HNO3 to 90 mL reagent water. 

7.4 Reagent water. All references to water 

in this method refer to ASTM Type I grade 

water.14

7.5 Ammonium hydroxide, concentrated 

(sp.gr. 0.902). 

7.6 Tartaric acid, ACS reagent grade. 

7.7 Hydrogen peroxide, 50%, stabilized 

certified reagent grade. 

7.8 Standard Stock Solutions—Stock 

standards may be purchased or prepared 

from ultra-high purity grade chemicals 

(99.99–99.999% pure). All compounds must 

be dried for one hour at 105 °C, unless 

otherwise specified. It is recommended that 

stock solutions be stored in FEP bottles. 

Replace stock standards when succeeding 

dilutions for preparation of calibration 

standards cannot be verified. 

CAUTION: Many of these chemicals are 

extremely toxic if inhaled or swallowed 

(Section 5.1). Wash hands thoroughly after 

handling. 

Typical stock solution preparation 

procedures follow for 1 L quantities, but for 

the purpose of pollution prevention, the 

analyst is encouraged to prepare smaller 

quantities when possible. Concentrations are 

calculated based upon the weight of the pure 

element or upon the weight of the compound 

multiplied by the fraction of the analyte in 

the compound 

From pure element, 


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where: gravimetric factor = the weight 

fraction of the analyte in the compound 

7.8.1 Aluminum solution, stock, 1 mL = 

1000 mg Al: Dissolve 1.000 g of aluminum 

metal, weighed accurately to at least four 

significant figures, in an acid mixture of 4.0 

mL of (1+1) HCl and 1 mL of concentrated 

HNO3 in a beaker. Warm beaker slowly to 

effect solution. When dissolution is 

complete, transfer solution quantitatively to 

a 1 L flask, add an additional 10.0 mL of 

(1+1) HCl and dilute to volume with reagent 

water. 

7.8.2 Antimony solution, stock, 1 mL = 

1000 mg Sb: Dissolve 1.000 g of antimony 

powder, weighed accurately to at least four 

significant figures, in 20.0 mL (1+1) HNO3

and 10.0 mL concentrated HCl. Add 100 mL 

reagent water and 1.50 g tartaric acid. Warm 

solution slightly to effect complete 

dissolution. Cool solution and add reagent 

water to volume in a 1 L volumetric flask. 

7.8.3 Arsenic solution, stock, 1 mL = 

1000 mg As: Dissolve 1.320 g of As2O3 (As 

fraction = 0.7574), weighed accurately to at 

least four significant figures, in 100 mL of 

reagent water containing 10.0 mL 

concentrated NH4OH. Warm the solution 

gently to effect dissolution. Acidify the 

solution with 20.0 mL concentrated HNO3

and dilute to volume in a 1 L volumetric 

flask with reagent water. 

7.8.4 Barium solution, stock, 1 mL = 1000 

mg Ba: Dissolve 1.437 g BaCO3 (Ba fraction = 

0.6960), weighed accurately to at least four 

significant figures, in 150 mL (1+2) HNO3

with heating and stirring to degas and 

dissolve compound. Let solution cool and 

dilute with reagent water in 1 L volumetric 

flask. 

7.8.5 Beryllium solution, stock, 1 mL = 

1000 mg Be: DO NOT DRY. Dissolve 19.66 g 

BeSO4•4H2O (Be fraction = 0.0509), weighed 

accurately to at least four significant figures, 

in reagent water, add 10.0 mL concentrated 

HNO3, and dilute to volume in a 1 L 

volumetric flask with reagent water. 

7.8.6 Boron solution, stock, 1 mL = 1000 

mg B: DO NOT DRY. Dissolve 5.716 g 

anhydrous H3BO3 (B fraction = 0.1749), 

weighed accurately to at least four significant 

figures, in reagent water and dilute in a 1 L 

volumetric flask with reagent water. Transfer 

immediately after mixing to a clean FEP 

bottle to minimize any leaching of boron 

from the glass volumetric container. Use of 

a nonglass volumetric flask is recommended 

to avoid boron contamination from 

glassware. 

7.8.7 Cadmium solution, stock, 1 mL = 

1000 mg Cd: Dissolve 1.000 g Cd metal, acid 

cleaned with (1+9) HNO3, weighed 

accurately to at least four significant figures, 

in 50 mL (1+1) HNO3 with heating to effect 

dissolution. Let solution cool and dilute with 

reagent water in a 1 L volumetric flask. 

7.8.8 Calcium solution, stock, 1 mL = 

1000 mg Ca: Suspend 2.498 g CaCO3 (Ca 

fraction = 0.4005), dried at 180 °C for one 

hour before weighing, weighed accurately to 

at least four significant figures, in reagent 

water and dissolve cautiously with a 

minimum amount of (1+1) HNO3. Add 10.0 

mL concentrated HNO3 and dilute to volume 

in a 1 L volumetric flask with reagent water. 

7.8.9 Cerium solution, stock, 1 mL = 1000 

mg Ce: Slurry 1.228 g CeO2 (Ce fraction = 

0.8141), weighed accurately to at least four 

significant figures, in 100 mL concentrated 

HNO3 and evaporate to dryness. Slurry the 

residue in 20 mL H2O, add 50 mL 

concentrated HNO3, with heat and stirring 

add 60 mL 50% H2O2 dropwise in 1 mL 

increments allowing periods of stirring 

between the 1 mL additions. Boil off excess 

H2O2 before diluting to volume in a 1 L 

volumetric flask with reagent water. 

7.8.10 Chromium solution, stock, 1 mL = 

1000 mg Cr: Dissolve 1.923 g CrO3 (Cr fraction 

= 0.5200), weighed accurately to at least four 

significant figures, in 120 mL (1+5) HNO3. 

When solution is complete, dilute to volume 

in a 1 L volumetric flask with reagent water. 

7.8.11 Cobalt solution, stock, 1 mL = 1000 

mg Co: Dissolve 1.000 g Co metal, acid 

cleaned with (1+9) HNO3, weighed 

accurately to at least four significant figures, 

in 50.0 mL (1+1) HNO3. Let solution cool and 

dilute to volume in a 1 L volumetric flask 

with reagent water. 

7.8.12 Copper solution, stock, 1 mL = 

1000 mg Cu: Dissolve 1.000 g Cu metal, acid 

cleaned with (1+9) HNO3, weighed 

accurately to at least four significant figures, 

in 50.0 mL (1+1) HNO3 with heating to effect 

dissolution. Let solution cool and dilute in a 

1 L volumetric flask with reagent water. 

7.8.13 Iron solution, stock, 1 mL = 1000 

mg Fe: Dissolve 1.000 g Fe metal, acid cleaned 

with (1+1) HCl, weighed accurately to four 

significant figures, in 100 mL (1+1) HCl with 

heating to effect dissolution. Let solution 

cool and dilute with reagent water in a 1 L 

volumetric flask. 

7.8.14 Lead solution, stock, 1 mL = 1000 

mg Pb: Dissolve 1.599 g Pb(NO3)2 (Pb fraction 

= 0.6256), weighed accurately to at least four 

significant figures, in a minimum amount of 

(1+1) HNO3. Add 20.0 mL (1+1) HNO3 and 

dilute to volume in a 1 L volumetric flask 

with reagent water. 

7.8.15 Lithium solution, stock, 1 mL = 

1000 mg Li: Dissolve 5.324 g Li2CO3 (Li 

fraction = 0.1878), weighed accurately to at 

least four significant figures, in a minimum 

amount of (1+1) HCl and dilute to volume in 

a 1 L volumetric flask with reagent water. 

7.8.16 Magnesium solution, stock, 1 mL = 

1000 mg Mg: Dissolve 1.000 g cleanly 

polished Mg ribbon, accurately weighed to at 

least four significant figures, in slowly added 

5.0 mL (1+1) HCl (CAUTION: reaction is 

vigorous). Add 20.0 mL (1+1) HNO3 and 

dilute to volume in a 1 L volumetric flask 

with reagent water. 

7.8.17 Manganese solution, stock, 1 mL = 

1000 mg Mn: Dissolve 1.000 g of manganese 

metal, weighed accurately to at least four 

significant figures, in 50 mL (1+1) HNO3 and 

dilute to volume in a 1 L volumetric flask 

with reagent water. 

7.8.18 Mercury solution, stock, 1 mL = 

1000 mg Hg: DO NOT DRY. CAUTION: highly 

toxic element. Dissolve 1.354 g HgCl2 (Hg 

fraction = 0.7388) in reagent water. Add 50.0 

mL concentrated HNO3 and dilute to volume 

in 1 L volumetric flask with reagent water. 

7.8.19 Molybdenum solution, stock, 1 mL 

= 1000 mg Mo: Dissolve 1.500 g MoO3 (Mo 

fraction = 0.6666), weighed accurately to at 

least four significant figures, in a mixture of 

100 mL reagent water and 10.0 mL 

concentrated NH4OH, heating to effect 

dissolution. Let solution cool and dilute with 

reagent water in a 1 L volumetric flask. 

7.8.20 Nickel solution, stock, 1 mL = 

1000 mg Ni: Dissolve 1.000 g of nickel metal, 

weighed accurately to at least four significant 

figures, in 20.0 mL hot concentrated HNO3, 

cool, and dilute to volume in a 1 L 

volumetric flask with reagent water. 

7.8.21 Phosphorus solution, stock, 1 mL = 

1000 mg P: Dissolve 3.745 g NH4H2PO4 (P 

fraction = 0.2696), weighed accurately to at 

least four significant figures, in 200 mL 

reagent water and dilute to volume in a 1 L 

volumetric flask with reagent water. 

7.8.22 Potassium solution, stock, 1 mL = 

1000 mg K: Dissolve 1.907 g KCl (K fraction 

= 0.5244) dried at 110 °C, weighed accurately 

to at least four significant figures, in reagent 

water, add 20 mL (1+1) HCl and dilute to 

volume in a 1 L volumetric flask with reagent 

water. 

7.8.23 Selenium solution, stock, 1 mL = 

1000 mg Se: Dissolve 1.405 g SeO2 (Se 

fraction = 0.7116), weighed accurately to at 

least four significant figures, in 200 mL 

reagent water and dilute to volume in a 1 L 

volumetric flask with reagent water. 

7.8.24 Silica solution, stock, 1 mL = 1000 

mg SiO2: DO NOT DRY. Dissolve 2.964 g 

(NH4)2SiF6, weighed accurately to at least 

four significant figures, in 200 mL (1+20) HCl 

with heating at 85 °C to effect dissolution. Let 

solution cool and dilute to volume in a 1 L 

volumetric flask with reagent water. 

7.8.25 Silver solution, stock, 1 mL = 1000 

mg Ag: Dissolve 1.000 g Ag metal, weighed 

accurately to at least four significant figures, 

in 80 mL (1+1) HNO3 with heating to effect 

dissolution. Let solution cool and dilute with 

reagent water in a 1 L volumetric flask. Store 


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solution in amber bottle or wrap bottle 

completely with aluminum foil to protect 

solution from light. 

7.8.26 Sodium solution, stock, 1 mL = 

1000 mg Na: Dissolve 2.542 g NaCl (Na 

fraction = 0.3934), weighed accurately to at 

least four significant figures, in reagent water. 

Add 10.0 mL concentrated HNO3 and dilute 

to volume in a 1 L volumetric flask with 

reagent water. 

7.8.27 Strontium solution, stock, 1 mL = 

1000 mg Sr: Dissolve 1.685 g SrCO3 (Sr 

fraction = 0.5935), weighed accurately to at 

least four significant figures, in 200 mL 

reagent water with dropwise addition of 100 

mL (1+1) HCl. Dilute to volume in a 1 L 

volumetric flask with reagent water. 

7.8.28 Thallium solution, stock, 1 mL = 

1000 mg Tl: Dissolve 1.303 g TlNO3 (Tl 

fraction = 0.7672), weighed accurately to at 

least four significant figures, in reagent water. 

Add 10.0 mL concentrated HNO3 and dilute 

to volume in a 1 L volumetric flask with 

reagent water. 

7.8.29 Tin solution, stock, 1 mL = 1000 mg 

Sn: Dissolve 1.000 g Sn shot, weighed 

accurately to at least four significant figures, 

in an acid mixture of 10.0 mL concentrated 

HCl and 2.0 mL (1+1) HNO3 with heating to 

effect dissolution. Let solution cool, add 200 

mL concentrated HCl, and dilute to volume 

in a 1 L volumetric flask with reagent water. 

7.8.30 Titanium solution, stock, 1 mL = 

1000 mg Ti: DO NOT DRY. Dissolve 6.138 g 

(NH4)2TiO(C2O4)2•H2O (Ti fraction = 0.1629), 

weighed accurately to at least four significant 

figures, in 100 mL reagent water. Dilute to 

volume in a 1 L volumetric flask with reagent 

water. 

7.8.31 Vanadium solution, stock, 1 mL = 

1000 mg V: Dissolve 1.000 g V metal, acid 

cleaned with (1+9) HNO3, weighed 

accurately to at least four significant figures, 

in 50 mL (1+1) HNO3 with heating to effect 

dissolution. Let solution cool and dilute with 

reagent water to volume in a 1 L volumetric 

flask. 

7.8.32 Yttrium solution, stock 1 mL = 

1000 mg Y: Dissolve 1.270 g Y2O3 (Y fraction 

= 0.7875), weighed accurately to at least four 

significant figures, in 50 mL (1+1) HNO3, 

heating to effect dissolution. Cool and dilute 

to volume in a 1 L volumetric flask with 

reagent water. 

7.8.33 Zinc solution, stock, 1 mL = 1000 

mg Zn: Dissolve 1.000 g Zn metal, acid 

cleaned with (1+9) HNO3, weighed 

accurately to at least four significant figures, 

in 50 mL (1+1) HNO3 with heating to effect 

dissolution. Let solution cool and dilute with 

reagent water to volume in a 1 L volumetric 

flask. 

7.9 Mixed Calibration Standard 

Solutions—For the analysis of total 

recoverable digested samples prepare mixed 

calibration standard solutions (see Table 3) 

by combining appropriate volumes of the 

stock solutions in 500 mL volumetric flasks 

containing 20 mL (1+1) HNO3 and 20 mL 

(1+1) HCl and dilute to volume with reagent 

water. Prior to preparing the mixed 

standards, each stock solution should be 

analyzed separately to determine possible 

spectral interferences or the presence of 

impurities. Care should be taken when 

preparing the mixed standards to ensure that 

the elements are compatible and stable 

together. To minimize the opportunity for 

contamination by the containers, it is 

recommended to transfer the mixed-standard 

solutions to acid-cleaned, never-used FEP 

fluorocarbon (FEP) bottles for storage. Fresh 

mixed standards should be prepared, as 

needed, with the realization that 

concentrations can change on aging. 

Calibration standards not prepared from 

primary standards must be initially verified 

using a certified reference solution. For the 

recommended wavelengths listed in Table 1 

some typical calibration standard 

combinations are given in Table 3. 

NOTE: If the addition of silver to the 

recommended mixed-acid calibration 

standard results in an initial precipitation, 

add 15 mL of reagent water and warm the 

flask until the solution clears. For this acid 

combination, the silver concentration should 

be limited to 0.5 mg/L. 

7.10 Blanks—Four types of blanks are 

required for the analysis. The calibration 

blank is used in establishing the analytical 

curve, the laboratory reagent blank is used to 

assess possible contamination from the 

sample preparation procedure, the laboratory 

fortified blank is used to assess routine 

laboratory performance and a rinse blank is 

used to flush the instrument uptake system 

and nebulizer between standards, check 

solutions, and samples to reduce memory 

interferences. 

7.10.1 The calibration blank for aqueous 

samples and extracts is prepared by 

acidifying reagent water to the same 

concentrations of the acids as used for the 

standards. The calibration blank should be 

stored in a FEP bottle. 

7.10.2 The laboratory reagent blank (LRB) 

must contain all the reagents in the same 

volumes as used in the processing of the 

samples. The LRB must be carried through 

the same entire preparation scheme as the 

samples including sample digestion, when 

applicable. 

7.10.3 The laboratory fortified blank 

(LFB) is prepared by fortifying an aliquot of 

the laboratory reagent blank with all analytes 

to a suitable concentration using the 

following recommended criteria: Ag 0.1 mg/ 

L, K 5.0 mg/L and all other analytes 0.2 mg/ 

L or a concentration approximately 100 times 

their respective MDL, whichever is greater. 

The LFB must be carried through the same 

entire preparation scheme as the samples 

including sample digestion, when applicable. 

7.10.4 The rinse blank is prepared by 

acidifying reagent water to the same 

concentrations of acids as used in the 

calibration blank and stored in a convenient 

manner. 

7.11 Instrument Performance Check (IPC) 

Solution—The IPC solution is used to 

periodically verify instrument performance 

during analysis. It should be prepared in the 

same acid mixture as the calibration 

standards by combining method analytes at 

appropriate concentrations. Silver must be 

limited to <0.5 mg/L; while potassium and 

phosphorus because of higher MDLs and 

silica because of potential contamination 

should be at concentrations of 10 mg/L. For 

other analytes a concentration of 2 mg/L is 

recommended. The IPC solution should be 

prepared from the same standard stock 

solutions used to prepare the calibration 

standards and stored in an FEP bottle. 

Agency programs may specify or request that 

additional instrument performance check 

solutions be prepared at specified 

concentrations in order to meet particular 

program needs. 

7.12 Quality Control Sample (QCS)— 

Analysis of a QCS is required for initial and 

periodic verification of calibration standards 

or stock standard solutions in order to verify 

instrument performance. The QCS must be 

obtained from an outside source different 

from the standard stock solutions and 

prepared in the same acid mixture as the 

calibration standards. The concentration of 

the analytes in the QCS solution should be 

1 mg/L, except silver, which must be limited 

to a concentration of 0.5 mg/L for solution 

stability. The QCS solution should be stored 

in a FEP bottle and analyzed as needed to 

meet data-quality needs. A fresh solution 

should be prepared quarterly or more 

frequently as needed. 

7.13 Spectral Interference Check (SIC) 

Solutions—When interelement corrections 

are applied, SIC solutions are needed 

containing concentrations of the interfering 

elements at levels that will provide an 

adequate test of the correction factors. 

7.13.1 SIC solutions containing (a) 300 

mg/L Fe; (b) 200 mg/L AL; (c) 50 mg/L Ba; 

(d) 50 mg/L Be; (e) 50 mg/L Cd; (f) 50 mg/ 

L Ce; (g) 50 mg/L Co; (h) 50 mg/L Cr; (i) 50 

mg/L Cu; (j) 50 mg/L Mn; (k) 50 mg/L Mo; 

(l) 50 mg/L Ni; (m) 50 mg/L Sn; (n) 50 mg/ 

L SiO2; (o) 50 mg/L Ti; (p) 50 mg/L Tl and 

(q) 50 mg/L V should be prepared in the same 

acid mixture as the calibration standards and 

stored in FEP bottles. These solutions can be 

used to periodically verify a partial list of the 

on-line (and possible off-line) interelement 

spectral correction factors for the 

recommended wavelengths given in Table 1. 

Other solutions could achieve the same 

objective as well. (Multielement SIC 

solutions3 may be prepared and substituted 

for the single element solutions provided an 

analyte is not subject to interference from 

more than one interferant in the solution.) 

Note: If wavelengths other than those 

recommended in Table 1 are used, other 

solutions different from those above (a 

through q) may be required. 

7.13.2 For interferences from iron and 

aluminum, only those correction factors 

(positive or negative) when multiplied by 100 

to calculate apparent analyte concentrations 

that exceed the determined analyte IDL or 

fall below the lower 3-sigma control limit of 

the calibration blank need be tested on a 

daily basis. 

7.13.3 For the other interfering elements, 

only those correction factors (positive or 

negative) when multiplied by 10 to calculate 

apparent analyte concentrations that exceed 

the determined analyte IDL or fall below the 

lower 3-sigma control limit of the calibration 

blank need be tested on a daily basis. 

7.13.4 If the correction routine is 

operating properly, the determined apparent 

analyte(s) concentration from analysis of 

each interference solution (a through q) 

should fall within a specific concentration 

range bracketing the calibration blank. This 


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concentration range is calculated by 

multiplying the concentration of the 

interfering element by the value of the 

correction factor being tested and dividing by 

10. If after subtraction of the calibration 

blank the apparent analyte concentration is 

outside (above or below) this range, a change 

in the correction factor of more than 10% 

should be suspected. The cause of the change 

should be determined and corrected and the 

correction factor should be updated. 

Note: The SIC solution should be analyzed 

more than once to confirm a change has 

occurred with adequate rinse time between 

solutions and before subsequent analysis of 

the calibration blank. 

7.13.5 If the correction factors tested on a 

daily basis are found to be within the 10% 

criteria for five consecutive days, the 

required verification frequency of those 

factors in compliance may be extended to a 

weekly basis. Also, if the nature of the 

samples analyzed is such (e.g., finished 

drinking water) that they do not contain 

concentrations of the interfering elements at 

the 10 mg/L level, daily verification is not 

required; however, all interelement spectral 

correction factors must be verified annually 

and updated, if necessary. 

7.13.6 If the instrument does not display 

negative concentration values, fortify the SIC 

solutions with the elements of interest at 1 

mg/L and test for analyte recoveries that are 

below 95%. In the absence of measurable 

analyte, over-correction could go undetected 

because a negative value could be reported as 

zero. 

7.14 For instruments without 

interelement correction capability or when 

interelement corrections are not used, SIC 

solutions (containing similar concentrations 

of the major components in the samples, e.g., 

10 mg/L) can serve to verify the absence of 

effects at the wavelengths selected. These 

data must be kept on file with the sample 

analysis data. If the SIC solution confirms an 

operative interference that is 10% of the 

analyte concentration, the analyte must be 

determined using a wavelength and 

background correction location free of the 

interference or by another approved test 

procedure. Users are advised that high salt 

concentrations can cause analyte signal 

suppressions and confuse interference tests. 

