Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures

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:

gomez-taylor.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 quality-based requirements of the Clean Water Act (CWA). These permits may include restrictions on the quantity of pollutants that may be discharged as well as pollutant measurement and reporting requirements. If EPA has approved a test procedure for analysis of a specific pollutant, the NPDES permittee must use an approved test procedure (or an approved alternate test procedure if specified by the permitting authority) for the specific pollutant when measuring the required waste constituent. Similarly, if EPA has established sampling requirements, measurements taken under an NPDES permit must comply with these requirements. Therefore, entities with NPDES permits will potentially be affected by the actions in this rulemaking. 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

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 Plasma-Atomic 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 re-considering whether it should add this

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, α-BHC, β-BHC, γ-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, PCB-1016, 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-NH

3

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-N

org

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

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-SiO

2

E-1997 and SM 4500-SiO

2

F-1997, Silica, Dissolved, automated molybdosilicate

22. SM 4500-SO

4

2−

C-1997, D-1997, E-1997, F-1997 and G-1997, Sulfate, gravimetric, and automated colorimetric

23. SM 4500-S

2−

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-tert-Octylphenol (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 BOD

5

and cBOD

5

, 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 bio-available 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. Hand-delivered 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

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, co-regulators, 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.

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 thirty-five 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 inter-laboratory 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

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

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

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 Non-Aqueous 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

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 on-line 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 EPA-developed 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 EPA-approved 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

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

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

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 EPA-approved 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.

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.

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 4

13

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, LC

50

, 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, LC

50

, percent effluent

Mysid,

Mysidopsis bahia,

acute

2007.0.

26

Sheepshead Minnow,

Cyprinodon variegatus,

acute

2004.0

26

Silverside,

Menidia beryllina, Menidia menidia,

and

Menidia peninsulae,

acute

2006.0

26

11. Toxicity, chronic, fresh water organisms, NOEC or IC

25

, percent effluent

Fathead minnow,

Pimephales promelas,

larval survival and growth

1000.0.

27

Fathead minnow,

Pimephales promelas,

embryo-larval survival and teratogenicity

1001.0.

27

Daphnia,

Ceriodaphnia dubia,

survival and reproduction

1002.0.

27

Green alga,

Selenastrum capricornutum,

growth

1003.0.

27

12. Toxicity, chronic, estuarine and marine organisms of the Atlantic Ocean and Gulf of Mexico, NOEC or IC

25

, percent effluent

Sheepshead minnow,

Cyprinodon variegatus,

larval survival and growth

1004.0.

28

Sheepshead minnow,

Cyprinodon variegatus,

embryo-larval survival and teratogenicity

1005.0.

28

Inland silverside,

Menidia beryllina,

larval survival and growth

1006.0.

28

Mysid,

Mysidopsis bahia,

survival, growth, and fecundity

1007.0.

28

Sea urchin,

Arbacia punctulata,

fertilization

1008.0.

28

Table IA notes:

1

The method must be specified when results are reported.

2

A 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.

5

Because the MF technique usually yields low and variable recovery from chlorinated wastewaters, the Most Probable Number method will be required to resolve any controversies.

6

Tests must be conducted to provide organism enumeration (density). Select the appropriate configuration of tubes/filtrations and dilutions/volumes to account for the quality, character, consistency, and anticipated organism density of the water sample.

7

When the MF method has been used previously to test waters with high turbidity, large numbers of noncoliform bacteria, or samples that may contain organisms stressed by chlorine, a parallel test should be conducted with a multiple-tube technique to demonstrate applicability and comparability of results.

8

To assess the comparability of results obtained with individual methods, it is suggested that side-by-side tests be conducted across seasons of the year with the water samples routinely tested in accordance with the most current Standard Methods for the Examination of Water and Wastewater or EPA alternate test procedure (ATP) guidelines.

9

Annual Book of ASTM Standards-Water and Environmental Technology, Section 11.02. 2000, 1999, 1996. ASTM International.

10

Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998. AOAC International.

11

Recommended for enumeration of target organism in sewage sludge.

12

The multiple-tube fermentation test is used in 9221B.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.

13

These tests are collectively known as defined enzyme substrate tests, where, for example, a substrate is used to detect the enzyme β-glucuronidase produced by

E. coli.

14

After 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.

16

Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube and dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert® 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.

19

A 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.

24

A 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-β-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.

27

Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms. EPA-821-R-02-013. Fourth Edition, October 2002. U.S. EPA.

