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-9189-4]

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:

Proposed rule.

SUMMARY:

EPA is proposing changes to analysis and sampling test procedures in wastewater regulations. These changes will provide increased flexibility to the regulated community and laboratories in their selection of analytical methods (test procedures) for use in Clean Water Act programs. The changes include proposal of EPA methods and methods published by voluntary consensus standard bodies, such as ASTM International and the Standard Methods Committee and updated versions of currently approved methods. EPA is also proposing to add certain methods reviewed under the alternate test procedures program. Further, EPA is proposing changes to the current regulations to clarify the process for EPA approval for use of alternate procedures for nationwide and Regional use. In addition, EPA is proposing minimum quality control requirements to improve consistency across method versions; corrections to previously approved methods; and changes to sample collection, preservation, and holding time requirements. Finally, EPA is proposing changes to how EPA cites methods in three effluent guideline regulations.

DATES:

EPA must receive your comments on this proposal on or before November 22, 2010.

ADDRESSES:

Submit your comments, identified by Docket ID No. EPA-HQ-OW-2010-0192, by one of the following methods:

•

http://www.regulations.gov:

Follow the on-line instructions for submitting comments.

•

E-mail: OW-Docket@epa.gov,

Attention Docket ID No. EPA-HQ-OW-2010-0192.

•

Mail:

Water Docket, U.S. Environmental Protection Agency, Mailcode: 2822T, 1200 Pennsylvania Ave., NW., Washington, DC 20460. Attention Docket ID No. EPA-HQ-OW-2010-0192. Please include a total of 3 copies.

•

Hand Delivery:

Water Docket, EPA Docket Center, EPA West Building Room 3334, 1301 Constitution Ave., NW., Washington, DC, Attention Docket ID No. EPA-HQ-OW-2010-0192. Such deliveries are only accepted during the Docket's normal hours of operation, and special arrangements should be made for deliveries of boxed information by calling 202-566-2426.

Instructions:

Direct your comments to Docket ID No. EPA-HQ-OW-2010-0192. EPA's policy is that all comments received will be included in the public docket without change and may be made available online at

http://www.regulations.gov,

including any personal information provided, unless the comment includes information claimed to be Confidential Business Information (CBI) or other information whose disclosure is restricted by statute. Do not submit information that you consider to be CBI or otherwise protected through

http://www.regulations.gov

or e-mail. The

http://www.regulations.gov

Web site is an “anonymous access” system, which means EPA will not know your identity or contact information unless you provide it in the body of your comment. If you send an e-mail comment directly to EPA without going through

http://www.regulations.gov

your e-mail address will be automatically captured and included as part of the comment that is placed in the public docket and made available on the Internet. If you submit an electronic comment, EPA recommends that you include your name and other contact information in the body of your comment and with any disk or CD-ROM you submit. If EPA cannot read your comment due to technical difficulties and cannot contact you for clarification, EPA may not be able to consider your comment. Electronic files should avoid the use of special characters, any form of encryption, and be free of any defects or viruses.

Docket:

All documents in the docket are listed in the

http://www.regulations.gov

index. Although listed in the index, some information is not publicly available,

e.g.,

CBI or other information whose disclosure is restricted by statute. Certain other material, such as copyrighted material, will be publicly available only in hard copy. Publicly available docket materials are available either electronically in

http://www.regulations.gov

or in hard copy at the Water Docket in the EPA 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 for the Water Docket is 202-566-2426.

FOR FURTHER INFORMATION CONTACT:

Lemuel Walker, Engineering and Analysis Division (4303T), USEPA Office of Science and Technology, 1200 Pennsylvania Ave., NW., Washington, DC 20460, 202-566-1077, (

e-mail: walker.lemuel@epa.gov

), or Meghan Hessenauer, Engineering and Analysis Division (4303T), USEPA Office of Science and Technology, 1200 Pennsylvania Ave., NW., Washington, DC 20460, 202-566-1040 (

e-mail: hessenauer.meghan@epa.gov

).

SUPPLEMENTARY INFORMATION:

A. General Information

1. Does this action apply to me?

This proposed rule could affect a number of different entities. Potential regulators may include EPA Regions, as well as States, Territories and Tribes authorized to implement the National Pollutant Discharge Elimination System (NPDES) program, and 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 permitee must use an approved test procedure (or an approved alternate test procedure) 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 regulated by the actions in this rulemaking. Categories and entities that may potentially be subject to the requirements of today's rule include:

Category

Examples of potentially regulated 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.

Industry

Facilities that must conduct monitoring to comply with NPDES permits.

Municipalities

POTWs 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 regulated by this action. This table lists types of entities that EPA is now aware that could potentially be regulated by this action. Other types of entities not listed in the table could also be regulated. To determine whether your facility is regulated by this action, you should carefully examine the applicability language at 40 CFR 136.1 (NPDES permits and CWA) and 40 CFR 403.1 (Pretreatment standards purpose and applicability). If you have questions regarding the applicability of this action to a particular entity, consult the appropriate person listed in the preceding

FOR FURTHER INFORMATION CONTACT

section.