7.15 Plasma Solution—The plasma 

solution is used for determining the optimum 

viewing height of the plasma above the work 

coil prior to using the method (Section 10.2). 

The solution is prepared by adding a 5 mL 

aliquot from each of the stock standard 

solutions of arsenic, lead, selenium, and 

thallium to a mixture of 20 mL (1+1) nitric 

acid and 20 mL (1+1) hydrochloric acid and 

diluting to 500 mL with reagent water. Store 

in a FEP bottle. 

8.0 Sample Collection, Preservation, and 

Storage 

8.1 Prior to the collection of an aqueous 

sample, consideration should be given to the 

type of data required, (i.e., dissolved or total 

recoverable), so that appropriate preservation 

and pretreatment steps can be taken. The pH 

of all aqueous samples must be tested 

immediately prior to aliquoting for 

processing or ‘‘direct analysis’’ to ensure the 

sample has been properly preserved. If 

properly acid preserved, the sample can be 

held up to six months before analysis. 

8.2 For the determination of the dissolved 

elements, the sample must be filtered 

through a 0.45 mm pore diameter membrane 

filter at the time of collection or as soon 

thereafter as practically possible. (Glass or 

plastic filtering apparatus are recommended 

to avoid possible contamination. Only plastic 

apparatus should be used when the 

determinations of boron and silica are 

critical.) Use a portion of the filtered sample 

to rinse the filter flask, discard this portion 

and collect the required volume of filtrate. 

Acidify the filtrate with (1+1) nitric acid 

immediately following filtration to pH <2. 

8.3 For the determination of total 

recoverable elements in aqueous samples, 

samples are not filtered, but acidified with 

(1+1) nitric acid to pH <2 (normally, 3 mL 

of (1+1) acid per liter of sample is sufficient 

for most ambient and drinking water 

samples). Preservation may be done at the 

time of collection, however, to avoid the 

hazards of strong acids in the field, transport 

restrictions, and possible contamination it is 

recommended that the samples be returned 

to the laboratory within two weeks of 

collection and acid preserved upon receipt in 

the laboratory. Following acidification, the 

sample should be mixed, held for 16 hours, 

and then verified to be pH <2 just prior 

withdrawing an aliquot for processing or 

‘‘direct analysis’’. If for some reason such as 

high alkalinity the sample pH is verified to 

be >2, more acid must be added and the 

sample held for 16 hours until verified to be 

pH <2. See Section 8.1. 

Note: When the nature of the sample is 

either unknown or is known to be hazardous, 

acidification should be done in a fume hood. 

See Section 5.2. 

8.4 Solid samples require no preservation 

prior to analysis other than storage at 4 °C. 

There is no established holding time 

limitation for solid samples. 

8.5 For aqueous samples, a field blank 

should be prepared and analyzed as required 

by the data user. Use the same container and 

acid as used in sample collection. 

9.0 Quality Control 

9.1 Each laboratory using this method is 

required to operate a formal quality control 

(QC) program. The minimum requirements of 

this program consist of an initial 

demonstration of laboratory capability, and 

the periodic analysis of laboratory reagent 

blanks, fortified blanks and other laboratory 

solutions as a continuing check on 

performance. The laboratory is required to 

maintain performance records that define the 

quality of the data thus generated. 

9.2 Initial Demonstration of Performance 

(mandatory). 

9.2.1 The initial demonstration of 

performance is used to characterize 

instrument performance (determination of 

linear dynamic ranges and analysis of quality 

control samples) and laboratory performance 

(determination of method detection limits) 

prior to analyses conducted by this method. 

9.2.2 Linear dynamic range (LDR)—The 

upper limit of the LDR must be established 

for each wavelength utilized. It must be 

determined from a linear calibration 

prepared in the normal manner using the 

established analytical operating procedure 

for the instrument. The LDR should be 

determined by analyzing succeedingly higher 

standard concentrations of the analyte until 

the observed analyte concentration is no 

more than 10% below the stated 

concentration of the standard. Determined 

LDRs must be documented and kept on file. 

The LDR which may be used for the analysis 

of samples should be judged by the analyst 

from the resulting data. Determined sample 

analyte concentrations that are greater than 

90% of the determined upper LDR limit must 

be diluted and reanalyzed. The LDRs should 

be verified annually or whenever, in the 

judgment of the analyst, a change in 

analytical performance caused by either a 

change in instrument hardware or operating 

conditions would dictate they be 

redetermined. 

9.2.3 Quality control sample (QCS)— 

When beginning the use of this method, on 

a quarterly basis, after the preparation of 

stock or calibration standard solutions or as 

required to meet data-quality needs, verify 

the calibration standards and acceptable 

instrument performance with the preparation 

and analyses of a QCS (Section 7.12). To 

verify the calibration standards the 

determined mean concentrations from three 

analyses of the QCS must be within 5% of 

the stated values. If the calibration standard 

cannot be verified, performance of the 

determinative step of the method is 

unacceptable. The source of the problem 

must be identified and corrected before either 

proceeding on with the initial determination 

of method detection limits or continuing 

with on-going analyses. 

9.2.4 Method detection limit (MDL)— 

MDLs must be established for all 

wavelengths utilized, using reagent water 

(blank) fortified at a concentration of two to 

three times the estimated instrument 

detection limit.15 To determine MDL values, 

take seven replicate aliquots of the fortified 

reagent water and process through the entire 

analytical method. Perform all calculations 

defined in the method and report the 

concentration values in the appropriate units. 

Calculate the MDL as follows: 

MDL = (t) × (S) 

Where: 

t = students’ t value for a 99% confidence 

level and a standard deviation estimate 

with n-1 degrees of freedom [t = 3.14 for 

seven replicates] 

S = standard deviation of the replicate 

analyses 

Note: If additional confirmation is desired, 

reanalyze the seven replicate aliquots on two 

more nonconsecutive days and again 

calculate the MDL values for each day. An 

average of the three MDL values for each 

analyte may provide for a more appropriate 

MDL estimate. If the relative standard 

deviation (RSD) from the analyses of the 

seven aliquots is <10%, the concentration 

used to determine the analyte MDL may have 

been inappropriately high for the 

determination. If so, this could result in the 

calculation of an unrealistically low MDL. 

Concurrently, determination of MDL in 


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reagent water represents a best case situation 

and does not reflect possible matrix effects of 

real world samples. However, successful 

analyses of LFMs (Section 9.4) and the 

analyte addition test described in Section 

9.5.1 can give confidence to the MDL value 

determined in reagent water. Typical single 

laboratory MDL values using this method are 

given in Table 4. 

The MDLs must be sufficient to detect 

analytes at the required levels according to 

compliance monitoring regulation (Section 

1.2). MDLs should be determined annually, 

when a new operator begins work or 

whenever, in the judgment of the analyst, a 

change in analytical performance caused by 

either a change in instrument hardware or 

operating conditions would dictate they be 

redetermined. 

9.3 Assessing Laboratory Performance 

(mandatory) 

9.3.1 Laboratory reagent blank (LRB)— 

The laboratory must analyze at least one LRB 

(Section 7.10.2) with each batch of 20 or 

fewer samples of the same matrix. LRB data 

are used to assess contamination from the 

laboratory environment. LRB values that 

exceed the MDL indicate laboratory or 

reagent contamination should be suspected. 

When LRB values constitute 10% or more of 

the analyte level determined for a sample or 

is 2.2 times the analyte MDL whichever is 

greater, fresh aliquots of the samples must be 

prepared and analyzed again for the affected 

analytes after the source of contamination 

has been corrected and acceptable LRB 

values have been obtained. 

9.3.2 Laboratory fortified blank (LFB)— 

The laboratory must analyze at least one LFB 

(Section 7.10.3) with each batch of samples. 

Calculate accuracy as percent recovery using 

the following equation: 

Where: 

R = percent recovery 

LFB = laboratory fortified blank 

LRB = laboratory reagent blank 

s = concentration equivalent of analyte added 

to fortify the LBR solution 

If the recovery of any analyte falls outside 

the required control limits of 85–115%, that 

analyte is judged out of control, and the 

source of the problem should be identified 

and resolved before continuing analyses. 

9.3.3 The laboratory must use LFB 

analyses data to assess laboratory 

performance against the required control 

limits of 85–115% (Section 9.3.2). When 

sufficient internal performance data become 

available (usually a minimum of 20–30 

analyses), optional control limits can be 

developed from the mean percent recovery 

(x) and the standard deviation (S) of the 

mean percent recovery. These data can be 

used to establish the upper and lower control 

limits as follows: 

UPPER CONTROL LIMIT = x + 3S 

LOWER CONTROL LIMIT = x ¥ 3S 

The optional control limits must be equal 

to or better than the required control limits 

of 85–115%. After each five to 10 new 

recovery measurements, new control limits 

can be calculated using only the most recent 

20–30 data points. Also, the standard 

deviation (S) data should be used to establish 

an on-going precision statement for the level 

of concentrations included in the LFB. These 

data must be kept on file and be available for 

review. 

9.3.4 Instrument performance check (IPC) 

solution—For all determinations the 

laboratory must analyze the IPC solution 

(Section 7.11) and a calibration blank 

immediately following daily calibration, after 

every 10th sample (or more frequently, if 

required) and at the end of the sample run. 

Analysis of the calibration blank should 

always be < the analyte IDL, but greater than 

the lower 3-sigma control limit of the 

calibration blank. Analysis of the IPC 

solution immediately following calibration 

must verify that the instrument is within 5% 

of calibration with a relative standard 

deviation <3% from replicate integrations 4. 

Subsequent analyses of the IPC solution must 

be within 10% of calibration. If the 

calibration cannot be verified within the 

specified limits, reanalyze either or both the 

IPC solution and the calibration blank. If the 

second analysis of the IPC solution or the 

calibration blank confirm calibration to be 

outside the limits, sample analysis must be 

discontinued, the cause determined, 

corrected and/or the instrument recalibrated. 

All samples following the last acceptable IPC 

solution must be reanalyzed. The analysis 

data of the calibration blank and IPC solution 

must be kept on file with the sample analyses 

data. 

9.3.5 Spectral interference check (SIC) 

solution—For all determinations the 

laboratory must periodically verify the 

interelement spectral interference correction 

routine by analyzing SIC solutions. The 

preparation and required periodic analysis of 

SIC solutions and test criteria for verifying 

the interelement interference correction 

routine are given in Section 7.13. Special 

cases where on-going verification is required 

are described in Section 7.14. 

9.4 Assessing Analyte Recovery and Data 

Quality. 

9.4.1 Sample homogeneity and the 

chemical nature of the sample matrix can 

affect analyte recovery and the quality of the 

data. Taking separate aliquots from the 

sample for replicate and fortified analyses 

can in some cases assess the effect. Unless 

otherwise specified by the data user, 

laboratory or program, the following 

laboratory fortified matrix (LFM) procedure 

(Section 9.4.2) is required. Also, other tests 

such as the analyte addition test (Section 

9.5.1) and sample dilution test (Section 9.5.2) 

can indicate if matrix effects are operative. 

9.4.2 The laboratory must add a known 

amount of each analyte to a minimum of 10% 

of the routine samples. In each case the LFM 

aliquot must be a duplicate of the aliquot 

used for sample analysis and for total 

recoverable determinations added prior to 

sample preparation. For water samples, the 

added analyte concentration must be the 

same as that used in the laboratory fortified 

blank (Section 7.10.3). For solid samples, 

however, the concentration added should be 

expressed as mg/kg and is calculated for a 

one gram aliquot by multiplying the added 

analyte concentration (mg/L) in solution by 

the conversion factor 100 (mg/L × 0.1L/ 

0.001kg = 100, Section 12.5). (For notes on 

Ag, Ba, and Sn see Sections 1.7 and 1.8.) 

Over time, samples from all routine sample 

sources should be fortified. 

Note: The concentration of calcium, 

magnesium, sodium and strontium in 

environmental waters, along with iron and 

aluminum in solids can vary greatly and are 

not necessarily predictable. Fortifying these 

analytes in routine samples at the same 

concentration used for the LFB may prove to 

be of little use in assessing data quality for 

these analytes. For these analytes sample 

dilution and reanalysis using the criteria 

given in Section 9.5.2 is recommended. Also, 

if specified by the data user, laboratory or 

program, samples can be fortified at higher 

concentrations, but even major constituents 

should be limited to <25 mg/L so as not to 

alter the sample matrix and affect the 

analysis. 

9.4.3 Calculate the percent recovery for 

each analyte, corrected for background 

concentrations measured in the unfortified 

sample, and compare these values to the 

designated LFM recovery range of 70–130% 

or a 3-sigma recovery range calculated from 

the regression equations given in Table 9.16

Recovery calculations are not required if the 

concentration added is less than 30% of the 

sample background concentration. Percent 

recovery may be calculated in units 

appropriate to the matrix, using the following 

equation: 

Where: 

R = percent recovery 

Cs = fortified sample concentration 

C = sample background concentration 

s = concentration equivalent of analyte added 

to fortify the sample 

9.4.4 If the recovery of any analyte falls 

outside the designated LFM recovery range, 

and the laboratory performance for that 

analyte is shown to be in control (Section 

9.3), the recovery problem encountered with 

the fortified sample is judged to be matrix 

related, not system related. The data user 

should be informed that the result for that 

analyte in the unfortified sample is suspect 

due to either the heterogeneous nature of the 

sample or matrix effects and analysis by 

method of standard addition or the use of an 

internal standard(s) (Section 11.5) should be 

considered. 

9.4.5 Where reference materials are 

available, they should be analyzed to provide 

additional performance data. The analysis of 

reference samples is a valuable tool for 

demonstrating the ability to perform the 

method acceptably. Reference materials 

containing high concentrations of analytes 

can provide additional information on the 

performance of the spectral interference 

correction routine. 

9.5 Assess the possible need for the 

method of standard additions (MSA) or 

internal standard elements by the following 

tests. Directions for using MSA or internal 

standard(s) are given in Section 11.5. 

9.5.1 Analyte addition test: An analyte(s) 

standard added to a portion of a prepared 


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sample, or its dilution, should be recovered 

to within 85% to 115% of the known value. 

The analyte(s) addition should produce a 

minimum level of 20 times and a maximum 

of 100 times the method detection limit. If 

the analyte addition is <20% of the sample 

analyte concentration, the following dilution 

test should be used. If recovery of the 

analyte(s) is not within the specified limits, 

a matrix effect should be suspected, and the 

associated data flagged accordingly. The 

method of additions or the use of an 

appropriate internal standard element may 

provide more accurate data. 

9.5.2 Dilution test: If the analyte 

concentration is sufficiently high (minimally, 

a factor of 50 above the instrument detection 

limit in the original solution but <90% of the 

linear limit), an analysis of a 1 + 4 dilution 

should agree (after correction for the fivefold 

dilution) within 10% of the original 

determination. If not, a chemical or physical 

interference effect should be suspected and 

the associated data flagged accordingly. The 

method of standard additions or the use of 

an internal-standard element may provide 

more accurate data for samples failing this 

test. 

10.0 Calibration and Standardization 

10.1 Specific wavelengths are listed in 

Table 1. Other wavelengths may be 

substituted if they can provide the needed 

sensitivity and are corrected for spectral 

interference. However, because of the 

difference among various makes and models 

of spectrometers, specific instrument 

operating conditions cannot be given. The 

instrument and operating conditions utilized 

for determination must be capable of 

providing data of acceptable quality to the 

program and data user. The analyst should 

follow the instructions provided by the 

instrument manufacturer unless other 

conditions provide similar or better 

performance for a task. Operating conditions 

for aqueous solutions usually vary from 

1100–1200 watts forward power, 15–16 mm 

viewing height, 15–19 L/min. argon coolant 

flow, 0.6–1 L/min. argon aerosol flow, 1–1.8 

mL/min. sample pumping rate with a one 

minute preflush time and measurement time 

near 1 s per wavelength peak (for sequential 

instruments) and near 10 s per sample (for 

simultaneous instruments). Use of the Cu/Mn 

intensity ratio at 324.754 nm and 257.610 nm 

(by adjusting the argon aerosol flow) has been 

recommended as a way to achieve repeatable 

interference correction factors.17

10.2 Prior to using this method optimize 

the plasma operating conditions. The 

following procedure is recommended for 

vertically configured plasmas. The purpose 

of plasma optimization is to provide a 

maximum signal-to-background ratio for the 

least sensitive element in the analytical array. 

The use of a mass flow controller to regulate 

the nebulizer gas flow rate greatly facilitates 

the procedure. 

10.2.1 Ignite the plasma and select an 

appropriate incident rf power with minimum 

reflected power. Allow the instrument to 

become thermally stable before beginning. 

This usually requires at least 30 to 60 

minutes of operation. While aspirating the 

1000 mg/mL solution of yttrium (Section 

7.8.32), follow the instrument manufacturer’s 

instructions and adjust the aerosol carrier gas 

flow rate through the nebulizer so a 

definitive blue emission region of the plasma 

extends approximately from 5–20 mm above 

the top of the work coil.18 Record the 

nebulizer gas flow rate or pressure setting for 

future reference. 

10.2.2 After establishing the nebulizer gas 

flow rate, determine the solution uptake rate 

of the nebulizer in mL/min. by aspirating a 

known volume calibration blank for a period 

of at least three minutes. Divide the spent 

volume by the aspiration time (in minutes) 

and record the uptake rate. Set the peristaltic 

pump to deliver the uptake rate in a steady 

even flow. 

10.2.3 After horizontally aligning the 

plasma and/or optically profiling the 

spectrometer, use the selected instrument 

conditions from Sections 10.2.1 and 10.2.2, 

and aspirate the plasma solution (Section 

7.15), containing 10 mg/mL each of As, Pb, Se 

and Tl. Collect intensity data at the 

wavelength peak for each analyte at 1 mm 

intervals from 14–18 mm above the top of the 

work coil. (This region of the plasma is 

commonly referred to as the analytical 

zone.)19 Repeat the process using the 

calibration blank. Determine the net signal to 

blank intensity ratio for each analyte for each 

viewing height setting. Choose the height for 

viewing the plasma that provides the largest 

intensity ratio for the least sensitive element 

of the four analytes. If more than one position 

provides the same ratio, select the position 

that provides the highest net intensity counts 

for the least sensitive element or accept a 

compromise position of the intensity ratios of 

all four analytes. 

10.2.4 The instrument operating 

condition finally selected as being optimum 

should provide the lowest reliable 

instrument detection limits and method 

detection limits. Refer to Tables 1 and 4 for 

comparison of IDLs and MDLs, respectively. 

10.2.5 If either the instrument operating 

conditions, such as incident power and/or 

nebulizer gas flow rate are changed, or a new 

torch injector tube having a different orifice 

i.d. is installed, the plasma and plasma 

viewing height should be reoptimized. 

10.2.6 Before daily calibration and after 

the instrument warmup period, the nebulizer 

gas flow must be reset to the determined 

optimized flow. If a mass flow controller is 

being used, it should be reset to the recorded 

optimized flow rate. In order to maintain 

valid spectral interelement correction 

routines the nebulizer gas flow rate should be 

the same from day-to-day (<2% change). The 

change in signal intensity with a change in 

nebulizer gas flow rate for both ‘‘hard’’ (Pb 

220.353 nm) and ‘‘soft’’ (Cu 324.754) lines is 

illustrated in Figure 1. 

10.3 Before using the procedure (Section 

11.0) to analyze samples, there must be data 

available documenting initial demonstration 

of performance. The required data and 

procedure is described in Section 9.2. This 

data must be generated using the same 

instrument operating conditions and 

calibration routine (Section 11.4) to be used 

for sample analysis. These documented data 

must be kept on file and be available for 

review by the data user. 

10.4 After completing the initial 

demonstration of performance, but before 

analyzing samples, the laboratory must 

establish and initially verify an interelement 

spectral interference correction routine to be 

used during sample analysis. A general 

description concerning spectral interference 

and the analytical requirements for 

background correction and for correction of 

interelement spectral interference in 

particular are given in Section 4.1. To 

determine the appropriate location for 

background correction and to establish the 

interelement interference correction routine, 

repeated spectral scan about the analyte 

wavelength and repeated analyses of the 

single element solutions may be required. 

Criteria for determining an interelement 

spectral interference is an apparent positive 

or negative concentration on the analyte that 

is outside the 3-sigma control limits of the 

calibration blank for the analyte. (The uppercontrol limit is the analyte IDL.) Once 

established, the entire routine must be 

initially and periodically verified annually, 

or whenever there is a change in instrument 

operating conditions (Section 10.2.5). Only a 

portion of the correction routine must be 

verified more frequently or on a daily basis. 

Test criteria and required solutions are 

described in Section 7.13. Initial and 

periodic verification data of the routine 

should be kept on file. Special cases where 

on-going verification are required is 

described in Section 7.14. 

11.0 Procedure 

11.1 Aqueous Sample Preparation— 

Dissolved Analytes 

11.1.1 For the determination of dissolved 

analytes in ground and surface waters, pipet 

an aliquot (20 mL) of the filtered, acid 

preserved sample into a 50 mL 

polypropylene centrifuge tube. Add an 

appropriate volume of (1 + 1) nitric acid to 

adjust the acid concentration of the aliquot 

to approximate a 1% (v/v) nitric acid 

solution (e.g., add 0.4 mL (1 + 1) HNO3 to a 

20 mL aliquot of sample). Cap the tube and 

mix. The sample is now ready for analysis 

(Section 1.3). Allowance for sample dilution 

should be made in the calculations. (If 

mercury is to be determined, a separate 

aliquot must be additionally acidified to 

contain 1% (v/v) HCl to match the signal 

response of mercury in the calibration 

standard and reduce memory interference 

effects. Section 1.9). 

Note: If a precipitate is formed during 

acidification, transport, or storage, the 

sample aliquot must be treated using the 

procedure described in Sections 11.2.2 

through 11.2.7 prior to analysis. 