28

Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms. EPA-821-R-02-014. Third Edition, October 2002. U.S. EPA.

Table IB—List of Approved Inorganic Test Procedures

Parameter

Methodology

58

EPA

52

Standard methods

ASTM

USGS/AOAC/Other

1. Acidity, as CaCO

3

, mg/L

Electrometric endpoint or phenolphthalein endpoint

2310 B-1997

D1067-06

I-1020-85.

2

2. Alkalinity, as CaCO

3

, 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/AES

36

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-NH

3

B-1997

973.49

3

.

Nesslerization

D1426-08 (A)

973.49

3

, I-3520-85.

2

Titration

4500-NH

3

C-1997

Electrode

4500-NH

3

D-1997 or E-1997

D1426-08 (B)

Manual phenate, salicylate, or other substituted phenols in Berthelot reaction based methods

4500-NH

3

F-1997

See footnote.

60

Automated phenate, salicylate, or other substituted phenols in Berthelot reaction based methods

350.1

30

, Rev. 2.0 (1993)

4500-NH

3

G-1997

4500-NH

3

H-1997.

I-4523-85.

2

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/AES

36

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/AES

36

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

Digestion

4

, 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/AES

36

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

DCP

36

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

973.44

3

, 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:

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/AES

36

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

DCP

36

D4190-08

See footnote.

34

Voltametry

11

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 (CBOD

5

), mg/L

12

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

993.30

3

, 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-point

15

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:

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/AES

36

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

36

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/AES

36

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/AES

36

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

36

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 MgCl

2

, 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)

Ion Selective Electrode

4500-CN

−

F-1999

D2036-09(A)

24. Cyanide-Available, mg/L

Cyanide Amenable to Chlorination (CATC); Manual distillation with MgCl

2

, 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 CaCO

3

, 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/AES

36

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

36

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-N

org

B-1997 or C-1997 and 4500-NH

3

B-1997

D3590-02(06) (A)

I-4515-91.

45

Titration

4500-NH

3

C-1997

973.48.

3

Nesslerization

D1426-08 (A)

Electrode

4500-NH

3

D-1997 or E-1997

D1426-08 (B)

Semi-automated phenate

350.1 Rev 2.0 1993

4500-NH

3

G-1997.

4500-NH

3

H-1997

Manual phenate, salicylate, or other substituted phenols in Berthelot reaction based methods

4500-NH

3

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-N

org

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/AES

36

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

36

D4190-08

See footnote.

34

Voltametry

11

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:

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/AES

36

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

36

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

1631E

43

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/AES

36

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/AES

36

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

36

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-NO

3

−

D-2000

Colorimetric (Brucine sulfate)

352.1 (Issued 1971)

1

973.50,

3

419D

1,7

, 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-NO

3

−

E-2000

D3867-04 (B)

Cadmium reduction, Automated

353.2, Rev. 2.0 (1993)

4500-NO

3

−

F-2000

D3867-04 (A)

I-2545-90.

51

Automated hydrazine

4500-NO

3

−

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-NO

2

−

B-2000

See footnote.

25

Automated (Diazotization)

I-4540-85

2

, See footnote.

62

Automated (*bypass cadmium reduction)

353.2, Rev. 2.0 (1993)

4500-NO

3

−

F-2000

D3867-04 (A)

I-4545-85.

2

Manual (*bypass cadmium reduction)

4500-NO

3

−

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. B

42

5520 B-2001

38

Silica gel treated HEM (SGT-HEM): Silica gel treatment and gravimetry

1664 Rev. A; 1664 Rev. B

42

5520 B-2001

38

and 5520 F-2001

38

42. Organic carbon—Total (TOC), mg/L

Combustion

5310 B-2000

D7573-09

973.47

3

, p. 14.

24

Heated persulfate or UV persulfate oxidation

5310 C 2000

5310 D 2000.

D4839-03

973.47

3,

, p. 14.

24

43. Organic nitrogen (as N), mg/L

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

44. Ortho-phosphate (as P), mg/L

Ascorbic acid method:

Automated

365.1, Rev. 2.0 (1993)

4500-P F-1999 or G-1999

973.56

3

, 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—Total

4

, mg/L

Digestion

4

, 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)

973.45B

3

, I-1575-78.

8

Electrode

4500-O G-2001

D888-09 (B)

I-1576-78.

8

Luminescence Based Sensor

D888-09 (C)

See footnote

63

See footnote.