B. What should I consider as I prepare my comments for EPA?

1.

Submitting Confidential Business Information (CBI).

Do not submit this information to EPA through

http://www.regulations.gov

or e-mail. Clearly mark the part or all of the information that you claim to be CBI. For CBI information in a disk or CD-ROM that you mail to EPA, mark the outside of the disk or CD-ROM as CBI and then identify electronically within the disk or CD-ROM the specific information that is claimed as CBI. In addition to one complete version of the comment that includes information claimed as CBI, a copy of the comment that does not contain the information claimed as CBI must be submitted for inclusion in the public docket. Information so marked will not be disclosed except in accordance with procedures set forth in 40 CFR part 2.

2.

Tips for Preparing Your Comments.

When submitting comments, remember to:

• Identify the rulemaking by docket number and other identifying information (subject heading,

Federal Register

date and page number).

• Follow directions—The agency may ask you to respond to specific questions or organize comments by referencing a Code of Federal Regulations (CFR) part or section number.

• Explain why you agree or disagree, suggest alternatives, and substitute language for your requested changes.

• Describe any assumptions and provide any technical information and/or data that you used.

• If you estimate potential costs or burdens, explain how you arrived at your estimate in sufficient detail to allow for it to be reproduced.

• Provide specific examples to illustrate your concerns, and suggest alternatives.

• Explain your views as clearly as possible, avoiding the use of profanity or personal threats.

• Make sure to submit your comments by the comment period deadline identified.

C. Abbreviations and Acronyms Used in the Preamble and Proposed Rule Text

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

MS: Mass Spectrometry

NPDES: National Pollutant Discharge Elimination System

QA: Quality Assurance

QC: Quality Control

SDWA: Safe Drinking Water Act

SM: Standard Methods

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 Proposed Rule

A. Changes to 40 CFR 136.3 To Include New EPA Methods and New Versions of Previously Approved EPA Methods

B. Changes to 40 CFR 136.3 To Include New Standard Methods and New Versions of Approved Standard Methods

C. Changes to 40 CFR 136.3 To Include New ASTM Methods or New Versions of Previously Approved ASTM Methods

D. Changes to 40 CFR 136.3 To Include Alternate Test Procedures

E. Clarifications and Corrections to Previously Approved Methods in 40 CFR 136.3

F. Proposed Revisions in Table II at 40 CFR 136.3(e) to Required Containers, Preservation Techniques, and Holding Times

G. Proposed Revisions to 40 CFR 136.4 and 136.5

H. Proposed Revisions to Method Modification Provisions at 40 CFR 136.6

I. Proposed New Quality Assurance and Quality Control Language at 40 CFR 136.7

J. Proposed Withdrawal of Appendices at 40 CFR 136

K. Proposed Revisions to 40 CFR 423

L. Proposed Revisions to 40 CFR 430

M. Proposed Revisions to 40 CFR 435

III. Statutory and Executive Order Reviews

A. Executive Order 12866: Regulatory Planning and 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

IV. References

I. Statutory Authority

EPA is proposing 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 Proposed Rule

EPA's regulations at 40 CFR part 136 identify test procedures that must be used for the analysis of pollutants in all applications and report under the CWA NPDES program as well as State certifications pursuant to section 401 of the CWA. Included among the approved test procedures are analytical methods developed by EPA as well as methods developed by voluntary standards development organizations such as ASTM International and by the joint efforts of the Standard Methods Committee which is comprised of three technical societies (American Public Health Association, American Water Works Association and the Water Environment Federation) and produce

Standard Methods for the Examination of Water and Wastewater.

EPA approves analytical methods (test procedures) for measuring regulated pollutants in wastewater. Regulated and regulatory entities use these approved methods for determining compliance with NPDES permits or other monitoring requirements. Often, these entities have a choice in deciding which approved method they will use because EPA has approved the use of more than one method. This rule proposes to add to this list of approved methods. Associated with the proposed approved methods are their regulated analytes (parameters) within the method. Some of these proposed methods introduce new technologies to the NPDES program, while others are updated versions of previously approved methods. These additions will improve data quality and provide the regulated community with greater flexibility. Further, EPA is aware that organizations sometimes republish methods to correct errors or revise the description. These changes do not affect the performance of the method. Therefore, if there are changes for methods in this proposed rule before publication of a final rule, EPA will include the updated versions. In the tables at Section 136.3, EPA lists the parameters in alphabetical order. To better identify new parameters proposed in this rule EPA added some of these parameters, such as bisphenol A and nonylphenol, at the end of these lists. In the final rule, EPA may choose to reorder the listings to arrange all parameters alphabetically.

A. Changes to 40 CFR 136.3 To Include New EPA Methods and New Versions of Previously Approved EPA Methods

EPA is proposing to add new EPA methods that require new technologies to its Part 136 test procedures. EPA also is proposing new versions of already approved EPA methods with technologies that have been in use for many years. The new EPA methods and new versions of EPA approved methods are described in the following paragraphs.