11.2 Aqueous Sample Preparation—Total 

Recoverable Analytes 

11.2.1 For the ‘‘direct analysis’’ of total 

recoverable analytes in drinking water 

samples containing turbidity <1 NTU, treat 

an unfiltered acid preserved sample aliquot 

using the sample preparation procedure 

described in Section 11.1.1 while making 

allowance for sample dilution in the data 

calculation (Section 1.2). For the 

determination of total recoverable analytes in 

all other aqueous samples or for 


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preconcentrating drinking water samples 

prior to analysis follow the procedure given 

in Sections 11.2.2 through 11.2.7. 

11.2.2 For the determination of total 

recoverable analytes in aqueous samples 

(other than drinking water with <1 NTU 

turbidity), transfer a 100 mL (1 mL) aliquot 

from a well mixed, acid preserved sample to 

a 250 mL Griffin beaker (Sections 1.2, 1.3, 

1.6, 1.7, 1.8, and 1.9). (When necessary, 

smaller sample aliquot volumes may be 

used.) 

Note: If the sample contains undissolved 

solids >1%, a well mixed, acid preserved 

aliquot containing no more than 1 g 

particulate material should be cautiously 

evaporated to near 10 mL and extracted using 

the acid-mixture procedure described in 

Sections 11.3.3 through 11.3.6. 

11.2.3 Add 2 mL (1+1) nitric acid and 1.0 

mL of (1+1) hydrochloric acid to the beaker 

containing the measured volume of sample. 

Place the beaker on the hot plate for solution 

evaporation. The hot plate should be located 

in a fume hood and previously adjusted to 

provide evaporation at a temperature of 

approximately but no higher than 85 °C. (See 

the following note.) The beaker should be 

covered with an elevated watch glass or other 

necessary steps should be taken to prevent 

sample contamination from the fume hood 

environment. 

Note: For proper heating adjust the 

temperature control of the hot plate such that 

an uncovered Griffin beaker containing 50 

mL of water placed in the center of the hot 

plate can be maintained at a temperature 

approximately but no higher than 85 °C. 

(Once the beaker is covered with a watch 

glass the temperature of the water will rise 

to approximately 95 °C.) 

11.2.4 Reduce the volume of the sample 

aliquot to about 20 mL by gentle heating at 

85 °C. DO NOT BOIL. This step takes about 

two hours for a 100 mL aliquot with the rate 

of evaporation rapidly increasing as the 

sample volume approaches 20 mL. (A spare 

beaker containing 20 mL of water can be used 

as a gauge.) 

11.2.5 Cover the lip of the beaker with a 

watch glass to reduce additional evaporation 

and gently reflux the sample for 30 minutes. 

(Slight boiling may occur, but vigorous 

boiling must be avoided to prevent loss of the 

HCl-H2O azeotrope.) 

11.2.6 Allow the beaker to cool. 

Quantitatively transfer the sample solution to 

a 50 mL volumetric flask, make to volume 

with reagent water, stopper and mix. 

11.2.7 Allow any undissolved material to 

settle overnight, or centrifuge a portion of the 

prepared sample until clear. (If after 

centrifuging or standing overnight the sample 

contains suspended solids that would clog 

the nebulizer, a portion of the sample may be 

filtered for their removal prior to analysis. 

However, care should be exercised to avoid 

potential contamination from filtration.) The 

sample is now ready for analysis. Because the 

effects of various matrices on the stability of 

diluted samples cannot be characterized, all 

analyses should be performed as soon as 

possible after the completed preparation. 

11.3 Solid Sample Preparation—Total 

Recoverable Analytes 

11.3.1 For the determination of total 

recoverable analytes in solid samples, mix 

the sample thoroughly and transfer a portion 

(>20 g) to tared weighing dish, weigh the 

sample and record the wet weight (WW). (For 

samples with <35% moisture a 20 g portion 

is sufficient. For samples with moisture 

>35% a larger aliquot 50–100 g is required.) 

Dry the sample to a constant weight at 60 °C 

and record the dry weight (DW) for 

calculation of percent solids (Section 12.6). 

(The sample is dried at 60 °C to prevent the 

loss of mercury and other possible volatile 

metallic compounds, to facilitate sieving, and 

to ready the sample for grinding.) 

11.3.2 To achieve homogeneity, sieve the 

dried sample using a 5-mesh polypropylene 

sieve and grind in a mortar and pestle. (The 

sieve, mortar and pestle should be cleaned 

between samples.) From the dried, ground 

material weigh accurately a representative 

1.0 ± 0.01 g aliquot (W) of the sample and 

transfer to a 250 mL Phillips beaker for acid 

extraction (Sections 1.6, 1.7, 1.8, and 1.9). 

11.3.3 To the beaker add 4 mL of (1+1) 

HNO3 and 10 mL of (1+4) HCl. Cover the lip 

of the beaker with a watch glass. Place the 

beaker on a hot plate for reflux extraction of 

the analytes. The hot plate should be located 

in a fume hood and previously adjusted to 

provide a reflux temperature of 

approximately 95 °C. (See the following 

note.) 

Note: For proper heating adjust the 

temperature control of the hot plate such that 

an uncovered Griffin beaker containing 50 

mL of water placed in the center of the hot 

plate can be maintained at a temperature 

approximately but no higher than 85 °C. 

(Once the beaker is covered with a watch 

glass the temperature of the water will rise 

to approximately 95 °C.) Also, a block 

digester capable of maintaining a temperature 

of 95 °C and equipped with 250 mL 

constricted volumetric digestion tubes may 

be substituted for the hot plate and conical 

beakers in the extraction step. 

11.3.4 Heat the sample and gently reflux 

for 30 minutes. Very slight boiling may 

occur, however vigorous boiling must be 

avoided to prevent loss of the HCl-H2O 

azeotrope. Some solution evaporation will 

occur (3–4 mL). 

11.3.5 Allow the sample to cool and 

quantitatively transfer the extract to a 100 mL 

volumetric flask. Dilute to volume with 

reagent water, stopper and mix. 

11.3.6 Allow the sample extract solution 

to stand overnight to separate insoluble 

material or centrifuge a portion of the sample 

solution until clear. (If after centrifuging or 

standing overnight the extract solution 

contains suspended solids that would clog 

the nebulizer, a portion of the extract 

solution may be filtered for their removal 

prior to analysis. However, care should be 

exercised to avoid potential contamination 

from filtration.) The sample extract is now 

ready for analysis. Because the effects of 

various matrices on the stability of diluted 

samples cannot be characterized, all analyses 

should be performed as soon as possible after 

the completed preparation. 

11.4 Sample Analysis 

11.4.1 Prior to daily calibration of the 

instrument inspect the sample introduction 

system including the nebulizer, torch, 

injector tube and uptake tubing for salt 

deposits, dirt and debris that would restrict 

solution flow and affect instrument 

performance. Clean the system when needed 

or on a daily basis. 

11.4.2 Configure the instrument system to 

the selected power and operating conditions 

as determined in Sections 10.1 and 10.2. 

11.4.3 The instrument must be allowed to 

become thermally stable before calibration 

and analyses. This usually requires at least 

30 to 60 minutes of operation. After 

instrument warmup, complete any required 

optical profiling or alignment particular to 

the instrument. 

11.4.4 For initial and daily operation 

calibrate the instrument according to the 

instrument manufacturer’s recommended 

procedures, using mixed calibration standard 

solutions (Section 7.9) and the calibration 

blank (Section 7.10.1). A peristaltic pump 

must be used to introduce all solutions to the 

nebulizer. To allow equilibrium to be 

reached in the plasma, aspirate all solutions 

for 30 seconds after reaching the plasma 

before beginning integration of the 

background corrected signal to accumulate 

data. When possible, use the average value of 

replicate integration periods of the signal to 

be correlated to the analyte concentration. 

Flush the system with the rinse blank 

(Section 7.10.4) for a minimum of 60 seconds 

(Section 4.4) between each standard. The 

calibration line should consist of a minimum 

of a calibration blank and a high standard. 

Replicates of the blank and highest standard 

provide an optimal distribution of calibration 

standards to minimize the confidence band 

for a straight-line calibration in a response 

region with uniform variance.20

11.4.5 After completion of the initial 

requirements of this method (Sections 10.3 

and 10.4), samples should be analyzed in the 

same operational manner used in the 

calibration routine with the rinse blank also 

being used between all sample solutions, 

LFBs, LFMs, and check solutions (Section 

7.10.4). 

11.4.6 During the analysis of samples, the 

laboratory must comply with the required 

quality control described in Sections 9.3 and 

9.4. Only for the determination of dissolved 

analytes or the ‘‘direct analysis’’ of drinking 

water with turbidity of <1 NTU is the sample 

digestion step of the LRB, LFB, and LFM not 

required. 

11.4.7 Determined sample analyte 

concentrations that are 90% or more of the 

upper limit of the analyte LDR must be 

diluted with reagent water that has been 

acidified in the same manner as calibration 

blank and reanalyzed (see Section 11.4.8). 

Also, for the interelement spectral 

interference correction routines to remain 

valid during sample analysis, the interferant 

concentration must not exceed its LDR. If the 

interferant LDR is exceeded, sample dilution 

with acidified reagent water and reanalysis is 

required. In these circumstances analyte 

detection limits are raised and determination 

by another approved test procedure that is 

either more sensitive and/or interference free 

is recommended. 


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11.4.8 When it is necessary to assess an 

operative matrix interference (e.g., signal 

reduction due to high dissolved solids), the 

tests described in Section 9.5 are 

recommended. 

11.4.9 Report data as directed in Section 

12.0. 

11.5 If the method of standard additions 

(MSA) is used, standards are added at one or 

more levels to portions of a prepared sample. 

This technique 21 compensates for 

enhancement or depression of an analyte 

signal by a matrix. It will not correct for 

additive interferences such as contamination, 

interelement interferences, or baseline shifts. 

This technique is valid in the linear range 

when the interference effect is constant over 

the range, the added analyte responds the 

same as the endogenous analyte, and the 

signal is corrected for additive interferences. 

The simplest version of this technique is the 

single-addition method. This procedure calls 

for two identical aliquots of the sample 

solution to be taken. To the first aliquot, a 

small volume of standard is added; while to 

the second aliquot, a volume of acid blank is 

added equal to the standard addition. The 

sample concentration is calculated by the 

following: 

Where: 

C = Concentration of the standard solution 

(mg/L) 

S1 = Signal for fortified aliquot 

S2 = Signal for unfortified aliquot 

V1 = Volume of the standard addition (L) 

V2 = Volume of the sample aliquot (L) used 

for MSA 

For more than one fortified portion of the 

prepared sample, linear regression analysis 

can be applied using a computer or calculator 

program to obtain the concentration of the 

sample solution. An alternative to using the 

method of standard additions is use of the 

internal standard technique by adding one or 

more elements (not in the samples and 

verified not to cause an uncorrected 

interelement spectral interference) at the 

same concentration (which is sufficient for 

optimum precision) to the prepared samples 

(blanks and standards) that are affected the 

same as the analytes by the sample matrix. 

Use the ratio of analyte signal to the internal 

standard signal for calibration and 

quantitation. 

12.0 Data Analysis and Calculations 

12.1 Sample data should be reported in 

units of mg/L for aqueous samples and mg/ 

kg dry weight for solid samples. 

12.2 For dissolved aqueous analytes 

(Section 11.1) report the data generated 

directly from the instrument with allowance 

for sample dilution. Do not report analyte 

concentrations below the IDL. 

12.3 For total recoverable aqueous 

analytes (Section 11.2), multiply solution 

analyte concentrations by the dilution factor 

0.5, when 100 mL aliquot is used to produce 

the 50 mL final solution, and report data as 

instructed in Section 12.4. If a different 

aliquot volume other than 100 mL is used for 

sample preparation, adjust the dilution factor 

accordingly. Also, account for any additional 

dilution of the prepared sample solution 

needed to complete the determination of 

analytes exceeding 90% or more of the LDR 

upper limit. Do not report data below the 

determined analyte MDL concentration or 

below an adjusted detection limit reflecting 

smaller sample aliquots used in processing or 

additional dilutions required to complete the 

analysis. 

12.4 For analytes with MDLs <0.01 mg/L, 

round the data values to the thousandth 

place and report analyte concentrations up to 

three significant figures. For analytes with 

MDLs <0.01 mg/L round the data values to 

the 100th place and report analyte 

concentrations up to three significant figures. 

Extract concentrations for solids data should 

be rounded in a similar manner before 

calculations in Section 12.5 are performed. 

12.5 For total recoverable analytes in 

solid samples (Section 11.3), round the 

solution analyte concentrations (mg/L) as 

instructed in Section 12.4. Report the data up 

to three significant figures as mg/kg dryweight basis unless specified otherwise by 

the program or data user. Calculate the 

concentration using the equation below: 

Where: 

C = Concentration in extract (mg/L) 

V = Volume of extract (L, 100 mL = 0.1L) 

D = Dilution factor (undiluted = 1) 

W = Weight of sample aliquot extracted (g x 

0.001 = kg) 

Do not report analyte data below the 

estimated solids MDL or an adjusted MDL 

because of additional dilutions required to 

complete the analysis. 

12.6 To report percent solids in solid 

samples (Section 11.3) calculate as follows: 

Where: 

DW = Sample weight (g) dried at 60 ßC 

WW = Sample weight (g) before drying 

Note: If the data user, program or 

laboratory requires that the reported percent 

solids be determined by drying at 105 °C, 

repeat the procedure given in Section 11.3 

using a separate portion (>20 g) of the sample 

and dry to constant weight at 103–105 °C. 

12.7 The QC data obtained during the 

analyses provide an indication of the quality 

of the sample data and should be provided 

with the sample results. 

13.0 Method Performance 

13.1 Listed in Table 4 are typical single 

laboratory total recoverable MDLs 

determined for the recommended 

wavelengths using simultaneous ICP–AES 

and the operating conditions given in Table 

5. The MDLs were determined in reagent 

blank matrix (best case situation). PTFE 

beakers were used to avoid boron and silica 

contamination from glassware with the final 

dilution to 50 mL completed in 

polypropylene centrifuged tubes. The listed 

MDLs for solids are estimates and were 

calculated from the aqueous MDL 

determinations. 

13.2 Data obtained from single laboratory 

method testing are summarized in Table 6 for 

five types of water samples consisting of 

drinking water, surface water, ground water, 

and two wastewater effluents. The data 

presented cover all analytes except cerium 

and titanium. Samples were prepared using 

the procedure described in Section 11.2. For 

each matrix, five replicate aliquots were 

prepared, analyzed and the average of the 

five determinations used to define the sample 

background concentration of each analyte. In 

addition, two pairs of duplicates were 

fortified at different concentration levels. For 

each method analyte, the sample background 

concentration, mean percent recovery, 

standard deviation of the percent recovery, 

and relative percent difference between the 

duplicate fortified samples are listed in Table 

6. The variance of the five replicate sample 

background determinations is included in the 

calculated standard deviation of the percent 

recovery when the analyte concentration in 

the sample was greater than the MDL. The 

tap and well waters were processed in Teflon 

and quartz beakers and diluted in 

polypropylene centrifuged tubes. The nonuse 

of borosilicate glassware is reflected in the 

precision and recovery data for boron and 

silica in those two sample types. 

13.3 Data obtained from single laboratory 

method testing are summarized in Table 7 for 

three solid samples consisting of EPA 884 

Hazardous Soil, SRM 1645 River Sediment, 

and EPA 286 Electroplating Sludge. Samples 

were prepared using the procedure described 

in Section 11.3. For each method analyte, the 

sample background concentration, mean 

percent recovery of the fortified additions, 

the standard deviation of the percent 


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29824 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

recovery, and relative percent difference 

between duplicate additions were 

determined as described in Section 13.2. Data 

presented are for all analytes except cerium, 

silica, and titanium. Limited comparative 

data to other methods and SRM materials are 

presented in Reference 23 of Section 16.0. 

13.4 Performance data for aqueous 

solutions independent of sample preparation 

from a multilaboratory study are provided in 

Table 8.22

13.5 Listed in Table 9 are regression 

equations for precision and bias for 25 

analytes abstracted from EPA Method Study 

27, a multilaboratory validation study of 

Method 200.7.1 These equations were 

developed from data received from 12 

laboratories using the total recoverable 

sample preparation procedure on reagent 

water, drinking water, surface water and 

three industrial effluents. For a complete 

review and description of the study, see 

Reference 16 of Section 16.0. 

14.0 Pollution Prevention 

14.1 Pollution prevention encompasses 

any technique that reduces or eliminates the 

quantity or toxicity of waste at the point of 

generation. Numerous opportunities for 

pollution prevention exist in laboratory 

operation. The EPA has established a 

preferred hierarchy of environmental 

management techniques that places pollution 

prevention as the management option of first 

choice. Whenever feasible, laboratory 

personnel should use pollution prevention 

techniques to address their waste generation 

(e.g., Section 7.8). When wastes cannot be 

feasibly reduced at the source, the Agency 

recommends recycling as the next best 

option. 

14.2 For information about pollution 

prevention that may be applicable to 

laboratories and research institutions, consult 

‘‘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. 

15.0 Waste Management 

15.1 The Environmental Protection 

Agency requires that laboratory waste 

management practices be conducted 

consistent with all applicable rules and 

regulations. The Agency urges laboratories to 

protect the air, water, and land by 

minimizing and controlling all releases from 

hoods and bench operations, complying with 

the letter and spirit of any sewer discharge 

permits and regulations, and by complying 

with all solid and hazardous waste 

regulations, particularly the hazardous waste 

identification rules and land disposal 

restrictions. For further information on waste 

management consult ‘‘The Waste 

Management Manual for Laboratory 

Personnel’’, available from the American 

Chemical Society at the address listed in the 

Section 14.2. 

16.0 References 

1. U.S. Environmental Protection 

Agency. Inductively Coupled 

Plasma—Atomic Emission 

Spectrometric Method for Trace 

Element Analysis of Water and 

Wastes—Method 200.7, Dec. 1982. 

EPA–600/4–79–020, revised March 

1983. 

2. U.S. Environmental Protection 

Agency. Inductively Coupled 

Plasma Atomic Emission 

Spectroscopy Method 6010, SW– 

846 Test Methods for Evaluating 

Solid Waste, 3rd Edition, 1986. 

3. U.S. Environmental Protection 

Agency. Method 200.7: 

Determination of Metals and Trace 

Elements in Water and Wastes by 

Inductively Coupled Plasma— 

Atomic Emission Spectrometry, 

revision 3.3, EPA 600 4–91/010, 

June 1991. 

4. U.S. Environmental Protection 

Agency. Inductively Coupled 

Plasma—Atomic Emission 

Spectrometry Method for the 

Analysis of Waters and Solids, 

EMMC, July 1992. 

5. Fassel, V.A. et al. Simultaneous 

Determination of Wear Metals in 

Lubricating Oils by InductivelyCoupled Plasma Atomic Emission 

Spectrometry. Anal. Chem. 48:516– 

519, 1976. 

6. Merryfield, R.N. and R.C. Loyd. 

Simultaneous Determination of 

Metals in Oil by Inductively 

Coupled Plasma Emission 

Spectrometry. Anal. Chem. 

51:1965–1968, 1979. 

7. Winge, R.K. et al. Inductively 

Coupled Plasma—Atomic Emission 

Spectroscopy: An Atlas of Spectral 

Information, Physical Science Data 

20. Elsevier Science Publishing, 

New York, New York, 1985. 

8. Boumans, P.W.J.M. Line Coincidence 

Tables for Inductively Coupled 

Plasma Atomic Emission 

Spectrometry, 2nd edition. 

Pergamon Press, Oxford, United 

Kingdom, 1984. 

9. 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, Aug. 1977. 

Available from the National 

Technical Information Service 

(NTIS) as PB–277256. 

10. OSHA Safety and Health Standards, 

General Industry, (29 CFR 1910), 

Occupational Safety and Health 

Administration, OSHA 2206, 

(Revised, January 1976). 

11. Safety in Academic Chemistry 

Laboratories, American Chemical 

Society Publication, Committee on 

Chemical Safety, 3rd Edition, 1979. 

12. Proposed OSHA Safety and Health 

Standards, Laboratories, 

Occupational Safety and Health 

Administration, Federal Register, 

July 24, 1986. 

13. Rohrbough, W.G. et al. Reagent 

Chemicals, American Chemical 

Society Specifications, 7th edition. 

American Chemical Society, 

Washington, DC, 1986. 

14. American Society for Testing and 

Materials. Standard Specification 

for Reagent Water, D1193–77. 

Annual Book of ASTM Standards, 

Vol. 11.01. Philadelphia, PA, 1991. 

15. Code of Federal Regulations 40, Ch. 

1, Pt. 136 Appendix B. 

16. Maxfield, R. and B. Mindak. EPA 

Method Study 27, Method 200.7 

Trace Metals by ICP, Nov. 1983. 

Available from National Technical 

Information Service (NTIS) as PB 

85–248–656. 

17. Botto, R.I. Quality Assurance in 

Operating a Multielement ICP 

Emission Spectrometer. 

Spectrochim. Acta, 39B(1):95–113, 

1984. 

18. Wallace, G.F., Some Factors 

Affecting the Performance of an ICP 

Sample Introduction System. 

Atomic Spectroscopy, Vol. 4, p. 

188–192, 1983. 

19. Koirtyohann, S.R. et al. 

Nomenclature System for the LowPower Argon Inductively Coupled 

Plasma, Anal. Chem. 52:1965, 1980. 

20. Deming, S.N. and S.L. Morgan. 

Experimental Design for Quality 

and Productivity in Research, 

Development, and Manufacturing, 

Part III, pp. 119–123. Short course 

publication by Statistical Designs, 

9941 Rowlett, Suite 6, Houston, TX 

77075, 1989. 

21. Winefordner, J.D., Trace Analysis: 

Spectroscopic Methods for 

Elements, Chemical Analysis, Vol. 

46, pp. 41–42. 

22. Jones, C.L. et al. An Interlaboratory 

Study of Inductively Coupled 

Plasma Atomic Emission 

Spectroscopy Method 6010 and 

Digestion Method 3050. EPA–600/ 

4–87–032, U.S. Environmental 

Protection Agency, Las Vegas, 

Nevada, 1987. 