64

47. Palladium—Total,

4

mg/L

Digestion

4

, followed by any of the following:

AA direct aspiration

3111 B-1999

AA furnace

253.2

1

(Issued 1978)

ICP/MS

3125 B-2009

DCP

See footnote.

34

48. Phenols, mg/L

Manual distillation

26

, followed by any of the following:

420.1

1

(Rev. 1978)

5530 B-2005

D1783-01

Colorimetric (4AAP) manual

420.1

1

(Rev. 1978)

5530 D-2005

27

D1783-01 (A or B)

Automated colorimetric (4AAP)

420.4 Rev. 1.0 (1993)

49. Phosphorus (elemental), mg/L

Gas-liquid chromatography

See footnote.

28

50. Phosphorus—Total, mg/L

Digestion

20

, followed by any of the following:

4500-P B(5)-1999

973.55.

3

Manual

365.3

1

(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

973.56

3

, I-4600-85.

2

ICP/AES

4, 36

200.7, Rev. 4.4 (1994)

3120 B-1999

I-4471-97.

50

Semi-automated block digestor (TKP digestion)

365.4

1

(Issued 1974)

D515-88 (B)

I-4610-91.

48

51. Platinum—Total,

4

mg/L

Digestion

4

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

Digestion

4

, followed by any of the following:

AA direct aspiration

3111 B-1999

973.53

3

, 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

Digestion

4

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

Digestion

4

followed by any of the following:

AA direct aspiration, or

3111 B-1999

AA furnace

267.2

1

ICP/MS

3125 B-2009

60. Selenium—Total,

4

mg/L

Digestion

4

, 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/AES

36

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

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-SiO

2

C-1997

D859-05

I-1700-85.

2

Automated (Molybdosilicate)

4500-SiO

2

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

Digestion

4, 29

, followed by any of the following:

AA direct aspiration

3111 B-1999 or

3111 C-1999

974.27

3

, p. 37

9

, I-3720-85.

2

AA furnace

3113 B-2004

I-4724-89.

51

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

200.5, Rev 4.2 (2003)

68

; 200.7, Rev. 4.4 (1994)

3120 B-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

63. Sodium—Total,

4

mg/L

Digestion

4,

, followed by any of the following:

AA direct aspiration

3111 B-1999

973.54

3

, 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

120.1

1

(Rev. 1982)

2510 B-1997

D1125-95(99) (A)

973.40

3

, I-2781-85.

2

65. Sulfate (as SO

4

), mg/L

Automated colorimetric

375.2, Rev. 2.0 (1993)

4500-SO

4

2-

F-1997 or G-1997

Gravimetric

4500-SO

4

2-

C-1997 or D-1997

925.54.

3

Turbidimetric

4500-SO

4

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

993.30

3

, 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-S

2−

B, C-2000

Titrimetric (iodine)

4500-S

2−

F-2000

I-3840-85.

2

Colorimetric (methylene blue)

4500-S

2−

D-2000

Ion Selective Electrode

4500-S

2−

G-2000

D4658-08

67. Sulfite (as SO

3

), mg/L

Titrimetric (iodine-iodate)

4500-SO

3

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

Digestion

4

, followed by any of the following:

AA direct aspiration

3111 B-1999

AA furnace

279.2

1

(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

993.14

3

, I-4471-97.

50

71. Tin-Total,

4

mg/L

Digestion

4

, followed by any of the following:

AA direct aspiration

3111 B-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

Digestion

4

followed by any of the following:

AA direct aspiration

3111 D-1999

AA furnace

283.2

1

(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

DCP

See footnote.

34

73. Turbidity, NTU

53

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

Digestion

4

, 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

993.14

3

, I-4020-05.

70

DCP

D4190-08

See footnote.

34

Colorimetric (Gallic Acid)

3500-V B-1997

75. Zinc-Total

4

, mg/L

Digestion

4

, followed by any of the following:

AA direct aspiration

36

3111 B-1999 or 3111 C-1999

D1691-02(07) (A or B)

974.27

3

, p. 37

9

, I-3900-85.

2

AA furnace

289.2

1

(Issued 1978)

ICP/AES

36

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

36

D4190-08

See footnote.

34

Colorimetric (Zincon)

3500 Zn B-1997

See footnote.

33

76. Acid Mine Drainage

1627

69

Table IB Notes:

1

Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020. Revised March 1983 and 1979, where applicable. U.S. EPA.

2

Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resource Investigations of the U.S. Geological Survey, Book 5, Chapter A1., unless otherwise stated. 1989. USGS.