23. Martin, T.D., E.R. Martin and SE. 

Long. Method 200.2: Sample 

Preparation Procedure for 

Spectrochemical Analyses of Total 

Recoverable Elements, EMSL ORD, 

USEPA, 1989. 

17.0 Tables, Diagrams, Flowcharts, 

and Validation Data 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29825 

TABLE 1—WAVELENGTHS, ESTIMATED INSTRUMENT DETECTION LIMITS, AND RECOMMENDED CALIBRATION

Analyte Wavelengtha

(nm) 

Estimated 

detection 

limitb (μg/L) 

Calibratec

to (mg/L) 

Aluminum ......................................................................................................................... 308.215 45 10 

Antimony .......................................................................................................................... 206.833 32 5 

Arsenic ............................................................................................................................. 193.759 53 10 

Barium .............................................................................................................................. 493.409 2.3 1 

Beryllium .......................................................................................................................... 313.042 0.27 1 

Boron ............................................................................................................................... 249.678 5.7 1 

Cadmium .......................................................................................................................... 226.502 3.4 2 

Calcium ............................................................................................................................ 315.887 30 10 

Cerium ............................................................................................................................. 413.765 48 2 

Chromium ........................................................................................................................ 205.552 6.1 5 

Cobalt ............................................................................................................................... 228.616 7.0 2 

Copper ............................................................................................................................. 324.754 5.4 2 

Iron ................................................................................................................................... 259.940 6.2 10 

Lead ................................................................................................................................. 220.353 42 10 

Lithium ............................................................................................................................. 670.784 d 3.7 5 

Magnesium ...................................................................................................................... 279.079 30 10 

Manganese ...................................................................................................................... 257.610 1.4 2 

Mercury ............................................................................................................................ 194.227 2.5 2 

Molybdenum .................................................................................................................... 203.844 12 10 

Nickel ............................................................................................................................... 231.604 15 2 

Phosphorus ...................................................................................................................... 214.914 76 10 

Potassium ........................................................................................................................ 766.491 e 700 20 

Selenium .......................................................................................................................... 196.090 75 5 

Silica (SiO2) ..................................................................................................................... 251.611 d 26 (SiO2) 10 

Silver ................................................................................................................................ 328.068 7.0 0.5 

Sodium ............................................................................................................................. 588.995 29 10 

Strontium .......................................................................................................................... 421.552 0.77 1 

Thallium ........................................................................................................................... 190.864 40 5 

Tin .................................................................................................................................... 189.980 25 4 

Titanium ........................................................................................................................... 334.941 3.8 10 

Vanadium ......................................................................................................................... 292.402 7.5 2 

Zinc .................................................................................................................................. 213.856 1.8 5 

aThe wavelengths listed are recommended because of their sensitivity and overall acceptability. Other wavelengths may be substituted if they 

can provide the needed sensitivity and are treated with the same corrective techniques for spectral interference (see Section 4.1). bThese estimated 3-sigma instrumental detection limits 16 are provided only as a guide to instrumental limits. The method detection limits are 

sample dependent and may vary as the sample matrix varies. Detection limits for solids can be estimated by dividing these values by the grams 

extracted per liter, which depends upon the extraction procedure. Divide solution detection limits by 10 for 1 g extracted to 100 mL for solid detection limits. cSuggested concentration for instrument calibration.2 Other calibration limits in the linear ranges may be used. d Calculated from 2-sigma data.5

e Highly dependent on operating conditions and plasma position. 


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29826 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

TABLE 2—ON-LINE METHOD INTERELEMENT SPECTRAL INTERFERANCES ARISING FROM INTERFERANTS AT THE 100 MG/L 

LEVEL

Analyte Wavelength (nm) Interferant* 

Ag .................................................................................................................................................

Al ...................................................................................................................................................

As ..................................................................................................................................................

B ...................................................................................................................................................

Ba .................................................................................................................................................

Be .................................................................................................................................................

Ca .................................................................................................................................................

Cd .................................................................................................................................................

Ce .................................................................................................................................................

Co .................................................................................................................................................

Cr ..................................................................................................................................................

Cu .................................................................................................................................................

Fe ..................................................................................................................................................

Hg .................................................................................................................................................

K ...................................................................................................................................................

Li ...................................................................................................................................................

Mg .................................................................................................................................................

Mn .................................................................................................................................................

Mo .................................................................................................................................................

Na .................................................................................................................................................

Ni ..................................................................................................................................................

P ...................................................................................................................................................

Pb .................................................................................................................................................

Sb .................................................................................................................................................

Se .................................................................................................................................................

SiO2 ..............................................................................................................................................

Sn .................................................................................................................................................

Sr ..................................................................................................................................................

Tl ...................................................................................................................................................

Ti ...................................................................................................................................................

V ...................................................................................................................................................

Zn ..................................................................................................................................................

328.068 

308.215 

193.759 

249.678 

493.409 

313.042 

315.887 

226.502 

413.765 

228.616 

205.552 

324.754 

259.940 

194.227 

766.491 

670.784 

279.079 

257.610 

203.844 

588.995 

231.604 

214.914 

220.353 

206.833 

196.099 

251.611 

189.980 

421.552 

190.864 

334.941 

292.402 

213.856 

Ce, Ti, Mn 

V, Mo, Ce, Mn 

V, Al, Co, Fe, Ni 

None 

None 

V, Ce 

Co, Mo, Ce 

Ni, Ti, Fe, Ce 

None 

Ti, Ba, Cd, Ni, Cr, Mo, Ce 

Be, Mo, Ni 

Mo, Ti 

None 

V, Mo 

None 

None 

Ce 

Ce 

Ce 

None 

Co, Tl 

Cu, Mo 

Co, Al, Ce, Cu, Ni, Ti, Fe 

Cr, Mo, Sn, Ti, Ce, Fe 

Fe 

None 

Mo, Ti, Fe, Mn, Si 

None 

Ti, Mo, Co, Ce, Al, V, Mn 

None 

Mo, Ti, Cr, Fe, Ce 

Ni, Cu, Fe 

* These on-line interferences from method analytes and titanium only were observed using an instrument with 0.035 nm resolution (see Section 

4.1.2). Interferant ranked by magnitude of intensity with the most severe interferant listed first in the row. 

TABLE 3—MIXED STANDARD SOLUTIONS

Solution Analytes 

I ..........................................................................................................................................................

II .........................................................................................................................................................

III ........................................................................................................................................................

IV .......................................................................................................................................................

V ........................................................................................................................................................

Ag, As, B, Ba, Ca, Cd, Cu, Mn, Sb, and Se 

K, Li, Mo, Na, Sr, and Ti 

Co, P, V, and Ce 

Al, Cr, Hg, SiO2, Sn, and Zn 

Be, Fe, Mg, Ni, Pb, and Tl 

TABLE 4—TOTAL RECOVERABLE METHOD DETECTION LIMITS (MDL) 

Analyte MDLs 

Aqueous, mg/L(1) Solids, mg/kg(2)

Ag ............................................................................................................................................................. 0.002 0.3 

Al .............................................................................................................................................................. 0.02 3 

As ............................................................................................................................................................. 0.008 2 

B ............................................................................................................................................................... 0.003 — 

Ba ............................................................................................................................................................. 0.001 0.2 

Be ............................................................................................................................................................. 0.0003 0.1 

Ca ............................................................................................................................................................ 0.01 2 

Cd ............................................................................................................................................................ 0.001 0.2 

Ce ............................................................................................................................................................ 0.02 3 

Co ............................................................................................................................................................ 0.002 0.4 

Cr ............................................................................................................................................................. 0.004 0.8 

Cu ............................................................................................................................................................ 0.003 0.5 

Fe ............................................................................................................................................................. *0.03 6 

Hg ............................................................................................................................................................ 0.007 2 

K ............................................................................................................................................................... 0.3 60 

Li .............................................................................................................................................................. 0.001 0.2 

Mg ............................................................................................................................................................ 0.02 3 

Mn ............................................................................................................................................................ 0.001 0.2 

Mo ............................................................................................................................................................ 0.004 1 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29827 

TABLE 4—TOTAL RECOVERABLE METHOD DETECTION LIMITS (MDL)—Continued 

Analyte MDLs 

Aqueous, mg/L(1) Solids, mg/kg(2)

Na ............................................................................................................................................................ 0.03 6 

Ni .............................................................................................................................................................. 0.005 1 

P ............................................................................................................................................................... 0.06 12 

Pb ............................................................................................................................................................. 0.01 2 

Sb ............................................................................................................................................................. 0.008 2 

Se ............................................................................................................................................................. 0.02 5 

SiO2 .......................................................................................................................................................... 0.02 — 

Sn ............................................................................................................................................................. 0.007 2 

Sr ............................................................................................................................................................. 0.0003 0.1 

Tl .............................................................................................................................................................. 0.001 0.2 

Ti .............................................................................................................................................................. 0.02 3 

V ............................................................................................................................................................... 0.003 1 

Zn ............................................................................................................................................................. 0.002 0.3 

(1) MDL concentrations are computed for original matrix with allowance for 2x sample preconcentration during preparation. Samples were processed in PTFE and diluted in 50-mL plastic centrifuge tubes. 

(2)Estimated, calculated from aqueous MDL determinations. 

— Boron not reported because of glassware contamination. Silica not determined in solid samples. 

* Elevated value due to fume-hood contamination. 

TABLE 5—INDUCTIVELY COUPLED

PLASMA INSTRUMENT OPERATING

CONDITIONS

Incident rf power ..................... 1100 watts 

Reflected rf power ................... <5 watts 

Viewing height above work 

coil.

15 mm 

TABLE 5—INDUCTIVELY COUPLED

PLASMA INSTRUMENT OPERATING

CONDITIONS—Continued 

Injector tube orifice i.d. ........... 1 mm 

Argon supply ........................... liquid argon 

Argon pressure ....................... 40 psi 

Coolant argon flow rate .......... 19 L/min. 

Aerosol carrier argon flow rate 620 mL/min. 

TABLE 5—INDUCTIVELY COUPLED

PLASMA INSTRUMENT OPERATING

CONDITIONS—Continued 

Auxiliary (plasma) argon flow 

rate.

300 mL/min. 

Sample uptake rate controlled 

to.

1.2 mL/min. 

TABLE 6—PRECISION AND RECOVERY DATA IN AQUEOUS MATRICES

Analyte 

Sample 

conc. 

mg/L 

Low spike 

mg/L 

Average 

recovery 

R (%) 

S (R) RPD High spike 

mg/L 

Average 

recovery 

R (%) 

S (R) RPD 

Tap Water 

Ag ............. <0.002 0.05 95 0.7 2.1 0.2 96 0.0 0.0 

Al .............. 0.185 0.05 98 8.8 1.7 0.2 105 3.0 3.1 

As ............. <0.008 0.05 108 1.4 3.7 0.2 101 0.7 2.0 

B ............... 0.023 0.1 98 0.2 0.0 0.4 98 0.2 0.5 

Ba ............. 0.042 0.05 102 1.6 2.2 0.2 98 0.4 0.8 

Be ............. <0.0003 0.01 100 0.0 0.0 0.1 99 0.0 0.0 

Ca ............. 35.2 5.0 101 8.8 1.7 20.0 103 2.0 0.9 

Cd ............. <0.001 0.01 105 3.5 9.5 0.1 98 0.0 0.0 

Co ............. <0.002 0.02 100 0.0 0.0 0.2 99 0.5 1.5 

Cr ............. <0.004 0.01 110 0.0 0.0 0.1 102 0.0 0.0 

Cu ............. <0.003 0.02 103 1.8 4.9 0.2 101 1.2 3.5 

Fe ............. 0.008 0.1 106 1.0 1.8 0.4 105 0.3 0.5 

Hg ............. <0.007 0.05 103 0.7 1.9 0.2 100 0.4 1.0 

K ............... 1.98 5.0 109 1.4 2.3 20. 107 0.7 1.7 

Li .............. 0.006 0.02 103 6.9 3.8 0.2 110 1.9 4.4 

Mg ............ 8.08 5.0 104 2.2 1.5 20.0 100 0.7 1.1 

Mn ............ <0.001 0.01 100 0.0 0.0 0.1 99 0.0 0.0 

Mo ............ <0.004 0.02 95 3.5 10.5 0.2 108 0.5 1.4 

Na ............. 10.3 5.0 99 3.0 2.0 20.0 106 1.0 1.6 

Ni .............. <0.005 0.02 108 1.8 4.7 0.2 104 1.1 2.9 

P ............... 0.045 0.1 102 13.1 9.4 0.4 104 3.2 1.3 

Pb ............. <0.01 0.05 95 0.7 2.1 0.2 100 0.2 0.5 

Sb ............. <0.008 0.05 99 0.7 2.0 0.2 102 0.7 2.0 

Se ............. <0.02 0.1 87 1.1 3.5 0.4 99 0.8 2.3 

SiO2 .......... 6.5 5.0 104 3.3 3.4 20.0 96 1.1 2.3 

Sn ............. <0.007 0.05 103 2.1 5.8 0.2 101 1.8 5.0 

Sr .............. 0.181 0.1 102 3.3 2.1 0.4 105 0.8 1.0 

Tl .............. <0.02 0.1 101 3.9 10.9 0.4 101 0.1 0.3 

V ............... <0.003 0.05 101 0.7 2.0 0.2 99 0.2 0.5 

Zn ............. 0.005 0.05 101 3.7 9.0 0.2 98 0.9 2.5 

Pond Water 

Ag ............. <0.002 0.05 92 0.0 0.0 0.2 94 0.0 0.0 


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29828 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

TABLE 6—PRECISION AND RECOVERY DATA IN AQUEOUS MATRICES—Continued 

Analyte 

Sample 

conc. 

mg/L 

Low spike 

mg/L 

Average 

recovery 

R (%) 

S (R) RPD High spike 

mg/L 

Average 

recovery 

R (%) 

S (R) RPD 

Al .............. 0.819 0.2 88 10.0 5.0 0.8 100 2.9 3.7 

As ............. <0.008 0.05 102 0.0 0.0 0.2 98 1.4 4.1 

B ............... 0.034 0.1 111 8.9 6.9 0.4 103 2.0 0.0 

Ba ............. 0.029 0.05 96 0.9 0.0 0.2 97 0.3 0.5 

Be ............. <0.0003 0.01 95 0.4 1.1 0.2 95 0.0 0.0 

Ca ............. 53.9 5.0 * * 0.7 20.0 100 2.0 1.5 

Cd ............. <0.001 0.01 107 0.0 0.0 0.1 97 0.0 0.0 

Co ............. <0.002 0.02 100 2.7 7.5 0.2 97 0.7 2.1 

Cr ............. <0.004 0.01 105 3.5 9.5 0.1 103 1.1 2.9 

Cu ............. <0.003 0.02 98 2.1 4.4 0.2 100 0.5 1.5 

Fe ............. 0.875 0.2 95 8.9 2.8 0.8 97 3.2 3.6 

Hg ............. <0.007 0.05 97 3.5 10.3 0.2 98 0.0 0.0 

K ............... 2.48 5.0 106 0.3 0.1 20.0 103 0.2 0.4 

Li .............. <0.001 0.02 110 0.0 0.0 0.2 106 0.2 0.5 

Mg ............ 10.8 5.0 102 0.5 0.0 20.0 96 0.7 1.3 

Mn ............ 0.632 0.01 * * 0.2 0.1 97 2.3 0.3 

Mo ............ <0.004 0.02 105 3.5 9.5 0.2 103 0.4 1.0 

Na ............. 17.8 5.0 103 1.3 0.4 20.0 94 0.3 0.0 

Ni .............. <0.005 0.02 96 5.6 9.1 0.2 100 0.7 1.5 

P ............... 0.196 0.1 91 14.7 0.3 0.4 108 3.9 1.3 

Pb ............. <0.01 0.05 96 2.6 7.8 0.2 100 0.7 2.0 

Sb ............. <0.008 0.05 102 2.8 7.8 0.2 104 0.4 1.0 

Se ............. <0.02 0.1 104 2.1 5.8 0.4 103 1.6 4.4 

SiO2 .......... 7.83 5.0 151 1.6 1.3 20.0 117 0.4 0.6 

Sn ............. <0.007 0.05 98 0.0 0.0 0.2 99 1.1 3.0 

Sr .............. 0.129 0.1 105 0.4 0.0 0.4 99 0.1 0.2 

Tl .............. <0.02 0.1 103 1.1 2.9 0.4 97 1.3 3.9 

V ............... 0.003 0.05 94 0.4 0.0 0.2 98 0.1 0.0 

Zn ............. 0.006 0.05 97 1.6 1.8 0.2 94 0.4 0.0 

Well Water 

Ag ............. <0.002 0.05 97 0.7 2.1 0.2 96 0.2 0.5 

Al .............. 0.036 0.05 107 7.6 10.1 0.2 101 1.1 0.8 

As ............. <0.008 0.05 107 0.7 1.9 0.2 104 0.4 1.0 

B ............... 0.063 0.1 97 0.6 0.7 0.4 98 0.8 2.1 

Ba ............. 0.102 0.05 102 3.0 0.0 0.2 99 0.9 1.0 

Be ............. <0.0003 0.01 100 0.0 0.0 0.1 100 0.0 0.0 

Ca ............. 93.8 5.0 * * 2.1 20.0 100 4.1 0.1 

Cd ............. 0.002 0.01 90 0.0 0.0 0.1 96 0.0 0.0 

Co ............. <0.002 0.02 94 0.4 1.1 0.2 94 0.4 1.1 

Cr ............. <0.004 0.01 100 7.1 20.0 0.1 100 0.4 1.0 

Cu ............. <0.005 0.02 100 1.1 0.4 0.2 96 0.5 1.5 

Fe ............. 0.042 0.1 99 2.3 1.4 0.4 97 1.4 3.3 

Hg ............. <0.007 0.05 94 2.8 8.5 0.2 93 1.2 3.8 

K ............... 6.21 5.0 96 3.4 3.6 20.0 101 1.2 2.3 

Li .............. 0.001 0.02 100 7.6 9.5 0.2 104 1.0 1.9 

Mg ............ 24.5 5.0 95 5.6 0.3 20.0 93 1.6 1.2 

Mn ............ 2.76 0.01 * * 0.4 0.1 * * 0.7 

Mo ............ <0.004 0.02 108 1.8 4.7 0.2 101 0.2 0.5 

Na ............. 35.0 5.0 101 11.4 0.8 20.0 100 3.1 1.5 

Ni .............. <0.005 0.02 112 1.8 4.4 0.2 96 0.2 0.5 

P ............... 0.197 0.1 95 12.7 1.9 0.4 98 3.4 0.9 

Pb ............. <0.01 0.05 87 4.9 16.1 0.2 95 0.2 0.5 

Sb ............. <0.008 0.05 98 2.8 8.2 0.2 99 1.4 4.0 

Se ............. <0.02 0.1 102 0.4 1.0 0.4 94 1.1 3.4 

SiO2 .......... 13.1 5.0 93 4.8 2.8 20.0 99 0.8 0.0 

Sn ............. <0.007 0.05 98 2.8 8.2 0.2 94 0.2 0.5 

Sr .............. 0.274 0.1 94 5.7 2.7 0.4 95 1.7 2.2 

Tl .............. <0.02 0.1 92 0.4 1.1 0.4 95 1.1 3.2 

V ............... <0.003 0.05 98 0.0 0.0 0.2 99 0.4 1.0 

Zn ............. 0.538 0.05 * * 0.7 0.2 99 2.5 1.1 

Sewage Treatment Effluent 

Ag ............. 0.009 0.05 92 1.5 3.6 0.2 95 0.1 0.0 

Al .............. 1.19 0.05 * * 0.9 0.2 113 12.4 2.1 

As ............. <0.008 0.05 99 2.1 6.1 0.2 93 2.1 6.5 

B ............... 0.226 0.1 217 16.3 9.5 0.4 119 13.1 20.9 

Ba ............. 0.189 0.05 90 6.8 1.7 0.2 99 1.6 0.5 


srobinson on DSK4SPTVN1PROD with RULES2
Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29829 

TABLE 6—PRECISION AND RECOVERY DATA IN AQUEOUS MATRICES—Continued 

Analyte 

Sample 

conc. 

mg/L 

Low spike 

mg/L 

Average 

recovery 

R (%) 

S (R) RPD High spike 

mg/L 

Average 

recovery 

R (%) 

S (R) RPD 

Be ............. <0.0003 0.01 94 0.4 1.1 0.1 100 0.4 1.0 

Ca ............. 87.9 5.0 * * 0.6 20.0 101 3.7 0.0 

Cd ............. 0.009 0.01 89 2.6 2.3 0.1 97 0.4 1.0 

Co ............. 0.016 0.02 95 3.1 0.0 0.2 93 0.4 0.5 

Cr ............. 0.128 0.01 * * 1.5 0.1 97 2.4 2.7 

Cu ............. 0.174 0.02 98 33.1 4.7 0.2 98 3.0 1.4 

Fe ............. 1.28 0.1 * * 2.8 0.4 111 7.0 0.6 

Hg ............. <0.007 0.05 102 1.4 3.9 0.2 98 0.5 1.5 

K ............... 10.6 5.0 104 2.8 1.3 20.0 101 0.6 0.0 

Li .............. 0.011 0.02 103 8.5 3.2 0.2 105 0.8 0.5 

Mg ............ 22.7 5.0 100 4.4 0.0 20.0 92 1.1 0.2 

Mn ............ 0.199 0.01 * * 2.0 0.1 104 1.9 0.3 

Mo ............ 0.125 0.02 110 21.2 6.8 0.2 102 1.3 0.9 

Na ............. 0.236 5.0 * * 0.0 20.0 * * 0.4 

Ni .............. 0.087 0.02 122 10.7 4.5 0.2 98 0.8 1.1 

P ............... 4.71 0.1 * * 2.6 0.4 * * 1.4 

Pb ............. 0.015 0.05 91 3.5 5.0 0.2 96 1.3 2.9 

Sb ............. <0.008 0.05 97 0.7 2.1 0.2 103 1.1 2.9 

Se ............. <0.02 0.1 108 3.9 10.0 0.4 101 2.6 7.2 

SiO2 .......... 16.7 5.0 124 4.0 0.9 20.0 108 1.1 0.8 

Sn ............. 0.016 0.05 90 3.8 0.0 0.2 95 1.0 0.0 

Sr .............. 0.515 0.1 103 6.4 0.5 0.4 96 1.6 0.2 

Tl .............. <0.02 0.1 105 0.4 1.0 0.4 95 0.0 0.0 

V ............... 0.003 0.05 93 0.9 2.0 0.2 97 0.2 0.5 

Zn ............. 0.160 0.05 98 3.3 1.9 0.2 101 1.0 1.4 

Industrial Effluent 

Ag ............. <0.0003 0.05 88 0.0 0.0 0.2 84 0.9 3.0 

Al .............. 0.054 0.05 88 11.7 12.2 0.2 90 3.9 8.1 

As ............. <0.02 0.05 82 2.8 9.8 0.2 88 0.5 1.7 

B ............... 0.17 0.1 162 17.6 13.9 0.4 92 4.7 9.3 

Ba ............. 0.083 0.05 86 8.2 1.6 0.2 85 2.3 2.4 

Be ............. <0.0006 0.01 94 0.4 1.1 0.1 82 1.4 4.9 

Ca ............. 500 5.0 * * 2.8 20.0 * * 2.3 

Cd ............. 0.008 0.01 85 4.7 6.1 0.1 82 1.4 4.4 

Co ............. <0.004 0.02 93 1.8 5.4 0.2 83 0.4 1.2 

Cr ............. 0.165 0.01 * * 4.5 0.1 106 6.6 5.6 

Cu ............. 0.095 0.02 93 23.3 0.9 0.2 95 2.7 2.8 

Fe ............. 0.315 0.1 88 16.4 1.0 0.4 99 6.5 8.0 

Hg ............. <0.01 0.05 87 0.7 2.3 0.2 86 0.4 1.2 

K ............... 2.87 5.0 101 3.4 2.4 20.0 100 0.8 0.4 

Li .............. 0.069 0.02 103 24.7 5.6 0.2 104 2.5 2.2 

Mg ............ 6.84 5.0 87 3.1 0.0 20.0 87 0.9 1.2 

Mn ............ 0.141 0.01 * * 1.2 0.1 89 6.6 4.8 

Mo ............ 1.27 0.02 * * 0.0 0.2 100 15.0 2.7 

Na ............. 1500 5.0 * * 2.7 20.0 * * 2.0 

Ni .............. 0.014 0.02 98 4.4 3.0 0.2 87 0.5 1.1 

P ............... 0.326 0.1 105 16.0 4.7 0.4 97 3.9 1.4 

Pb ............. 0.251 0.05 80 19.9 1.4 0.2 88 5.0 0.9 

Sb ............. 2.81 0.05 * * 0.4 0.2 * * 2.0 

Se ............. 0.021 0.1 106 2.6 3.2 0.4 105 1.9 4.6 

SiO2 .......... 6.83 5.0 99 6.8 1.7 20.0 100 2.2 3.0 

Sn ............. <0.01 0.05 87 0.7 2.3 0.2 86 0.4 1.2 

Sr .............. 6.54 0.1 * * 2.0 0.4 * * 2.7 

Tl .............. <0.03 0.1 87 1.8 5.8 0.4 84 1.1 3.6 

V ............... <0.005 0.05 90 1.4 4.4 0.2 84 1.1 3.6 

Zn ............. 0.024 0.05 89 6.0 4.4 0.2 91 3.5 8.9 

S (R) Standard deviation of percent recovery. 

RPD Relative percent difference between duplicate spike determinations. 

< Sample concentration below established method detection limit. 

* Spike concentration <10% of sample background concentration. 


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TABLE 7—PRECISION AND RECOVERY DATA IN SOLID MATRICES

Analyte 

Sample 

conc. 

mg/kg 

Low + spike 

mg/kg 

Average 

recovery R 

(%) 

S (R) RPD 

High + 

spike 

mg/kg 

Average 

recovery R 

(%) 

S (R) RPD 

EPA Hazardous Soil #884 

Ag ............. 1.1 20 98 0.7 1.0 100 96 0.2 0.6 

Al .............. 5080 20 * * 7.2 100 * * 5.4 

As ............. 5.7 20 95 5.4 10.6 100 96 1.4 3.6 

B ............... 20.4 100 93 2.7 5.3 400 100 2.1 5.5 

Ba ............. 111 20 98 71.4 22.2 100 97 10.0 1.0 

Be ............. 0.66 20 97 0.7 2.3 100 99 0.1 0.2 

Ca ............. 85200 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ 

Cd ............. 2 20 93 0.7 1.0 100 94 0.2 0.4 

Co ............. 5.5 20 96 3.5 7.7 100 93 0.8 2.1 

Cr ............. 79.7 20 87 28.8 16.5 100 104 1.3 1.1 

Cu ............. 113 20 110 16.2 4.4 100 104 4.0 4.2 

Fe ............. 16500 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ 

Hg ............. <1.4 10 92 2.5 7.7 40 98 0.0 0.0 

K ............... 621 500 121 1.3 0.0 2000 107 0.9 1.8 

Li .............. 6.7 10 113 3.5 4.4 40 106 0.6 0.6 

Mg ............ 24400 500 * * 8.4 2000 * * 10.1 

Mn ............ 343 20 * * 8.5 100 95 11.0 1.6 

Mo ............ 5.3 20 88 5.3 13.2 100 91 1.4 4.1 

Na ............. 195 500 102 2.2 2.4 2000 100 1.5 3.7 

Ni .............. 15.6 20 100 1.8 0.0 100 94 1.5 3.6 

P ............... 595 500 106 13.4 8.0 2000 103 3.2 2.7 

Pb ............. 145 20 88 51.8 17.9 100 108 15.6 17.4 

Sb ............. 6.1 20 83 3.9 7.5 100 81 1.9 5.9 

Se ............. <5 20 79 14.7 52.4 100 99 0.7 2.1 

Sn ............. 16.6 20 91 34.6 5.8 80 112 8.7 2.8 

Sr .............. 102 100 84 9.6 10.8 400 94 2.5 4.6 

Tl .............. <4 20 92 4.8 14.6 100 91 1.5 4.6 

V ............... 16.7 20 104 4.2 5.4 100 99 0.8 1.7 

Zn ............. 131 20 103 31.2 7.3 100 104 7.2 6.4 

EPA Electroplating Sludge #286 

Ag ............. 6 20 96 0.2 0.4 100 93 0.1 0.4 

Al .............. 4980 20 * * 4.4 100 * * 5.6 

As ............. 32 20 94 1.3 0.8 100 97 0.7 1.6 

B ............... 210 100 113 2.0 1.6 400 98 1.9 3.5 

Ba ............. 39.8 20 0 6.8 0.3 100 0 1.6 5.7 

Be ............. 0.32 20 96 0.2 0.5 100 101 0.7 2.0 

Ca ............. 48500 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ 

Cd ............. 108 20 98 2.5 0.8 100 96 0.5 0.5 

Co ............. 5.9 20 93 2.9 5.7 100 93 0.6 1.5 

Cr ............. 7580 20 * * 0.7 100 * * 1.3 

Cu ............. 806 20 * * 1.5 100 94 8.3 0.7 

Fe ............. 31100 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ 

Hg ............. 6.1 10 90 2.5 4.0 40 97 1.7 4.3 

K ............... 2390 500 75 8.3 4.0 2000 94 2.9 3.8 

Li .............. 9.1 10 101 2.8 0.5 40 106 1.6 3.1 

Mg ............ 1950 500 110 2.0 0.8 2000 108 2.3 3.2 

Mn ............ 262 20 * * 1.8 100 91 1.2 0.9 

Mo ............ 13.2 20 92 2.1 2.9 100 92 0.3 0.0 

Na ............. 73400 500 * * 1.7 2000 * * 1.4 

Ni .............. 456 20 * * 0.4 100 88 2.7 0.9 

P ............... 9610 500 * * 2.9 2000 114 7.4 3.4 

Pb ............. 1420 20 * * 2.1 100 * * 1.3 

Sb ............. <2 20 76 0.9 3.3 100 75 2.8 10.7 

Se ............. 6.3 20 86 9.0 16.6 100 103 1.6 2.7 

Sn ............. 24.0 20 87 4.0 2.7 80 92 0.7 0.0 

Sr .............. 145 100 90 8.1 8.1 400 93 2.4 4.6 

Tl .............. 16 20 89 4.6 5.3 100 92 0.8 0.9 

V ............... 21.7 20 95 1.2 1.0 100 96 0.4 0.9 

Zn ............. 12500 20 * * 0.8 100 * * 0.8 

NBS 1645 River Sediment 

Ag ............. 1.6 20 92 0.4 1.0 100 96 0.3 0.9 

Al .............. 5160 20 * * 8.4 100 * * 2.4 

As ............. 62.8 20 89 14.4 9.7 100 97 2.9 5.0 

B ............... 31.9 100 116 7.1 13.5 400 95 0.6 1.5 

Ba ............. 54.8 20 95 6.1 2.8 100 98 1.2 1.3 


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TABLE 7—PRECISION AND RECOVERY DATA IN SOLID MATRICES—Continued 

Analyte 

Sample 

conc. 

mg/kg 

Low + spike 

mg/kg 

Average 

recovery R 

(%) 

S (R) RPD 

High + 

spike 

mg/kg 

Average 

recovery R 

(%) 

S (R) RPD 

Be ............. 0.72 20 101 0.4 1.0 100 103 1.4 3.9 

Ca ............. 28000 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ 

Cd ............. 9.7 20 100 1.1 0.0 100 101 0.7 1.8 

Co ............. 9.4 20 98 3.8 4.8 100 98 0.9 1.8 

Cr ............. 28500 20 * * 0.4 100 * * 0.7 

Cu ............. 109 20 115 8.5 0.0 100 102 1.8 1.0 

Fe ............. 84800 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ 

Hg ............. 3.1 10 99 4.3 7.7 40 96 0.7 1.0 

K ............... 452 500 98 4.1 2.0 2000 106 1.4 2.3 

Li .............. 3.7 10 101 2.0 0.7 40 108 1.3 3.0 

Mg ............ 6360 500 * * 1.8 2000 93 2.7 1.0 

Mn ............ 728 20 * * 3.5 100 97 12.4 2.2 

Mo ............ 17.9 20 97 12.5 18.5 100 98 0.6 0.0 

Na ............. 1020 500 92 2.6 0.0 2000 97 1.1 1.7 

Ni .............. 36.2 20 94 5.9 4.0 100 100 1.1 1.5 

P ............... 553 500 102 1.4 0.9 2000 100 0.8 1.6 

Pb ............. 707 20 * * 0.8 100 103 5.9 0.4 

Sb ............. 22.8 20 86 2.3 0.0 100 88 0.6 0.9 

Se ............. 6.7 20 103 14.3 27.1 100 98 3.1 7.6 

Sn ............. 309 20 * * 1.0 80 101 7.9 2.7 

Sr .............. 782 100 91 12.3 3.0 400 96 3.3 2.6 

Tl .............. <4 20 90 0.0 0.0 100 95 1.3 4.0 

V ............... 20.1 20 89 5.4 5.8 100 98 0.7 0.0 

Zn ............. 1640 20 * * 1.8 100 * * 1.1 

S (R) Standard deviation of percent recovery. 

RPD Relative percent difference between duplicate spike determinations. 

< Sample concentration below established method detection limit. 

* Spike concentration <10% of sample background concentration. 

¥Not spiked. 

+ Equivalent. 

TABLE 8—ICP–AES INSTRUMENTAL PRECISION AND ACCURACY FOR AQUEOUS SOLUTIONS a

Element Mean conc. 

(mg/L) N b RSD (%) Accurace c(% of Nominal) 

Al ...................................................................................................... 14.8 8 6.3 100 

Sb ..................................................................................................... 15.1 8 7.7 102 

As ..................................................................................................... 14.7 7 6.4 99 

Ba ..................................................................................................... 3.66 7 3.1 99 

Be ..................................................................................................... 3.78 8 5.8 102 

Cd .................................................................................................... 3.61 8 7.0 97 

Ca .................................................................................................... 15.0 8 7.4 101 

Cr ..................................................................................................... 3.75 8 8.2 101 

Co .................................................................................................... 3.52 8 5.9 95 

Cu .................................................................................................... 3.58 8 5.6 97 

Fe ..................................................................................................... 14.8 8 5.9 100 

Pb ..................................................................................................... 14.4 7 5.9 97 

Mg .................................................................................................... 14.1 8 6.5 96 

Mn .................................................................................................... 3.70 8 4.3 100 

Mo .................................................................................................... 3.70 8 6.9 100 

Ni ...................................................................................................... 3.70 7 5.7 100 

K ....................................................................................................... 14.1 8 6.6 95 

Se ..................................................................................................... 15.3 8 7.5 104 

Na .................................................................................................... 14.0 8 4.2 95 

Tl ...................................................................................................... 15.1 7 8.5 102 

V ....................................................................................................... 3.51 8 6.6 95 

Zn ..................................................................................................... 3.57 8 8.3 96 

aThese performance values are independent of sample preparation because the labs analyzed portions of the same solutions using sequential 

or simultaneous instruments. b N = Number of measurements for mean and relative standard deviation (RSD). 

cAccuracy is expressed as a percentage of the nominal value for each analyte in the acidified, multi-element solutions. 

TABLE 9—MULTILABORATORY ICP PRECISION AND ACCURACY DATA* 

Analyte Concentration 

μg/L 

Total recoverable digestion 

μ/L 

Aluminum ...................................................................................................................................... 69–4792 X = 0.9380 (C) + 22.1 


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TABLE 9—MULTILABORATORY ICP PRECISION AND ACCURACY DATA*—Continued 

Analyte Concentration 

μg/L 

Total recoverable digestion 

μ/L 

SR = 0.0481 (X) + 18.8 

Antimony ....................................................................................................................................... 77–1406 0.8908 (C) + 0.9 

SR = 0.0682 (X) + 2.5 

Arsenic .......................................................................................................................................... 69–1887 X = 1.0175 (C) + 3.9 

SR = 0.0643 (X) + 10.3 

Barium .......................................................................................................................................... 9–377 X = 0.8.80 (C) + 1.68 

SR = 0.0826 (X) + 3.54 

Beryllium ....................................................................................................................................... 3–1906 X = 1.0177 (C) ¥ 0.55 

SR = 0.0445 (X) ¥ 0.10 

Boron ............................................................................................................................................ 19–5189 X = 0.9676 (C) + 18.7 

SR = 0.0743 (X) + 21.1 

Cadmium ...................................................................................................................................... 9–1943 X = 1.0137 (C) ¥ 0.65 

SR = 0.0332 (X) + 0.90 

Calcium ......................................................................................................................................... 17–47170 X = 0.9658 (C) + 0.8 

SR = 0.0327 (X) + 10.1 

Chromium ..................................................................................................................................... 13–1406 X = 1.0049 (C) ¥ 1.2 

SR = 0.0571 (X) + 1.0 

Cobalt ........................................................................................................................................... 17–2340 X = 0.9278 (C) + 1.5 

SR = 0.0407 (X) + 0.4 

Copper .......................................................................................................................................... 8–1887 X = 0.9647 (C) ¥ 3.64 

SR = 0.0406 (X) + 0.96 

Iron ............................................................................................................................................... 13–9359 X = 0.9830 (C) + 5.7 

SR = 0.0790 (X) + 11.5 

Lead ............................................................................................................................................. 42–4717 X = 1.0056 (C) + 4.1 

SR = 0.0448 (X) + 3.5 

Magnesium ................................................................................................................................... 34–13868 X = 0.9879 (C) + 2.2 

SR = 0.0268 (X) + 8.1 

Manganese ................................................................................................................................... 4–1887 X = 0.9725 (C) + 0.07 

SR = 0.0400 (X) + 0.82 

Molybdenum ................................................................................................................................. 17–1830 X = 0.9707 (C) ¥ 2.3 

SR = 0.0529 (X) + 2.1 

Nickel ............................................................................................................................................ 17–47170 X = 0.9869 (C) + 1.5 

SR = 0.0393 (X) + 2.2 

Potassium ..................................................................................................................................... 347–14151 X = 0.9355 (C) ¥ 183.1 

SR = 0.0329 (X) + 60.9 

Selenium ....................................................................................................................................... 69–1415 X = 0.9737 (C) ¥ 1.0 

SR = 0.0443 (X) + 6.6 

Silicon ........................................................................................................................................... 189–9434 X = 0.9737 (C) ¥ 22.6 

SR = 0.2133 (X) + 22.6 

Silver ............................................................................................................................................. 8–189 X = 0.3987 (C) + 8.25 

SR = 0.1836 (X) ¥ 0.27 

Sodium ......................................................................................................................................... 35–47170 X = 1.0526 (C) + 26.7 

SR = 0.0884 (X) + 50.5 

Thallium ........................................................................................................................................ 79–1434 X = 0.9238 (C) + 5.5 

SR = 0.0106 (X) + 48.0 

Vanadium ..................................................................................................................................... 13–4698 X = 0.9551 (C) + 0.4 

SR = 0.0472 (X) + 0.5 

Zinc ............................................................................................................................................... 7–7076 X = 0.9500 (C) + 1.82 

SR = 0.0153 (X) + 7.78 

*

—Regression equations abstracted from Reference 16. 

X = Mean Recovery, μg/L. 

C = True Value for the Concentration, μg/L. 

SR = Single-analyst Standard Deviation, μg/L. 

BILLING CODE 6560–50–P 


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BILLING CODE 6560–50–C 

■ 9. Revise Appendix D to Part 136 to 

read as follows: 

Appendix D to Part 136—Precision and 

Recovery Statements for Methods for 

Measuring Metals 

Two selected methods from ‘‘Methods for 

Chemical Analysis of Water and Wastes,’’ 

EPA–600/4–79–020 (1979) have been 

subjected to interlaboratory method 

validation studies. The two selected methods 

are for Thallium and Zinc. The following 

precision and recovery statements are 

presented in this appendix and incorporated 

into Part 136: 

Method 279.2 

For Thallium, Method 279.2 (Atomic 

Absorption, Furnace Technique) replace the 

Precision and Accuracy Section statement 

with the following: 

Precision and Accuracy 

An interlaboratory study on metal analyses 

by this method was conducted by the Quality 

Assurance Branch (QAB) of the 


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Environmental Monitoring Systems 

Laboratory—Cincinnati (EMSL–CI). Synthetic 

concentrates containing various levels of this 

element were added to reagent water, surface 

water, drinking water and three effluents. 

These samples were digested by the total 

digestion procedure, 4.1.3 in this manual. 

Results for the reagent water are given below. 

Results for other water types and study 

details are found in ‘‘EPA Method Study 31, 

Trace Metals by Atomic Absorption (Furnace 

Techniques),’’ National Technical 

Information Service, 5285 Port Royal Road, 

Springfield, VA 22161 Order No. PB 86–121 

704/AS, by Copeland, F.R. and Maney, J.P., 

January 1986. 

For a concentration range of 10.00–252 

mg/L 

X = 0.8781(C) ¥ 0.715 

S = 0.1112(X) + 0.669 

SR = 0.1005(X) + 0.241 

Where: 

C = True Value for the Concentration, mg/L 

X = Mean Recovery, mg/L 

S = Multi-laboratory Standard Deviation, mg/ 

L 

SR = Single-analyst Standard Deviation, mg/ 

L 

Method 289.2 

For Zinc, Method 289.2 (Atomic 

Absorption, Furnace Technique) replace the 

Precision and Accuracy Section statement 

with the following: 

Precision and Accuracy 

An interlaboratory study on metal analyses 

by this method was conducted by the Quality 

Assurance Branch (QAB) of the 

Environmental Monitoring Systems 

Laboratory—Cincinnati (EMSL–CI). Synthetic 

concentrates containing various levels of this 

element were added to reagent water, surface 

water, drinking water and three effluents. 

These samples were digested by the total 

digestion procedure, 4.1.3 in this manual. 

Results for the reagent water are given below. 

Results for other water types and study 

details are found in ‘‘EPA Method Study 31, 

Trace Metals by Atomic Absorption (Furnace 

Techniques),’’ National Technical 

Information Service, 5285 Port Royal Road, 

Springfield, VA 22161 Order No. PB 86–121 

704/AS, by Copeland, F.R. and Maney, J.P., 

January 1986. 

For a concentration range of 0.51–189 mg/L 

X = 1.6710(C) + 1.485 

S = 0.6740(X) ¥ 0.342 

SR = 0.3895(X)¥ 0.384 

Where: 

C = True Value for the Concentration, mg/L 

X = Mean Recovery, mg/L 

S = Multi-laboratory Standard Deviation, 

mg/L 

SR = Single-analyst Standard Deviation, mg/L 

PART 260—HAZARDOUS WASTE 

MANAGEMENT SYSTEM: GENERAL 

■ 10. The authority citation for Part 260 

continues to read as follows: 

Authority: 42 U.S.C. 6905, 6912(a), 6921– 

6927, 6930, 6934, 6935, 6937, 6938, 6939, 

and 6974. 

Subpart B—Definitions 

■ 11. Section 260.11 is amended by 

revising paragraph (c)(2) to read as 

follows: 

§ 260.11 References. 

* * * * * 

(c) * * * 

(2) Method 1664, n-Hexane 

Extractable Material (HEM; Oil and 

Grease) and Silica Gel Treated n-Hexane 

Extractable Material SGT–HEM; Nonpolar Material) by Extraction and 

Gravimetry: 

(i) Revision A, EPA–821–R–98–002, 

February 1999, IBR approved for Part 

261, Appendix IX. 

(ii) Revision B, EPA–821–R–10–001, 

February 2010, IBR approved for Part 

261, Appendix IX. 