3

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

4

For the determination of total metals (which are equivalent to total recoverable metals) the sample is not filtered before processing. A digestion procedure is required to solubilize analytes in suspended material and to break down organic-metal complexes (to convert the analyte to a detectable form for colorimetric analysis). For non-platform graphite furnace atomic absorption determinations a digestion using nitric acid (as specified in Section 4.1.3 of Methods for the Chemical Analysis of Water and Wastes) is required prior to analysis. The procedure used should subject the sample to gentle, acid refluxing and at no time should the sample be taken to dryness. For direct aspiration flame atomic absorption determinations (FLAA) a combination acid (nitric and hydrochloric acids) digestion is preferred prior to analysis. The approved total recoverable digestion is described as Method 200.2 in Supplement I of “Methods for the Determination of Metals in Environmental Samples” EPA/600R-94/111, May, 1994, and is reproduced in EPA Methods 200.7, 200.8, and 200.9 from the same Supplement. However, when using the gaseous hydride technique or for the determination of certain elements such as antimony, arsenic, selenium, silver, and tin by non-EPA graphite furnace atomic absorption methods, mercury by cold vapor atomic absorption, the noble metals and titanium by FLAA, a specific or modified sample digestion procedure may be required and in all cases the referenced method write-up should be consulted for specific instruction and/or cautions. For analyses using inductively coupled plasma-atomic emission spectrometry (ICP-AES), the direct current plasma (DCP) technique or 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.

8

The approved method is that cited in Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1979. USGS.

9

American National Standard on Photographic Processing Effluents. April 2, 1975. American National Standards Institute.

10

In-Situ Method 1003-8-2009, Biochemical Oxygen Demand (BOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.

11

The use of normal and differential pulse voltage ramps to increase sensitivity and resolution is acceptable.

12

Carbonaceous biochemical oxygen demand (CBOD

5

) must not be confused with the traditional BOD

5

test method which measures “total BOD.” The addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD

5

parameter. A discharger whose permit requires reporting the traditional BOD

5

may not use a nitrification inhibitor in the procedure for reporting the results. Only when a discharger's permit specifically states CBOD

5

is required can the permittee report data using a nitrification inhibitor.

13

OIC Chemical Oxygen Demand Method. 1978. Oceanography International Corporation.

14

Method 8000, Chemical Oxygen Demand, Hach Handbook of Water Analysis, 1979. Hach Company.

15

The back titration method will be used to resolve controversy.

16

Orion Research Instruction Manual, Residual Chlorine Electrode Model 97-70. 1977. Orion Research Incorporated. The calibration graph for the Orion residual chlorine method must be derived using a reagent blank and three standard solutions, containing 0.2, 1.0, and 5.0 mL 0.00281 N potassium iodate/100 mL solution, respectively.

17

Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-05-001. Revision 2.0, February 2005. US EPA.

18

National Council of the Paper Industry for Air and Stream Improvement (NCASI) Technical Bulletin 253, December 1971.

19

Method 8506, Biocinchoninate Method for Copper, Hach Handbook of Water Analysis. 1979. Hach Company.

20

When using a method with block digestion, this treatment is not required.

21

Industrial Method Number 378-75WA, Hydrogen ion (pH) Automated Electrode Method, Bran & Luebbe (Technicon) Autoanalyzer II. October 1976. Bran & Luebbe Analyzing Technologies.

22

Method 8008, 1,10-Phenanthroline Method using FerroVer Iron Reagent for Water. 1980. Hach Company.

23

Method 8034, Periodate Oxidation Method for Manganese, Hach Handbook of Wastewater Analysis. 1979. Hach Company.

24

Methods for Analysis of Organic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A3, (1972 Revised 1987) 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.

27

The colorimetric reaction must be conducted at a pH of 10.0 ± 0.2.

28

Addison, R.F., and R.G. Ackman. 1970. Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography,

Journal of Chromatograph

y, 47(3):421-426.

29

Approved methods for the analysis of silver in industrial wastewaters at concentrations of 1 mg/L and above are inadequate where silver exists as an inorganic halide. Silver halides such as the bromide and chloride are relatively insoluble in reagents such as nitric acid but are readily soluble in an aqueous buffer of sodium thiosulfate and sodium hydroxide to pH of 12. Therefore, for levels of silver above 1 mg/L, 20 mL of sample should be diluted to 100 mL by adding 40 mL each of 2 M Na

2

S

2

O

3

and NaOH. Standards should be prepared in the same manner. For levels of silver below 1 mg/L the approved method is satisfactory.