* * * * * 

PART 423—STEAM ELECTRIC POWER 

GENERATING POINT SOURCE 

CATEGORY 

■ 12. The authority citation for Part 423 

continues to read as follows: 

Authority: Secs. 301; 304(b), (c), (e), and 

(g); 306(b) and (c); 307(b) and (c); and 501, 

Clean Water Act (Federal Water Pollution 

Control Act Amendments of 1972, as 

amended by Clean Water Act of 1977) (the 

‘‘Act’’; 33 U.S.C. 1311; 1314(b), (c), (e), and 

(g); 1316(b) and (c); 1317(b) and (c); and 

1361; 86 Stat. 816, Pub. L. 92–500; 91 Stat. 

1567, Pub. L. 95–217), unless otherwise 

noted. 

■ 13. Section 423.11 is amended by 

revising paragraphs (a) and (l) to read as 

follows: 

§ 423.11 Specialized definitions. 

* * * * * 

(a) The term total residual chlorine (or 

total residual oxidants for intake water 

with bromides) means the value 

obtained using any of the ‘‘chlorine— 

total residual’’ methods in Table IB in 

40 CFR 136.3(a), or other methods 

approved by the permitting authority. 

* * * * * 

(l) The term free available chlorine 

means the value obtained using any of 

the ‘‘chlorine—free available’’ methods 

in Table IB in 40 CFR 136.3(a) where the 

method has the capability of measuring 

free available chlorine, or other methods 

approved by the permitting authority. 

* * * * * 

PART 430—PULP, PAPER, AND 

PAPERBOARD POINT SOURCE 

CATEGORY 

■ 14. The authority citation for Part 430 

continues to read as follows: 

Authority: Secs. 301, 304, 306, 307, 308, 

402, and 501, Clean Water Act as amended, 

(33 U.S.C. 1311, 1314, 1316, 1317, 1318, 

1342, and 1361) and Section 112 of the Clean 

Air Act, as amended (42 U.S.C. 7412). 

■ 15. Section 430.01 is amended by 

revising paragraph (a) and by adding 

paragraphs (s) through (v) to read as 

follows: 

§ 430.01 General definitions. 

* * * * * 

(a) Adsorbable organic halides (AOX). 

A bulk parameter that measures the total 

mass of chlorinated organic matter in 

water and wastewater. The approved 

method of analysis for AOX is Method 

1650, which is available in Appendix A 

of this part, and online at http:// 

water.epa.gov/scitech/methods/cwa/ 

index.cfm. 

* * * * * 

(s) TCDD. 2,3,7,8-tetrachlorodibenzop-dioxin. The approved method of 

analysis for TCDD is Method 1613B, 

which is available in Appendix A of this 

part, and online at http://water.epa.gov/ 

scitech/methods/cwa/index.cfm. 

(t) TCDF. 2,3,7,8- 

tetrachlorodibenzofuran. The approved 

method of analysis for TCDF is Method 

1613B, which is available in Appendix 

A of this part, and online at http:// 

water.epa.gov/scitech/methods/cwa/ 

index.cfm. 

(u) Chloroform. The approved 

methods of analysis for chloroform are 

listed in Table IC at 40 CFR 136.3. 

(v) The approved method of analysis 

for the following chlorinated phenolic 

compounds is Method 1653, which is 

available in Appendix A of this part, 

and online at http://water.epa.gov/ 

scitech/methods/cwa/index.cfm: 

(1) Trichlorosyringol. 

(2) 3,4,5-Trichlorocatechol. 

(3) 3,4,6-Trichlorocatechol. 

(4) 3,4,5-Trichloroguaiacol. 

(5) 3,4,6-Trichloroguaiacol. 

(6) 4,5,6-Trichloroguaiacol. 

(7) 2,4,5-Trichlorophenol. 

(8) 2,4,6-Trichlorophenol. 

(9) Tetrachlorocatechol. 

(10) Tetrachloroguaiacol. 

(11) 2,3,4,6–Tetrachlorophenol. 

(12) Pentachlorophenol. 

PART 435—OIL AND GAS 

EXTRACTION POINT SOURCE 

CATEGORY 

■ 16. The authority citation for part 435 

continues to read as follows: 

Authority: 33 U.S.C. 1311, 1314, 1316, 

1317, 1318, 1342, and 1361. 

■ 17. Section 435.11 is amended as 

follows: 

■ a. By revising paragraph (d). 

■ b. By revising paragraph (e). 

■ c. By revising paragraph (k)(2). 


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■ d. By revising paragraph (o). 

■ e. By revising paragraph (t). 

■ f. By revising paragraph (u). 

■ g. By revising paragraph (v). 

■ h. By revising paragraph (x). 

■ i. By revising paragraph (ee). 

■ j. By revising paragraph (gg). 

■ k. By revising paragraph (hh). 

■ l. By revising paragraph (ss). 

■ m. By adding paragraph (uu). 

§ 435.11 Special definitions. 

* * * * * 

(d) Base fluid retained on cuttings as 

applied to BAT effluent limitations and 

NSPS refers to the ‘‘Determination of the 

Amount of Non-Aqueous Drilling Fluid 

(NAF) Base Fluid from Drill Cuttings by 

a Retort Chamber (Derived from API 

Recommended Practice 13B–2)’’, EPA 

Method 1674, which is published as an 

appendix to Subpart A of this part and 

in ‘‘Analytic Methods for the Oil and 

Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See paragraph (uu) 

of this section. 

(e) Biodegradation rate as applied to 

BAT effluent limitations and NSPS for 

drilling fluids and drill cuttings refers to 

the ‘‘Protocol for the Determination of 

Degradation of Non Aqueous Base 

Fluids in a Marine Closed Bottle 

Biodegradation Test System: Modified 

ISO 11734:1995,’’ EPA Method 1647, 

supplemented with ‘‘Procedure for 

Mixing Base Fluids With Sediments,’’ 

EPA Method 1646. Both EPA Method 

1646 and 1647 are published as 

appendices to Subpart A of this part and 

in ‘‘Analytic Methods for the Oil and 

Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See paragraph (uu) 

of this section. 

* * * * * 

(k) * * * 

(2) Dry drill cuttings means the 

residue remaining in the retort vessel 

after completing the retort procedure 

specified in EPA Method 1674, which is 

published as an appendix to Subpart A 

of this part and in ‘‘Analytic Methods 

for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. 

See paragraph (uu) of this section. 

* * * * * 

(o) Formation oil means the oil from 

a producing formation which is detected 

in the drilling fluid, as determined by 

the GC/MS compliance assurance 

method, EPA Method 1655, when the 

drilling fluid is analyzed before being 

shipped offshore, and as determined by 

the RPE method, EPA Method 1670, 

when the drilling fluid is analyzed at 

the offshore point of discharge. The GC/ 

MS compliance assurance method and 

the RPE method approved for use with 

this part are published as appendices to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction 

Point Source Category,’’ EPA–821–R– 

11–004. See paragraph (uu) of this 

section. Detection of formation oil by 

the RPE method may be confirmed by 

the GC/MS compliance assurance 

method, and the results of the GC/MS 

compliance assurance method shall 

apply instead of those of the RPE 

method. 

* * * * * 

(t) Maximum weighted mass ratio 

averaged over all NAF well sections for 

BAT effluent limitations and NSPS for 

base fluid retained on cuttings means 

the weighted average base fluid 

retention for all NAF well sections as 

determined by EPA Method 1674, 

which is published as an appendix to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction 

Point Source Category,’’ EPA–821–R– 

11–004. See paragraph (uu) of this 

section. 

(u) Method 1654A refers to EPA 

Method 1654, Revision A, entitled 

‘‘PAH Content of Oil by HPLC/UV,’’ 

December 1992, which is published as 

an appendix to Subpart A of this part 

and in ‘‘Analytic Methods for the Oil 

and Gas Extraction Point Source 

Category,’’ EPA–821–R–11–004. See 

paragraph (uu) of this section. 

(v) Minimum as applied to BAT 

effluent limitations and NSPS for 

drilling fluids and drill cuttings means 

the minimum 96-hour LC50 value 

allowed as measured in any single 

sample of the discharged waste stream. 

Minimum as applied to BPT and BCT 

effluent limitations and NSPS for 

sanitary wastes means the minimum 

concentration value allowed as 

measured in any single sample of the 

discharged waste stream. 

* * * * * 

(x) No discharge of free oil means that 

waste streams may not be discharged 

that contain free oil as evidenced by the 

monitoring method specified for that 

particular stream, e.g., deck drainage or 

miscellaneous discharges cannot be 

discharged when they would cause a 

film or sheen upon or discoloration of 

the surface of the receiving water; 

drilling fluids or cuttings may not be 

discharged when they fail EPA Method 

1617 (Static Sheen Test), which is 

published as an appendix to Subpart A 

of this part and in ‘‘Analytic Methods 

for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. 

See paragraph (uu) of this section. 

* * * * * 

(ee) Sediment toxicity as applied to 

BAT effluent limitations and NSPS for 

drilling fluids and drill cuttings refers to 

EPA Method 1644: ‘‘Method for 

Conducting a Sediment Toxicity Test 

with Leptocheirus plumulosus and NonAqueous Drilling Fluids or SyntheticBased Drilling Muds’’ and sediment 

preparation procedures specified in EPA 

Method 1646. EPA Method 1644 is 

published in ‘‘Analytic Methods for the 

Oil and Gas Extraction Point Source 

Category,’’ (see paragraph (uu) of this 

section) and EPA Method 1646 is 

published as an appendix to Subpart A 

of this part. 

* * * * * 

(gg) SPP toxicity as applied to BAT 

effluent limitations and NSPS for 

drilling fluids and drill cuttings refers to 

the bioassay test procedure, ‘‘Suspended 

Particulate Phase (SPP) Toxicity Test,’’ 

presented in EPA Method 1619, which 

is published as an appendix to Subpart 

A of this part and in ‘‘Analytic Methods 

for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. 

See paragraph (uu) of this section. 

(hh) Static sheen test means the 

standard test procedure that has been 

developed for this industrial 

subcategory for the purpose of 

demonstrating compliance with the 

requirement of no discharge of free oil. 

The methodology for performing the 

static sheen test is presented in EPA 

Method 1617, which is published as an 

appendix to Subpart A of this part and 

in ‘‘Analytic Methods for the Oil and 

Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See paragraph (uu) 

of this section. 

* * * * * 

(ss) C16-C18 internal olefin drilling 

fluid means a C16-C18 internal olefin 

drilling fluid formulated as specified in 

appendix 1 of subpart A of this part. 

* * * * * 

(uu) Analytic Methods for the Oil and 

Gas Extraction Point Source Category is 

the EPA document, ‘‘Analytic Methods 

for the Oil and Gas Point Source 

Category,’’ December 2011, EPA–821– 

R–11–004, that compiles analytic 

methods for this category. This 

incorporation by reference was 

approved by the Director of the Federal 

Register in accordance with 5 U.S.C. 

552(a) and 1 CFR part 51. Copies may 

be inspected at the National Archives 

and Records Administration (NARA). 

For information on the availability of 

this material at NARA, call 202–741– 

6030, or go to: http://www.archives.gov/ 

federal_register/ 

code_of_federal_regulations/ 

ibr_locations.html. A copy may also be 

inspected at EPA’s Water Docket, 1200 

Pennsylvania Ave. NW., Washington, 

DC 20460. This method may be obtained 


srobinson on DSK4SPTVN1PROD with RULES2
29836 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

at http://water.epa.gov/scitech/ 

methods/cwa/index.cfm. 

■ 18. In § 435.12, Footnote 1 to the table 

is revised to read as follows: 

§ 435.12 Effluent limitations guidelines 

representing the degree of effluent 

reduction attainable by the application of 

the best practicable control technology 

currently available (BPT). 

* * * * * 1No discharge of free oil. See § 435.11(x). 

* * * * * 

■ 19. In § 435.13: 

■ a. Remove ‘‘LC5’’ and add in its place 

‘‘LC50’’ wherever it appears. 

■ b. Footnotes 2, 3, and 5 through 11 to 

the table are revised to read as follows: 

§ 435.13 Effluent limitations guidelines 

representing the degree of effluent 

reduction attainable by the application of 

the best available technology economically 

achievable (BAT). 

* * * * * 2As determined by the suspended 

particulate phase (SPP) toxicity test. See 

§ 435.11(gg). 3As determined by the static sheen test. 

See § 435.11(hh). 

* * * * * 5PAH mass ratio = Mass (g) of PAH (as 

phenanthrene)/Mass (g) of stock base fluid as 

determined by EPA Method 1654, Revision 

A, [specified at § 435.11(u)] entitled ‘‘PAH 

Content of Oil by HPLC/UV,’’ December 

1992, which is published as an appendix to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. See 

§ 435.11(uu). 6Base fluid sediment toxicity ratio = 

10-day LC50 of C16-C18 internal olefin/10-day 

LC50 of stock base fluid as determined by 

EPA Method 1644: ‘‘Method for Conducting 

a Sediment Toxicity Test with Leptocheirus 

plumulosus and Non-Aqueous Drilling 

Fluids or Synthetic-Based Drilling Muds’’ 

after preparing the sediment according to the 

procedure specified in EPA Method 1646, 

which are published as appendices to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. See 

§ 435.11(ee) and (uu). 7Biodegradation rate ratio = Cumulative 

headspace gas production (ml) of C16-C18

internal olefin/Cumulative headspace gas 

production (ml) of stock base fluid, both at 

275 days as determined by EPA Method 

1647, which is published as an appendix to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. See 

§ 435.11(e) and (uu). 8 Drilling fluid sediment toxicity ratio = 4- 

day LC50 of C16-C18 internal olefin drilling 

fluid/4-day LC50 of drilling fluid removed 

from drill cuttings at the solids control 

equipment as determined by EPA Method 

1644: ‘‘Method for Conducting a Sediment 

Toxicity Test with Leptocheirus plumulosus 

and Non-Aqueous Drilling Fluids or 

Synthetic-Based Drilling Muds’’ after 

sediment preparation procedures specified in 

EPA Method 1646, which are published as 

appendices to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(ee) and (uu). 9As determined before drilling fluids are 

shipped offshore by the GC/MS compliance 

assurance method (EPA Method 1655), and 

as determined prior to discharge by the RPE 

method (EPA Method 1670) applied to 

drilling fluid removed from drill cuttings. If 

the operator wishes to confirm the results of 

the RPE method (EPA Method 1670), the 

operator may use the GC/MS compliance 

assurance method (EPA Method 1655). 

Results from the GC/MS compliance 

assurance method (EPA Method 1655) shall 

supersede the results of the RPE method 

(EPA Method 1670). EPA Method 1655 and 

1670 are published as appendices to Subpart 

A of this part and in ‘‘Analytic Methods for 

the Oil and Gas Extraction Point Source 

Category,’’ EPA–821–R–11–004. See 

§ 435.11(uu). 10Maximum permissible retention of nonaqueous drilling fluid (NAF) base fluid on 

wet drill cuttings averaged over drilling 

intervals using NAFs as determined by EPA 

Method 1674, which is published as an 

appendix to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(uu). This 

limitation is applicable for NAF base fluids 

that meet the base fluid sediment toxicity 

ratio (Footnote 6), biodegradation rate ratio 

(Footnote 7), PAH, mercury, and cadmium 

stock limitations (C16-C18 internal olefin) 

defined above in this table. 11Maximum permissible retention of nonaqueous drilling fluid (NAF) base fluid on 

wet drill cuttings average over drilling 

intervals using NAFs as determined by EPA 

Method 1674, which is published as an 

appendix to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(uu). This 

limitation is applicable for NAF base fluids 

that meet the ester base fluid sediment 

toxicity ratio and ester biodegradation rate 

ratio stock limitations defined as: 

(a) ester base fluid sediment toxicity ratio 

= 10-day LC50 of C12-C14 ester or C8 ester/10- 

day LC50 of stock base fluid as determined by 

EPA Method 1644: ‘‘Method for Conducting 

a Sediment Toxicity Test with Leptocheirus 

plumulosus and Non-Aqueous Drilling 

Fluids or Synthetic-Based Drilling Muds’’ 

after sediment preparation procedures 

specified in EPA Method 1646, which are 

published as appendices to Subpart A of this 

part and in ‘‘Analytic Methods for the Oil 

and Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See § 435.11(ee) and 

(uu); 

(b) ester biodegradation rate ratio = 

Cumulative headspace gas production (ml) of 

C12-C14 ester or C8 ester/Cumulative 

headspace gas production (ml) of stock base 

fluid, both at 275 days as determined by EPA 

Method 1647, which is published as an 

appendix to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(e) and (uu); and 

(c) PAH mass ratio (Footnote 5), mercury, 

and cadmium stock limitations (C16-C18

internal olefin) defined above in this table. 

■ 20. In § 435.14 footnote 2 to the table 

is revised to read as follows: 

§ 435.14 Effluent limitations guidelines 

representing the degree of effluent 

reduction attainable by the application of 

the best conventional pollutant control 

technology (BCT). 

* * * * * 2As determined by the static sheen test. 

See § 435.11(hh). 

* * * * * 

■ 21. In § 435.15: 

■ a. Remove ‘‘LC5’’ and add in its place 

‘‘LC50’’wherever it appears. 

■ b. Footnotes 2, 3, and 5 through 11 to 

the table are revised to read as follows: 

§ 435.15 Standards of performance for 

new sources (NSPS). 

* * * * * 2As determined by the suspended 

particulate phase (SPP) toxicity test. See 

§ 435.11(gg). 3As determined by the static sheen test. 

See § 435.11(hh). 

* * * * * 5PAH mass ratio = Mass (g) of PAH (as 

phenanthrene)/Mass (g) of stock base fluid as 

determined by EPA Method 1654, Revision 

A, [specified at § 435.11(u)] entitled ‘‘PAH 

Content of Oil by HPLC/UV,’’ December 

1992, which is published as an appendix to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. See 

§ 435.11(uu). 6Base fluid sediment toxicity ratio = 10- 

day LC50 of C16-C18 internal olefin/10-day 

LC50 of stock base fluid as determined by 

EPA Method 1644: ‘‘Method for Conducting 

a Sediment Toxicity Test with Leptocheirus 

plumulosus and Non-Aqueous Drilling 

Fluids or Synthetic-Based Drilling Muds’’ 

after preparing the sediment according to the 

procedure specified in EPA Method 1646, 

which are published as appendices to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. See 

§ 435.11(ee) and (uu). 7Biodegradation rate ratio = Cumulative 

headspace gas production (ml) of C16-C18

internal olefin/Cumulative headspace gas 

production (ml) of stock base fluid, both at 

275 days as determined by EPA Method 

1647, which is published as an appendix to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. See 

§ 435.11(e) and (uu). 8 Drilling fluid sediment toxicity ratio = 

4-day LC50 of C16-C18 internal olefin drilling 

fluid/4-day LC50 of drilling fluid removed 

from drill cuttings at the solids control 

equipment as determined by EPA Method 

1644: ‘‘Method for Conducting a Sediment 

Toxicity Test with Leptocheirus plumulosus 

and Non-Aqueous Drilling Fluids or 

Synthetic-Based Drilling Muds’’ after 

sediment preparation procedures specified in 


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EPA Method 1646, which are published as 

appendices to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(ee) and (uu). 9As determined before drilling fluids are 

shipped offshore by the GC/MS compliance 

assurance method (EPA Method 1655), and 

as determined prior to discharge by the RPE 

method (EPA Method 1670) applied to 

drilling fluid removed from drill cuttings. If 

the operator wishes to confirm the results of 

the RPE method (EPA Method 1670), the 

operator may use the GC/MS compliance 

assurance method (EPA Method 1655). 

Results from the GC/MS compliance 

assurance method (EPA Method 1655) shall 

supersede the results of the RPE method 

(EPA Method 1670). EPA Method 1655 and 

1670 are published as appendices to Subpart 

A of this part and in ‘‘Analytic Methods for 

the Oil and Gas Extraction Point Source 

Category,’’ EPA–821–R–11–004. See 

§ 435.11(uu). 10Maximum permissible retention of nonaqueous drilling fluid (NAF) base fluid on 

wet drill cuttings averaged over drilling 

intervals using NAFs as determined by EPA 

Method 1674, which is published as an 

appendix to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(uu). This 

limitation is applicable for NAF base fluids 

that meet the base fluid sediment toxicity 

ratio (Footnote 6), biodegradation rate ratio 

(Footnote 7), PAH, mercury, and cadmium 

stock limitations (C16-C18 internal olefin) 

defined above in this table. 11Maximum permissible retention of nonaqueous drilling fluid (NAF) base fluid on 

wet drill cuttings average over drilling 

intervals using NAFs as determined by EPA 

Method 1674, which is published as an 

appendix to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(uu). This 

limitation is applicable for NAF base fluids 

that meet the ester base fluid sediment 

toxicity ratio and ester biodegradation rate 

ratio stock limitations defined as: 

(a) ester base fluid sediment toxicity ratio 

= 10-day LC50 of C12-C14 ester or C8 ester/10- 

day LC50 of stock base fluid as determined by 

EPA Method 1644: ‘‘Method for Conducting 

a Sediment Toxicity Test with Leptocheirus 

plumulosus and Non-Aqueous Drilling 

Fluids or Synthetic-Based Drilling Muds’’ 

after sediment preparation procedures 

specified in EPA Method 1646, which are 

published as appendices to Subpart A of this 

part and in ‘‘Analytic Methods for the Oil 

and Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See § 435.11(ee) and 

(uu); 

(b) ester biodegradation rate ratio = 

Cumulative headspace gas production (ml) of 

C12-C14 ester or C8 ester/Cumulative 

headspace gas production (ml) of stock base 

fluid, both at 275 days as determined by EPA 

Method 1647, which is published as an 

appendix to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(e) and (uu); and 

(c) PAH mass ratio (Footnote 5), mercury, 

and cadmium stock limitations (C16-C18

internal olefin) defined above in this table. 

■ 22. The heading of Appendix 1 to 

Subpart A of Part 435 is revised to read 

as follows: 

Appendix 1 to Subpart A of Part 435— 

Static Sheen Test (EPA Method 1617) 

* * * * * 

■ 23. Appendix 2 to Subpart A of Part 

435 is amended as follows: 

■ a. Revise the appendix heading. 

■ b. Remove the fourth sentence from 

Section II.C.6. 

■ c. Revise Section III.A.1. 

■ d. Revise Section III.E.2. 

The revisions read as follows: 

Appendix 2 to Subpart A of Part 435— 

Drilling Fluids Toxicity Test (EPA 

Method 1619) 

* * * * * 

III–A. * * * 

(1) Each definitive test consists of 18 test 

containers: 3 replicates of a control and 5 

SPP dilutions. Test containers should be 

Pyrex or equivalent glass. For definitive tests, 

5 SPP dilutions with 3 replicates of at least 

500 ml each are required. Twenty mysids per 

replicate, 360 per definitive test are required. 

* * * * * 

III–E. * * * 

(2) Establish the definitive test 

concentrations based on results of a range 

finding test or based on prior experience and 

knowledge of the mud system. 

* * * * * 

■ 24. The heading of Appendix 3 to 

Subpart A of Part 435 is amended to 

read as follows: 

Appendix 3 to Subpart A of Part 435— 

Procedure for Mixing Base Fluids With 

Sediments (EPA Method 1646) 

* * * * * 

■ 25. Appendix 4 to Subpart A of Part 

435 is revised to read as follows: 

Appendix 4 to Subpart A of Part 435— 

Protocol for the Determination of 

Degradation of Non-Aqueous Base 

Fluids in a Marine Closed Bottle 

Biodegradation Test System: Modified 

ISO 11734:1995 (EPA Method 1647) 

1.0. Summary of EPA Method 1647 

a. This method determines the anaerobic 

degradation potential of mineral oils, paraffin 

oils and non-aqueous fluids (NAF) in 

sediments. These substrates are base fluids 

for formulating offshore drilling fluids. The 

test evaluates base fluid biodegradation rates 

by monitoring gas production due to 

microbial degradation of the test fluid in 

natural marine sediment. 

b. The test procedure places a mixture of 

marine/estuarine sediment, test substrate 

(hydrocarbon or controls) and seawater into 

clean 120 mL (150 mL actual volume) 

Wheaton serum bottles. The test is run using 

four replicate serum bottles containing 2,000 

mg carbon/kg dry weight concentration of 

test substrate in sediment. The use of 

resazurin dye solution (1 ppm) evaluates the 

anaerobic (redox) condition of the bottles 

(dye is blue when oxygen is present, reddish 

in low oxygen conditions and colorless if 

oxygen free). After capping the bottles, a 

nitrogen sparge removes air in the headspace 

before incubation begins. During the 

incubation period, the sample should be kept 

at a constant temperature of 29 ± 1°C. Gas 

production and composition is measured 

approximately every two weeks. The samples 

need to be brought to ambient temperature 

before making the measurements. Measure 

gas production using a pressure gauge. 

Barometric pressure is measured at the time 

of testing to make necessary volume 

adjustments. 

c. ISO 11734:1995 specifies that total gas 

is the standard measure of biodegradation. 

While modifying this test for evaluating 

biodegradation of NAFs, methane was also 

monitored and found to be an acceptable 

method of evaluating biodegradation. Section 

7 contains the procedures used to follow 

biodegradation by methane production. 

Measurement of either total gas or methane 

production is permitted. If methane is 

followed, determine the composition of the 

gas by using gas chromatography (GC) 

analysis at each sampling. At the end of the 

test when gas production stops, or at around 

275 days, an analysis of sediment for 

substrate content is possible. Common 

methods which have been successfully used 

for analyzing NAFs from sediments are listed 

in Section 8. 

2.0 System Requirements 

This environmental test system has three 

phases, spiked sediment, overlying seawater, 

and a gas headspace. The sediment/test 

compound mixture is combined with 

synthetic sea water and transferred into 120- 

mL serum bottles. The total volume of 

sediment/sea water mixture in the bottles is 

75 mL. The volume of the sediment layer will 

be approximately 50 mL, but the exact 

volume of the sediment will depend on 

sediment characteristics (wet:dry ratio and 

density). The amount of synthetic sea water 

will be calculated to bring the total volume 

in the bottles to 75 mL. The test systems are 

maintained at a temperature of 29 ± 1°C 

during incubation. The test systems are 

brought to ambient temperatures prior to 

measuring pressure or gas volume. 

2.1 Sample Requirements 

a. The concentration of base fluids are at 

least 2,000 mg carbon test material/kg dry 

sediment. Carbon concentration is 

determined by theoretical composition based 

on the chemical formula or by chemical 

analysis by ASTM D5291–96. Sediments 

with positive, intermediate and negative 

control substances as well as a C16-C18

internal olefin type base fluid will be run in 

conjunction with test materials under the 

same conditions. The positive control is ethyl 

oleate (CAS 111–62–6), the intermediate 

control is 1-hexadecene (CAS 629–73–2), and 

the negative control is squalane (CAS 111– 

01–3). Controls must be of analytical grade or 


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29838 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

the highest grade available. Each test control 

concentration should be prepared according 

to the mixing procedure described in Section 

3.1. 

b. Product names will be used for examples 

or clarification in the following text. Any use 

of trade or product names in this publication 

is for descriptive use only, and does not 

constitute endorsement by EPA or the 

authors. 

2.2. Seawater Requirements 

Synthetic seawater at a salinity of 25 ± 1 

ppt should be used for the test. The synthetic 

seawater should be prepared by mixing a 

commercially available artificial seawater 

mix, into high purity distilled or de-ionized 

water. The seawater should be aerated and 

allowed to age for approximately one month 

prior to use. 

2.3. Sediment Requirements 

a. The dilution sediment must be from a 

natural estuarine or marine environment and 

be free of the compounds of interest. The 

collection location, date and time will be 

documented and reported. The sediment is 

prepared by press-sieving through a 2,000- 

micron mesh sieve to remove large debris, 

then press-sieving through a 500-micron 

sieve to remove indigenous organisms that 

may confound test results. The water content 

of the sediment should be less than 60% 

(w/w) or a wet to dry ratio of 2.5. The 

sediment should have a minimum organic 

matter content of 3% (w/w) as determined by 

ASTM D2974–07a (Method A and D and 

calculate organic matter as in Section 8.3 of 

method ASTM D2974–07a). 

b. To reduce the osmotic shock to the 

microorganisms in the sediment the salinity 

of the sediment’s pore water should be 

between 20–30 ppt. Sediment should be used 

for testing as soon as possible after field 

collection. If required, sediment can be 

stored in the dark at 4 °C with 3–6 inches of 

overlying water in a sealed container for a 

maximum period of 2 months prior to use. 

3.0 Test Set Up 

The test is set up by first mixing the test 

or control substrates into the sediment 

inoculum, then mixing in seawater to make 

a pourable slurry. The slurry is then poured 

into serum bottles, which are then flushed 

with nitrogen and sealed. 

3.1. Mixing Procedure 

Because base fluids are strongly 

hydrophobic and do not readily mix with 

sediments, care must be taken to ensure base 

fluids are thoroughly homogenized within 

the sediment. All concentrations are weightto-weight comparisons (mg of base fluid to kg 

of dry control sediment). Sediment and base 

fluid mixing will be accomplished by using 

the following method. 

3.1.1. Determine the wet to dry weight ratio 

for the control sediment by weighing 

approximately 10 sub-samples of 

approximately 1 g each of the screened and 

homogenized wet sediment into tared 

aluminum weigh pans. Dry sediment at 105 

°C for 18–24 h. Remove the dried sediments 

and cool in a desiccator. Repeat the drying, 

cooling, and weighing cycle until a constant 

weight is achieved (within 4% of previous 

weight). Re-weigh the samples to determine 

the dry weight. Calculate the mean wet and 

dry weights of the 10 sub samples and 

determine the wet/dry ratio by dividing the 

mean wet weight by the mean dry weight 

using Equation 5–1. This is required to 

determine the weight of wet sediment needed 

to prepare the test samples. 

3.1.2. Determine the density (g/ml) of the 

wet sediment. This will be used to determine 

total volume of wet sediment needed for the 

various test treatments. One method is to tare 

a 5 ml graduated cylinder and add about 5 

ml of homogenized sediment. Carefully 

record the volume then weigh this volume of 

sediment. Repeat this a total of three times. 

To determine the wet sediment density, 

divide the weight by volume per the 

following formula: 

3.1.3. Determine the amount of base fluid 

to be spiked into wet sediment in order to 

obtain the desired initial base fluid 

concentration of 2,000 mg carbon/kg dry 

weight. An amount of wet sediment that is 

the equivalent of 30 g of dry sediment will 

be added to each bottle. A typical procedure 

is to prepare enough sediment for 8 serum 

bottles (3 bottles to be sacrificed at the start 

of the test, 4 bottles incubated for headspace 

analysis, and enough extra sediment for 2 

extra bottles). Extra sediment is needed 

because some of the sediment will remain 

coated onto the mixing bowl and utensils. 

Experience with this test may indicate that 

preparing larger volumes of spiked sediment 

is a useful practice, then the following 

calculations should be adjusted accordingly. 

a. Determine the total weight of dry 

sediment needed to add 30 g dry sediment 

to 8 bottles. If more bottles are used then the 

calculations should be modified accordingly. 

For example: 

b. Determine the weight of base fluid, in 

terms of carbon, needed to obtain a final base 

fluid concentration of 2,000 mg carbon/kg 

dry weight. For example: 

c. i. Convert from mg of carbon to mg of 

base fluid. This calculation will depend on 

the % fraction of carbon present in the 

molecular structure of each base fluid. For 

the control fluids, ethyl oleate is composed 

of 77.3% carbon, hexadecene is composed of 

85.7% carbon, and squalane is composed of 

85.3% carbon. The carbon fraction of each 

base fluid should be supplied by the 

manufacturer or determined before use. 

ASTM D5291–96 or equivalent will be used 

to determine composition of fluid. 

ii. To calculate the amount of base fluid to 

add to the sediment, divide the amount of 

carbon (480 mg) by the percent fraction of 

carbon in the fluid. 

iii. For example, the amount of ethyl oleate 

added to 240 g dry weight sediment can be 

calculated from the following equation: 


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Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 29839 

iv. Therefore, add 621 mg of ethyl oleate 

to 240 g dry weight sediment for a final 

concentration of 2,000 mg carbon/kg 

sediment dry weight. 

3.1.4. Mix the calculated amount of base 

fluid with the appropriate weight of wet 

sediment. 

a. Use the wet:dry ratio to convert from g 

sediment dry weight to g sediment wet 

weight, as follows: 

b. i. Weigh the appropriate amount of base 

fluid (calculated in Section 3.1.3.c) into 

stainless mixing bowls, tare the vessel 

weight, then add the wet sediment calculated 

in Equation 5, and mix with a high shear 

dispersing impeller for 9 minutes. 

ii. The sediment is now mixed with 

synthetic sea water to form a slurry that will 

be transferred into the bottles. 

3.2. Creating Seawater/Sediment Slurry 

Given that the total volume of sediment/ 

sea water slurry in each bottle is to be 75 mL, 

determine the volume of sea water to add to 

the wet sediment. 

3.2.1. If each bottle is to contain 30 g dry 

sediment, calculate the weight, and then the 

volume, of wet sediment to be added to each 

bottle. 

3.2.4. Convert the wet sediment weight 

from Equation 6 into a volume using the 

sediment density. 

3.2.5. Determine the amount of sea water 

to mix with the wet sediment. 

Mix sea water thoroughly with wet 

sediment to form a sediment/sea water 

slurry. 

3.3. Bottling the Sediment Seawater Slurry 

The total volume of sediment/sea water 

slurry in each bottle is to be 75 mL. Convert 

the volume (mL) of sediment/sea water slurry 

into a weight (g) using the density of the 

sediment and the seawater. 


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This should provide each bottle with 30 g 

dry sediment in a total volume of 75 mL. 

3.3.4. Putting the sediment:seawater slurry 

in the serum bottles. 

a. Note: The slurry will need to be 

constantly stirred to keep the sediment 

suspended. 

b. Place a tared serum bottle on a balance 

and add the appropriate amount of slurry to 

the bottle using a funnel. Once the required 

slurry is in the bottle remove the funnel, add 

2–3 drops (25 mL) of a 1 gram/L resazurin dye 

stock solution. Cap the bottle with a butyl 

rubber stopper (Bellco Glass, Part #2048– 

11800) and crimp with an aluminum seal 

(Bellco Glass Part #2048–11020). 

c. Using a plastic tube with a (23-gauge, 1- 

inch long) needle attached to one side and a 

nitrogen source to the other, puncture the 

serum cap with the needle. Puncture the 

serum cap again with a second needle to 

sparge the bottle’s headspace of residual air 

for two minutes. The nitrogen should be 

flowing at no more than 100 mL/min to 

encourage gentle displacement of oxygenated 

air with nitrogen. Faster nitrogen flow rates 

would cause mixing and complete oxygen 

removal would take much longer. Remove 

the nitrogen needle first to avoid any initial 

pressure problems. The second (vent) needle 

should be removed within 30 seconds of 

removing the nitrogen needle. 

d. Triplicate blank test systems are 

prepared, with similar quantities of sediment 

and seawater without any base fluid. 

Incubate in the dark at a constant 

temperature of 29 ± 1 °C. 

e. Record the test temperature. The test 

duration is dependent on base fluid 

performance, but at a maximum should be no 

more than 275 days. Stop the test after all 

base fluids have achieved a plateau of gas 

production. At termination, base fluid 

concentrations can be verified in the 

terminated samples by extraction and GC 

analysis according to Section 8. 

4.0. Concentration Verification Chemical 

Analyses 

a. Because of the difficulty of 

homogeneously mixing base fluid with 

sediment, it is important to demonstrate that 

the base fluid is evenly mixed within the 

sediment sea water slurry that was added to 

each bottle. Of the seven serum bottles set up 

for each test or control condition, three are 

randomly selected for concentration 

verification analyses. These should be 

immediately placed at 4 °C and a sample of 

sediment from each bottle should be 

analyzed for base fluid content as soon as 

possible. The coefficient of variation (CV) for 

the replicate samples must be less than 20%. 

The results should show recovery of at least 

70% of the spiked base fluid. Use an 

appropriate analytical procedure described in 

Section 8 to perform the extractions and 

analyses. If any set of sediments fail the 

criteria for concentration verification, then 

the corrective action for that set of sediments 

is also outlined in Section 8. 

b. The nominal concentrations and the 

measured concentrations from the three 

bottles selected for concentration verification 

should be reported for the initial test 

concentrations. The coefficient of variation 

(CV) for the replicate samples must be less 

than 20%. If base fluid content results are not 

within the 20% CV limit, the test must be 

stopped and restarted with adequately mixed 

sediment. 

5.0. Gas Monitoring Procedures 

Biodegradation is measured by total gas as 

specified in ISO 11734:1995. Methane 

production can also be tracked and is 

described in Section 7. 

5.1. Total Gas Monitoring Procedures 

Bottles should be brought to room 

temperature before readings are taken. a. The 

bottles are observed to confirm that the 

resazurin has not oxidized to pink or blue. 

Total gas production in the culture bottles 

should be measured using a pressure 

transducer (one source is Biotech 

International). The pressure readings from 

test and control cultures are evaluated 

against a calibration curve created by 

analyzing the pressure created by known 

additions of gas to bottles established 

identically to the culture bottles. Bottles used 

for the standard curve contain 75 mL of 

water, and are sealed with the same rubber 

septa and crimp cap seals used for the bottles 

containing sediment. After the bottles used in 

the standard curve have been sealed, a 

syringe needle inserted through the septa is 

used to equilibrate the pressure inside the 

bottles to the outside atmosphere. The 

syringe needle is removed and known 

volumes of air are injected into the 

headspace of the bottles. Pressure readings 

provide a standard curve relating the volume 

of gas injected into the bottles and headspace 

pressure. No less than three points may be 

used to generate the standard curve. A 

typical standard curve may use 0, 1, 5, 10, 

20 and 40 mL of gas added to the standard 

curve bottles. 

b. The room temperature and barometric 

pressure (to two digits) should be recorded at 

the time of sampling. One option for the 

barometer is Fisher Part #02–400 or 02–401. 

Gas production by the sediment is expressed 

in terms of the volume (mL) of gas at 

standard temperature (0 °C = 273 °K) and 

pressure (1 atm = 30 inches of Hg) using Eq. 

16. 

Where: 

V2 = Volume of gas production at standard 

temperature and pressure 

P1 = Barometric pressure on day of sampling 

(inches of Hg) 

V1 = Volume of gas measured on day of 

sampling (mL) 

T2 = Standard temperature = 273 °K 

T1 = Temperature on day of sampling (°C + 

273 = °K) 

P2 = Standard pressure = 30 inches Hg 

c. An estimate can be made of the total 

volume of anaerobic gas that will be 

produced in the bottles. The gas production 

measured for each base fluid can be 

expressed as a percent of predicted total 

anaerobic gas production. 

5.1.1. Calculate the total amount of carbon 

in the form of the base fluid present in each 

bottle. 

a. Each bottle is to contain 30 g dry weight 

sediment. The base fluid concentration is 

2,000 mg carbon/kg dry weight sediment. 

Therefore: 


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5.1.2. Theory states that anaerobic 

microorganisms will convert 1 mole of 

carbon substrate into 1 mole of total 

anaerobic gas production. 

a. Calculate the number of moles of carbon 

in each bottle. 

b. The molecular weight of carbon is 12 

(i.e., 1 mole of carbon = 12 g). Therefore, the 

number of moles of carbon in each bottle can 

be calculated. 

5.1.3. Calculate the predicted volume of 

anaerobic gas. 

One mole of gas equals 22.4 L (at standard 

temperature and pressure), therefore, 

5.2. Gas Venting 

a. If the pressure in the serum bottle is too 

great for the pressure transducer or syringe, 

some of the excess gas must be wasted. The 

best method to do this is to vent the excess 

gas right after measurement. To do this, 

remove the barrel from a 10-mL syringe and 

fill it 1⁄3 full with water. This is then inserted 

into the bottle through the stopper using a 

small diameter (high gauge) needle. The 

excess pressure is allowed to vent through 

the water until the bubbles stop. This allows 

equalization of the pressure inside the bottle 

to atmospheric without introducing oxygen. 

The amount of gas vented (which is equal to 

the volume determined that day) must be 

kept track of each time the bottles are vented. 

A simple way to do this in a spreadsheet 

format is to have a separate column in which 

cumulative vented gas is tabulated. Each time 

the volume of gas in the cultures is analyzed, 

the total gas produced is equal to the gas in 

the culture at that time plus the total of the 

vented gas. 

b. To keep track of the methane lost in the 

venting procedure, multiply the amount of 

gas vented each time by the corrected % 

methane determined on that day. The answer 

gives the volume of methane wasted. This 

must be added into the cumulative totals 

similarly to the total gas additions. 

6.0. Test Acceptability and Interpretation 

6.1. Test Acceptability 

At day 275 or when gas production has 

plateaued, whichever is first, the controls are 

evaluated to confirm that the test has been 

performed appropriately. In order for this 

modification of the closed bottle 

biodegradation test to be considered 

acceptable, all the controls must meet the 

biodegradation levels indicated in Table 1. 

The intermediate control hexadecene must 

produce at least 30% of the theoretical gas 

production. This level may be reexamined 

after two years and more data has been 

generated. 

TABLE 1—TEST ACCEPTABILITY CRITERIA

Concentration Percent biodegradability as a function of gas measurement 

Positive control Squalane negative control Hexadecene intermediate control 

2,000 mg carbon/kg ................................ ≥60% theoretical .................................... ≤5% theoretical ...................................... ≥30% theoretical. 

6.2 Interpretation 

a. In order for a fluid to pass the closed 

bottle test, the biodegradation of the base 

fluid as indicated by the total amount of total 

gas (or methane) generated once gas 

production has plateaued (or at the end of 

275 days, which ever is first) must be greater 

than or equal to the volume of gas (or 

methane) produced by the reference standard 

(internal elefin or ester). 

b. The method for evaluating the data to 

determine whether a fluid has passed the 

biodegradation test must use the equations: 

Where: 

NAF = Stock base fluid being tested for 

compliance 

Reference fluid = C16-C18 internal olefin or 

C12 –C14 or C8 ester reference fluid 

7.0. Methane Measurement 

7.1. Methane Monitoring Procedures 

a. The use of total gas production alone 

may result in an underestimation of the 

actual metabolism occurring since CO2 is 

slightly soluble in water. An acceptable 

alternative method is to monitor methane 

production and total gas production. This is 

easily done using GC analysis. A direct 

injection of headspace gases can be made 

into a GC using almost any packed or 

capillary column with an FID detector. 

Unless volatile fuels or solvents are present 

in the test material or the inocula, the only 

component of the headspace gas that can be 

detected using an FID detector is methane. 

The percent methane in the headspace gas is 

determined by comparing the response of the 

sample injections to the response from 

injections of known percent methane 

standards. The percent methane is corrected 

for water vapor saturation using Eq. 21 and 

then converted to a volume of dry methane 

using Eq. 22. 


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Where: D = The density of water vapor at saturation 

(g/m3, can be found in CRC Handbook of 

Chemistry and Physics) for the 

temperature of sampling. 