30

The use of EDTA decreases method sensitivity. Analysts may omit EDTA or replace with another suitable complexing reagent provided that all method specified quality control acceptance criteria are met.

31

For samples known or suspected to contain high levels of silver (

e.g.,

in excess of 4 mg/L), cyanogen iodide should be used to keep the silver in solution for analysis. Prepare a cyanogen iodide solution by adding 4.0 mL of concentrated NH

4

OH, 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 NH

4

OH. Add 1 mL of the cyanogen iodide solution and let stand 1 hour. Transfer to a 100-mL volumetric flask and dilute to volume with water.

32

“Water Temperature-Influential Factors, Field Measurement and Data Presentation,” Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 1, Chapter D1. 1975. USGS.

33

Method 8009, Zincon Method for Zinc, Hach Handbook of Water Analysis, 1979. Hach Company.

34

Method AES0029, Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes. 1986-Revised 1991. Thermo Jarrell Ash Corporation.

35

In-Situ Method 1004-8-2009, Carbonaceous Biochemical Oxygen Demand (CBOD) Measurement by Optical Probe. 2009. In-Situ Incorporated.

36

Microwave-assisted digestion may be employed for this metal, when analyzed by this methodology. Closed Vessel Microwave Digestion of Wastewater Samples for Determination of Metals. April 16, 1992. CEM Corporation

37

When determining boron and silica, only plastic, PTFE, or quartz laboratory ware may be used from start until completion of analysis.

38

Only use n-hexane (n-Hexane—85% minimum purity, 99.0% min. saturated C6 isomers, residue less than 1 mg/L) extraction solvent when determining Oil and Grease parameters—Hexane Extractable Material (HEM), or Silica Gel Treated HEM (analogous to EPA Methods 1664 Rev. A and 1664 Rev. B). Use of other extraction solvents is prohibited.

39

Method PAI-DK01, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Titrimetric Detection. Revised December 22, 1994. OI Analytical.

40

Method PAI-DK02, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Colorimetric Detection. Revised December 22, 1994. OI Analytical.

41

Method PAI-DK03, Nitrogen, Total Kjeldahl, Block Digestion, Automated FIA Gas Diffusion. Revised December 22, 1994. OI Analytical.

42

Method 1664 Rev. B is the revised version of EPA Method 1664 Rev. A. U.S. EPA. February 1999, Revision A. Method 1664, n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM; Non-polar Material) by Extraction and Gravimetry. EPA-821-R-98-002. U.S. EPA. February 2010, Revision B. Method 1664, n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM; Non-polar Material) by Extraction and Gravimetry. EPA-821-R-10-001.

43

Method 1631, Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry, EPA-821-R-02-019. Revision E. August 2002, U.S. EPA. The application of clean techniques described in EPA's Method 1669:

Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Levels,

EPA-821-R-96-011, are recommended to preclude contamination at low-level, trace metal determinations.

44

Method OIA-1677-09, Available Cyanide by Ligand Exchange and Flow Injection Analysis (FIA). 2010. OI Analytical.

45

Open File Report 00-170, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Ammonium Plus Organic Nitrogen by a Kjeldahl Digestion Method and an Automated Photometric Finish that Includes Digest Cleanup by Gas Diffusion. 2000. USGS.

46

Open File Report 93-449, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Chromium in Water by Graphite Furnace Atomic Absorption Spectrophotometry. 1993. USGS.

47

Open File Report 97-198, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Molybdenum by Graphite Furnace Atomic Absorption Spectrophotometry. 1997.. USGS.

48

Open File Report 92-146, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Total Phosphorus by Kjeldahl Digestion Method and an Automated Colorimetric Finish That Includes Dialysis. 1992. USGS.

49

Open File Report 98-639, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Arsenic and Selenium in Water and Sediment by Graphite Furnace-Atomic Absorption Spectrometry. 1999. USGS.

50

Open File Report 98-165, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Elements in Whole-water Digests Using Inductively Coupled Plasma-Optical Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry. 1998. USGS.

51

Open File Report 93-125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993.. USGS.

52

Unless otherwise indicated, all EPA methods, excluding EPA Method 300.1-1, are published in U.S. EPA. May 1994. Methods for the Determination of Metals in Environmental Samples, Supplement I, EPA/600/R-94/111; or U.S. EPA. August 1993. Methods for the Determination of Inorganic Substances in Environmental Samples, EPA/600/R-93/100. EPA Method 300.1 is US EPA. Revision 1.0, 1997, including errata cover sheet April 27, 1999. Determination of Inorganic Ions in Drinking Water by Ion Chromatography.