Where: 

VCH4 = Volume of methane in the bottle 

S = Volume of excess gas production 

(measured with a pressure transducer) 

V = Volume of the headspace in the culture 

bottle (total volume—liquid phase) 

P = Barometric pressure (mm Hg, measured 

with barometer) 

T = Temperature (°C) 

Pw = Vapor pressure of water at T (mm Hg, 

can be found in CRC Handbook of 

Chemistry and Physics) 

CH4 = % methane in headspace gas (after 

correction for water vapor) 

b. The total volume of serum bottles sold 

as 125 mL bottles (Wheaton) is 154.8 mL. 

c. The volumes of methane produced are 

then compared to the volumes of methane in 

the controls to determine if a significant 

inhibition of methane production or a 

significant increase of methane production 

has been observed. Effective statistical 

analyses are important, as variability in the 

results is common due to the heterogeneity 

of the inoculum’s source. It is also common 

to observe that the timing of the initiation of 

culture activity is not equal in all of the 

cultures. Expect a great variability over the 

period when the cultures are active, some 

replicates will start sooner than others, but 

all of the replicates should eventually reach 

similar levels of base fluid degradation and 

methane production. 

7.2. Expected Methane Production 

Calculations 

a. The amount of methane expected can be 

calculated using the equation of Symons and 

Buswell (Eq. 23). In the case of complete 

mineralization, all of the carbon will appear 

as wither CO2 or CH4, thus the total moles 

of gas produced will be equal to the total 

moles of carbon in the parent molecule. The 

use of the Buswell equation allows you to 

calculate the effects the redox potential will 

have on the distribution of the products in 

methanogenic cultures. More reduced 

electron donors will allow the production of 

more methane, while more oxidized electron 

donors will cause a production of more 

carbon dioxide. 

b. An example calculation of the expected 

methane volume in a culture fed 2,000 mg/ 

kg hexadecene is as follows. The application 

of Symons and Buswell’s equation reveals 

that hexadecene (C16H32) will yield 4 moles 

of CO2 and 12 moles of CH4. Assuming 30 g 

of dry sediment are added to the bottles with 

2,334 mg hexadecene/kg dry sediment (i.e., 

equivalent to 2,000 mg carbon/kg dry 

sediment) the calculation is as follows. 

c. By subtracting the average amount of 

methane in control bottles from the test 

bottles and then dividing by the expected 

volume an evaluation of the completion of 

the process may be conducted. 

8.0. Concentration Verification Analysis 

The Concentration Verification analysis is 

required at the beginning of the test to ensure 

homogeneity and confirm that the required 

amount of fluid was delivered to the 

sediments at the start of the test. 

8.1. Three samples per fluid need to be 

analyzed and achieve ≤20% Coefficient of 

Variability and an average of ≥70% to ≤120% 

of fluid delivered to sediment. 

8.2. If a third party performs the analysis, 

then the laboratory should be capable of 

delivering the homogeneity data within 

seven days, in order to identify any samples 

that do not meet the homogeneity 

requirement as quickly as possible. 

8.3. If one sediment/fluid set, out a 

multiple set batch of samples, fails these 

criteria, then that one set of samples must be 

discarded and a fresh set of spiked sediment 

prepared, started, and analyzed to ensure 

homogeneity. The same stock sediment is 

used to prepare the replacement set(s). The 

remaining sets do not need to be re-mixed or 

restarted. 

8.4. The re-mixed set(s) will need to be run 

the additional days as appropriate to ensure 

that the total number of days is the same for 

all sets of bottles, even though the specific 

days are not aligned. 

8.5. Re-mixing of bottle sets can be 

performed multiple times as a result of a 

failure of the analytical criteria, until the 

holding time for the stock sediment has 

expired (60 days). If the problem set(s) has 

not fallen within the acceptable analytical 

criteria by then, it must not be part of the 

batch of bottles run. If the problem batch is 

one of the controls, and those controls were 

not successfully prepared when the sediment 

holding time expired, then the entire test 

must be restarted. 

9.0 Program Quality Assurance and 

Quality Control 

9.1 Calibration 

9.1.1. All equipment/instrumentation will 

be calibrated in accordance with the test 

method or the manufacturer’s instructions 

and may be scheduled or triggered. 

9.1.2. Where possible, standards used in 

calibration will be traceable to a nationally 

recognized standard (e.g., certified standard 

by NIST). 

9.1.3. All calibration activities will be 

documented and the records retained. 

9.1.4. The source, lot, batch number, and 

expiration date of all reagents used with be 

documented and retained. 


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9.2. Maintenance 

9.2.1. All equipment/instrumentation will 

be maintained in accordance with the test 

method or the manufacturer’s instructions 

and may be scheduled or triggered. 

9.2.2. All maintenance activities will be 

documented and the records retained. 

9.3. Data Management and Handling 

9.3.1. All primary (raw) data will be 

correct, complete, without selective 

reporting, and will be maintained. 

9.3.2. Hand-written data will be recorded 

in lab notebooks or electronically at the time 

of observation. 

9.3.3. All hand-written records will be 

legible and amenable to reproduction by 

electrostatic copiers. 

9.3.4. All changes to data or other records 

will be made by: 

a. Using a single line to mark-through the 

erroneous entry (maintaining original data 

legibility). 

b. Write the revision. 

c. Initial, date, and provide revision code 

(see attached or laboratory’s equivalent). 

9.3.5. All data entry, transcriptions, and 

calculations will be verified by a qualified 

person. 

a. Verification will be documented by 

initials of verifier and date. 

9.3.6. Procedures will be in place to 

address data management procedures used 

(at minimum): 

a. Significant figures. 

b. Rounding practices. 

c. Identification of outliers in data series. 

d. Required statistics. 

9.4. Document Control 

9.4.1. All technical procedures, methods, 

work instructions, standard operating 

procedures must be documented and 

approved by laboratory management prior to 

the implementation. 

9.4.2. All primary data will be maintained 

by the contractor for a minimum of five (5) 

years. 

9.5. Personnel and Training 

9.5.1. Only qualified personnel shall 

perform laboratory activities. 

9.5.2. Records of staff training and 

experience will be available. This will 

include initial and refresher training (as 

appropriate). 

9.6. Test Performance 

9.6.1. All testing will done in accordance 

with the specified test methods. 

9.6.2. Receipt, arrival condition, storage 

conditions, dispersal, and accountability of 

the test article will be documented and 

maintained. 

9.6.3. Receipt or production, arrival or 

initial condition, storage conditions, 

dispersal, and accountability of the test 

matrix (e.g., sediment or artificial seawater) 

will be documented and maintained. 

9.6.4. Source, receipt, arrival condition, 

storage conditions, dispersal, and 

accountability of the test organisms 

(including inoculum) will be documented 

and maintained. 

9.6.5. Actual concentrations administered 

at each treatment level will be verified by 

appropriate methodologies. 

9.6.6. Any data originating at a different 

laboratory will be identified and the 

laboratory fully referenced in the final report. 

9.7. The following references identify 

analytical methods that have historically 

been successful for achieving the analytical 

quality criteria. 

9.7.1. Continental Shelf Associates Report 

1998. Joint EPA/Industry Screening Survey to 

Assess the Deposition of Drill Cuttings and 

Associated Synthetic Based Mud on the 

Seabed of the Louisiana Continental Shelf, 

Gulf of Mexico. Analysis by Charlie Henry 

Report Number IES/RCAT97–36 GC–FID and 

GC/MS. 

9.7.2. EPA Method 3550 for extraction with 

EPA Method 8015 for GC–FID. EPA Method 

3550C, Revision 3. February 2007. Ultrasonic 

Extraction. EPA Method 8015C, Revision 3. 

February 2007. Nonhalogenated Organics by 

Gas Chromatography. 

9.7.3. Chandler, J.E., S.P. Rabke, and A.J.J. 

Leuterman. 1999. Predicting the Potential 

Impact of Synthetic-Based Muds With the 

Use of Biodegradation Studies. Society of 

Petroleum Engineers SPE 52742. 

9.7.4. Chandler, J.E., B. Lee, S.P. Rabke, 

J.M. Geliff, R. Stauffer, and J. Hein. 2000. 

Modification of a Standardized Anaerobic 

Biodegradation Test to Discriminate 

Performance of Various Non-Aqueous Base 

Fluids. Society of Petroleum Engineers SPE 

61203. 

9.7.5. Munro, P.D., B Croce, C.F. Moffet, 

N.A Brown, A.D. McIntosh, S.J. Hird, and 

R.M. Stagg. 1998. Solid-Phase Test for 

Comparison for Degradation Rates of 

Synthetic Mud Base Fluids Used in the Offshore Drilling Industry. Environ. Toxicol. 

Chem. 17:1951–1959. 

9.7.6. Webster, L., P.R. Mackie, S.J. Hird, 

P.D. Munro, N.A. Brown, and C.F. Moffat. 

1997. Development of Analytical Methods for 

the Determination of Synthetic Mud Base 

Fluids in Marine Sediments. The Analyst 

122:1485–1490. 

9.8 The following standards are approved 

for incorporation by reference by the Director 

of the Federal Register in accordance with 5 

U.S.C. 552(a) and 1 CFR part 51. Copies may 

also be inspected at EPA’s Water Docket, 

1200 Pennsylvania Ave. NW., Washington, 

DC 20460 and at at the National Archives and 

Records Administration (NARA). For 

information on the availability of this 

material at NARA, call 202–741–6030, or go 

to: http://www.archives.gov/federal_register/ 

code_of_federal_regulations/ 

ibr_locations.html. 

9.8.1 ASTM International. Available from 

ASTM International, 100 Barr Harbor Drive, 

P.O. Box C700, West Conshohocken, PA 

19428–2959, or online at http:// 

www.astm.org. 

9.8.1.1 ASTM D5291–96, Standard Test 

Methods for Instrumental Determination of 

Carbon, Hydrogen, and Nitrogen in 

Petroleum Products and Lubricants, 

approved April 10, 1996. 

9.8.1.2 ASTM D2974–07a, Standard Test 

Methods for Moisture, Ash, and Organic 

Matter of Peat and Other Organic Soils, 

approved March 15, 2007. 

■ 26. Amend Appendix 5 to Subpart A 

of Part 435 by: 

■ a. Revising the appendix heading. 

■ b. Removing ‘‘35 to 500 amu’’ and 

adding in its place ‘‘35 to 600 amu’’ in 

Section 6.3.2. 

■ c. Revising section 9.5. introductory 

text. 

■ d. Revising the equation in section 

9.5.2. 

■ e. Revising sections 9.6, 11.3 

introductory text, 11.3.1, and 11.5.4.2. 

■ f. Adding section 6.17. 

Appendix 5 to Subpart A of Part 435— 

Determination of Crude Oil 

Contamination in Non-Aqueous Drilling 

Fluids by Gas Chromatography/Mass 

Spectrometry (GC/MS) (EPA Method 

1655) 

* * * * * 

9.5 Duplicates—A duplicate field sample 

shall be prepared and analyzed according to 

Section 11. The relative percent difference 

(RPD) of the calculated concentrations shall 

be less than 15%. 

* * * * * 

9.6 A clean NAF sample shall be 

prepared and analyzed according to Section 

11. Ultimately the oil-equivalent 

concentration from the TIC or EIP signal 

measured in the clean NAF sample shall be 

subtracted from the corresponding authentic 

field samples in order to calculate the true 

contaminant concentration (% oil) in the 

field samples (see Section 12). 

* * * * * 

11.3 Qualitative Identification—See 

Section 17 of this method for schematic 

flowchart. 

11.3.1 Qualitative identification shall be 

accomplished by comparison of the TIC and 

EIP area data from an authentic sample to the 

TIC and EIP area data from the calibration 

standards (see Section 10.4). Crude oil shall 

be identified by the presence of C10 to C13 nalkanes and corresponding target aromatics. 

* * * * * 

11.5.4.2 Asphaltene crude oils with API 

gravity <20 may not produce 

chromatographic peaks strong enough to 

show contamination at levels of the 

calibration. Extracted ion peaks should be 

easier to see than increased intensities for the 

C8 to C13 peaks. If a sample of asphaltene 

crude from the formation is available, a 

calibration standard shall be prepared. 

BILLING CODE 6560–50–P 


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BILLING CODE 6560–50–C 

■ 27. The heading of Appendix 6 to 

Subpart A of Part 435 is revised to read 

as follows: 

Appendix 6 to Subpart A of Part 435— 

Reverse Phase Extraction (RPE) Method 

for Detection of Oil Contamination in 

Non-Aqueous Drilling Fluids (NAF) 

(GC/MS) (EPA Method 1670) 

* * * * * 

■ 28. The heading of Appendix 7 to 

Subpart A of Part 435 is revised to read 

as follows: 

Appendix 7 to Subpart A of Part 435— 

Determination of the Amount of NonAqueous Drilling Fluid (NAF) Base 

Fluid From Drill Cuttings by a Retort 

Chamber (Derived From API 

Recommended Practice 13B–2) (EPA 

Method 1674) 

* * * * * 

■ 29. Appendix 8 to Subpart A of Part 

435 is amended by: 

■ a. Revising the second paragraph. 

■ b. Adding ‘‘>’’ before ‘‘11–14’’ in 

Table 1. 

Appendix 8 to Subpart A of Part 435— 

Reference C16-C18 Internal Olefin 

Drilling Fluid Formulation 

* * * * * 

Drilling fluid sediment toxicity ratio = 4- 

day LC50 of C16-C18 internal olefin drilling 

fluid/4-day LC50 of drilling fluid removed 

from drill cuttings at the solids control 

equipment as determined by EPA Method 

1644: ‘‘Method for Conducting a Sediment 

Toxicity Test with Leptocheirus plumulosus 

and Non-Aqueous Drilling Fluids or 

Synthetic-Based Drilling Muds’’ after 

sediment preparation procedures specified in 

EPA Method 1646, which are published as 

appendices to Subpart A of this part and in 

‘‘Analytic Methods for the Oil and Gas 

Extraction Point Source Category,’’ EPA– 

821–R–11–004. See § 435.11(ee) and (uu). 

* * * * * 

Subpart D—Coastal Subcategory 

■ 30. Section 435.41 is amended: 

■ a. By revising paragraph (d). 

■ b. By revising paragraph (e). 

■ c. By revising paragraph (k). 

■ d. By revising paragraph (m)(2). 

■ e. By revising paragraph (q). 

■ f. By revising paragraph (r). 

■ g. By amending paragraph (w) to 

remove ‘‘LC5’’ and add in its place 

‘‘LC50’’. 

■ h. By revising paragraph (y). 

■ i. By revising paragraph (ee). 

■ j. By revising paragraph (ff). 

■ k. By adding paragraph (mm). 

§ 435.41 Special definitions. 

* * * * * 

(d) Base fluid retained on cuttings as 

applied to BAT effluent limitations and 

NSPS refers to the ‘‘Determination of the 

Amount of Non-Aqueous Drilling Fluid 

(NAF) Base Fluid from Drill Cuttings by 

a Retort Chamber (Derived from API 

Recommended Practice 13B–2)’’, EPA 

Method 1674, which is published as an 

appendix to Subpart A of this part and 

in ‘‘Analytic Methods for the Oil and 

Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See paragraph 

(mm) of this section. 

(e) Biodegradation rate as applied to 

BAT effluent limitations and NSPS for 

drilling fluids and drill cuttings refers to 

the ‘‘Protocol for the Determination of 

Degradation of Non Aqueous Base 

Fluids in a Marine Closed Bottle 

Biodegradation Test System: Modified 

ISO 11734:1995,’’ EPA Method 1647, 

supplemented with ‘‘Procedure for 

Mixing Base Fluids With Sediments,’’ 

EPA Method 1646. Both EPA Method 

1646 and 1647 are published as 

appendices to Subpart A of this part and 

in ‘‘Analytic Methods for the Oil and 

Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See paragraph 

(mm) of this section. 

* * * * * 

(k) Diesel oil refers to the grade of 

distillate fuel oil, as specified in the 

American Society for Testing and 

Materials Standard Specification for 

Diesel Fuel Oils D975–91, that is 

typically used as the continuous phase 

in conventional oil-based drilling fluids. 

This incorporation by reference was 

approved by the Director of the Federal 

Register in accordance with 5 U.S.C. 

552(a) and 1 CFR part 51. Copies may 

be obtained from the American Society 

for Testing and Materials, 100 Barr 

Harbor Drive, West Conshohocken, PA 

19428. Copies may be inspected at the 

National Archives and Records 

Administration (NARA). For 

information on the availability of this 

material at NARA, call 202–741–6030, 

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

federal_register/ 

code_of_federal_regulations/ 

ibr_locations.html. A copy may also be 

inspected at EPA’s Water Docket, 1200 

Pennsylvania Ave. NW., Washington, 

DC 20460. 

* * * * * 

(m) * * * 

(2) Dry drill cuttings means the 

residue remaining in the retort vessel 

after completing the retort procedure 

specified in EPA Method 1674, which is 

published as an appendix to Subpart A 

of this part and in ‘‘Analytic Methods 

for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. 

See paragraph (mm) of this section. 

* * * * * 

(q) Formation oil means the oil from 

a producing formation which is detected 

in the drilling fluid, as determined by 

the GC/MS compliance assurance 

method, EPA Method 1655, when the 

drilling fluid is analyzed before being 

shipped offshore, and as determined by 

the RPE method, EPA Method 1670, 

when the drilling fluid is analyzed at 

the offshore point of discharge. The GC/ 

MS compliance assurance method and 

the RPE method approved for use with 

this part are published as appendices to 

Subpart A of this part and in ‘‘Analytic 

Methods for the Oil and Gas Extraction 

Point Source Category,’’ EPA–821–R– 

11–004. See paragraph (mm) of this 

section. Detection of formation oil by 

the RPE method may be confirmed by 

the GC/MS compliance assurance 

method, and the results of the GC/MS 

compliance assurance method shall 

supersede those of the RPE method. 

(r) Garbage means all kinds of victual, 

domestic, and operational waste, 

excluding fresh fish and parts thereof, 

generated during the normal operation 

of coastal oil and gas facility and liable 

to be disposed of continuously or 

periodically, except dishwater, 

graywater, and those substances that are 

defined or listed in other Annexes to 

MARPOL 73/78. A copy of MARPOL 

may be inspected at EPA’s Water 

Docket, 1200 Pennsylvania Ave. NW., 

Washington, DC 20460. 

* * * * * 

(y) No discharge of free oil means that 

waste streams may not be discharged 

that contain free oil as evidenced by the 

monitoring method specified for that 

particular stream, e.g., deck drainage or 

miscellaneous discharges cannot be 

discharged when they would cause a 

film or sheen upon or discoloration of 

the surface of the receiving water; 

drilling fluids or cuttings may not be 

discharged when they fail EPA Method 

1617 (Static Sheen Test), which is 

published as an appendix to Subpart A 

of this part and in ‘‘Analytic Methods 

for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. 

See paragraph (mm) of this section. 

* * * * * 

(ee) SPP toxicity as applied to BAT 

effluent limitations and NSPS for 

drilling fluids and drill cuttings refers to 

the bioassay test procedure, ‘‘Suspended 

Particulate Phase (SPP) Toxicity Test,’’ 

presented in EPA Method 1619, which 

is published as an appendix to Subpart 

A of this part and in ‘‘Analytic Methods 

for the Oil and Gas Extraction Point 

Source Category,’’ EPA–821–R–11–004. 

See paragraph (mm) of this section. 

(ff) Static sheen test means the 

standard test procedure that has been 


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29846 Federal Register / Vol. 77, No. 97 / Friday, May 18, 2012 / Rules and Regulations 

developed for this industrial 

subcategory for the purpose of 

demonstrating compliance with the 

requirement of no discharge of free oil. 

The methodology for performing the 

static sheen test is presented in EPA 

Method 1617, which is published as an 

appendix to Subpart A of this part and 

in ‘‘Analytic Methods for the Oil and 

Gas Extraction Point Source Category,’’ 

EPA–821–R–11–004. See paragraph 

(mm) of this section. 

* * * * * 

(mm) Analytic Methods for the Oil 

and Gas Extraction Point Source 

Category is the EPA document, EPA– 

821–R–11–004, that compiles analytic 

methods for this category. Copies may 

be inspected at the National Archives 

and Records Administration (NARA). 

For information on the availability of 

this material at NARA, call 202–741– 

6030, or go to: http://www.archives.gov/ 

federal_register/ 

code_of_federal_regulations/ 

ibr_locations.html. A copy may also be 

inspected at EPA’s Water Docket, 1200 

Pennsylvania Ave. NW., Washington, 

DC 20460. This method may be obtained 

at http://water.epa.gov/scitech/ 

methods/cwa/index.cfm. 

■ 31. In § 435.42 footnote 1 to the table 

is revised to read as follows: 

§ 435.42 Effluent limitations guidelines 

representing the degree of effluent 

reduction attainable by the application of 

the best practicable control technology 

currently available (BPT). 

* * * * * 1No discharge of free oil. See § 435.41(y). 

* * * * * 

■ 32. In § 435.43: 

■ a. Remove ‘‘LC5’’ and add in its place 

‘‘LC50’’ in the table. 

■ b. Footnotes 2 and 4 to the table are 

revised to read as follows: 

§ 435.43 Effluent limitations guidelines 

representing the degree of effluent 

reduction attainable by the application of 

the best available technology economically 

achievable (BAT). 

* * * * * 2As determined by the static sheen test. 

See § 435.41(ff). 

* * * * * 4As determined by the suspended 

particulate phase (SPP) toxicity test. See 

§ 435.41(ee). 

* * * * * 

■ 33. In § 435.44 footnote 2 to the table 

is revised to read as follows: 

§ 435.44 Effluent limitations guidelines 

representing the degree of effluent 

reduction attainable by the application of 

the best conventional pollutant control 

technology (BCT). 

* * * * * 2As determined by the static sheen test. 

See § 435.41(ff). 

* * * * * 

■ 34. In § 435.45: 

■ a. Remove ‘‘LC5’’ and add in its place 

‘‘LC50’’in the table. 

■ b. Footnotes 2 and 4 to the table are 

revised to read as follows: 

§ 435.45 Standards of performance for 

new sources (NSPS). 

* * * * * 2As determined by the static sheen test. 

See § 435.41(ff). 

* * * * * 4As determined by the suspended 

particulate phase (SPP) toxicity test. See 

§ 435.41(ee). 

* * * * * 

[FR Doc. 2012–10210 Filed 5–17–12; 8:45 am] 

BILLING CODE 6560–50–P 


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