53

Styrene divinyl benzene beads (

e.g.,

AMCO-AEPA-1 or equivalent) and stabilized formazin (

e.g.,

Hach StablCal

TM

or equivalent) are acceptable substitutes for formazin.

54

Method D6508, Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and Chromate Electrolyte. December 2000. Waters Corp.

55

Kelada-01, Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, and Thiocyanate, EPA 821-B-01-009, Revision 1.2, August 2001. US EPA. Note: A 450-W UV lamp may be used in this method instead of the 550-W lamp specified if it provides performance within the quality control (QC) acceptance criteria of the method in a given instrument. Similarly, modified flow cell configurations and flow conditions may be used in the method, provided that the QC acceptance criteria are met.

56

QuikChem Method 10-204-00-1-X, Digestion and Distillation of Total Cyanide in Drinking and Wastewaters using MICRO DIST and Determination of Cyanide by Flow Injection Analysis. Revision 2.2, March 2005. Lachat Instruments.

57

When using sulfide removal test procedures described in EPA Method 335.4-1, reconstitute particulate that is filtered with the sample prior to distillation.

58

Unless otherwise stated, if the language of this table specifies a sample digestion and/or distillation “followed by” analysis with a method, approved digestion and/or distillation are required prior to analysis.

59

Samples analyzed for available cyanide using OI Analytical method OIA-1677-09 or ASTM method D6888-09 that contain particulate matter may be filtered only after the ligand exchange reagents have been added to the samples, because the ligand exchange process converts complexes containing available cyanide to free cyanide, which is not removed by filtration. Analysts are further cautioned to limit the time between the addition of the ligand exchange reagents and sample filtration to no more than 30 minutes to preclude settling of materials in samples.

60

Analysts should be aware that pH optima and chromophore absorption maxima might differ when phenol is replaced by a substituted phenol as the color reagent in Berthelot Reaction (“phenol-hypochlorite reaction”) colorimetric ammonium determination methods. For example when phenol is used as the color reagent, pH optimum and wavelength of maximum absorbance are about 11.5 and 635 nm, respectively—see, Patton, C.J. and S.R. Crouch. March 1977. Anal. Chem. 49:464-469. These reaction parameters increase to pH > 12.6 and 665 nm when salicylate is used as the color reagent—see, Krom, M.D. April 1980. The Analyst 105:305-316.

61

If atomic absorption or ICP instrumentation is not available, the aluminon colorimetric method detailed in the 19th Edition of

Standard Methods

may be used. This method has poorer precision and bias than the methods of choice.

62

Easy (1-Reagent) Nitrate Method, Revision November 12, 2011. Craig Chinchilla.

63

Hach Method 10360, Luminescence Measurement of Dissolved Oxygen in Water and Wastewater and for Use in the Determination of BOD

5

and cBOD

5.

Revision 1.2, October 2011. Hach Company. This method may be used to measure dissolved oxygen when performing the methods approved in Table IB for measurement of biochemical oxygen demand (BOD) and carbonaceous biochemical oxygen demand (CBOD).

64

In-Situ Method 1002-8-2009, Dissolved Oxygen (DO) Measurement by Optical Probe. 2009. In-Situ Incorporated.

65

Mitchell Method M5331, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.

66

Mitchell Method M5271, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Leck Mitchell.

67

Orion Method AQ4500, Determination of Turbidity by Nephelometry. Revision 5, March 12, 2009. Thermo Scientific.

68

EPA Method 200.5, Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry, EPA/600/R-06/115. Revision 4.2, October 2003. US EPA.

69

Method 1627, Kinetic Test Method for the Prediction of Mine Drainage Quality, EPA-821-R-09-002. December 2011. US EPA.

70

Techniques and Methods Book 5-B1, Determination of Elements in Natural-Water, Biota, Sediment and Soil Samples Using Collision/Reaction Cell Inductively Coupled Plasma-Mass Spectrometry, Chapter 1, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis, 2006. USGS.

71

Water-Resources Investigations Report 01-4132, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural Water With Cold Vapor-Atomic Fluorescence Spectrometry, 2001. USGS.

Table IC—List of Approved Test Procedures for Non-Pesticide Organic Compounds

Parameter

1

Method

EPA

2,7

Standard

methods

ASTM

Other

1. Acenaphthene

GC

610.

GC/MS

625, 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

D4

This text is long and has been trimmed here. Open the source document for the complete record.