1. EPA is proposing a new version of EPA Method 1664, 1664B: 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. In addition, EPA is proposing to amend the RCRA regulations at 40 CFR 260.11, which currently specify use of method 1664A, to additionally specify the revised version, 1664B.

Currently, Method 1664A is used as a required testing method to determine eligibility of materials for certain conditional exclusions from RCRA regulations under 40 CFR 260.20 and 260.22. These exclusions are known as “delistings.” These delistings provide that certain wastes generated at particular facilities are no longer classified as hazardous wastes under RCRA. When delistings are granted by EPA, the Agency describes them, along with applicable conditions, in appendix IX to 40 CFR part 261.

A number of delistings specify, among other things, the following test method: “Method 9070A (uses EPA Method 1664, Rev. A).” This testing method must be used by waste generators to determine if their wastes are an oily waste for delisting purposes. The language used in Appendix IX reads this way because Method 9070A in SW-846 (including on the SW-846 Web site,

http://www.epa.gov/epawaste/hazard/testmethods/sw846/pdfs/9070a.pdf

) simply reads that Method 1664A is to be used. Thus, although Method 9070A is cited, it is actually Method 1664A. Method 9070A does not exist independently of Method 1664A.

Once this rule becomes final, we would encourage future delistings, if applicable, to cite the test method as “Method 9070A (uses Method EPA 1664, Rev. B).” EPA is not proposing to amend delistings granted in previous years that reference Method 1664A at this time, since it would require additional review to assess the need for such a change and an analysis of each delisting.

Oil and Grease is a method-defined parameter that measures hexane extractable material (HEM) using n-hexane (85% minimum purity, 99.0% minimum saturated C6 isomer, residue < 1mg/L.) Before the use of Freon® was banned, EPA defined oil and grease as Freon®-extractable material. To replace Freon® for oil and grease determinations (64 FR 26315, May 14, 1999) EPA conducted extensive side-by-side studies of several extracting solvents on a variety of samples to determine how the values compared to Freon®-extractable material values.

In today's proposed rule, EPA describes six oil and grease methods, and proposes only the three methods in Table IB that use n-hexane to extract the sample because the solvent-defined definition of oil and grease measurements precludes use of any other extraction solvent or extraction technique. Without extensive side-by-side testing, permit writers, permitees, and data reviewers lack a basis for comparing HEM permit limits or measurements to values obtained with other extraction solvents or techniques. EPA lacks information about whether permit writers or permitees would value having more ways to extract oil and grease samples, or about how much effort they or others would be willing to exert to determine if the alternate values were equal to HEM values or convertible to HEM values by a conversion factor.

Although solvents may not be changed, EPA has described some allowable changes to the proposed EPA Method 1664B. This method describes (1) modifications allowable for nationwide use without prior EPA reviews (cf. documentation procedures described at 40 CFR 136.6), and (2) describes modifications not allowable including the use of any extraction solvent other than n-hexane or determination technique other than gravimetry. Although Method 1664B allows use of alternate extraction techniques, such as solid phase extraction (SPE) some discharges or waste streams may not be amenable to SPE. For these samples, 1664B should be applied as written. Conditioning of the solid-phase disk or device with solvents other than n-hexane (

e.g.,

alcohol, acetone, etc) is allowed, only if this solvent(s) is completely removed from the SPE disk or device prior to passing the sample through the SPE disk or device.

2. EPA is proposing to include in Table IB new EPA Method 200.5 and clarifying that the axial orientation of the torch is allowed for use with 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). It also 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 elements the axial orientation results in greater sensitivity and lower detection limits than the radial orientation. EPA now authorizes the use of Method 200.5 in testing under its Safe Drinking Water Act Program (73 FR 31616, June 6, 2008). Approval of Method 200.5 and the flexibility within Method 200.7 will allow laboratories to use either axial instruments or radial instruments to measure metals in water samples.

3. EPA is proposing to add EPA Method 525.2, an updated version of EPA Method 525.1, in Table IG (Test Methods for Pesticide Active Ingredients) as an additional approved method for all parameters for which EPA has previously approved Method 525.1. Further, EPA is soliciting comment on whether EPA should substitute Method 525.2 for Method 525.1.

EPA is proposing to include Pesticide Methods from Table IG in Table ID (Test Procedures for Pesticides). Specifically, EPA is proposing to add EPA Method 525.2 for the same pesticides for which EPA has approved Method 525.1 in Table IG. Both methods use GC/MS methodology.

EPA is proposing to add some of the Pesticide Active Ingredients methods in Table IG that have been in use for more than 10 years to Table ID for general use. These methods are:

a. EPA Method 608.1, “The Determination of Organochloride Pesticides in Municipal and Industrial Wastewater.” This is a gas chromatographic (GC) method used to determine certain organochlorine pesticide compounds listed in industrial and municipal discharges. 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 is a GC method used to determine certain organochlorine pesticides compounds in industrial and municipal discharges. This method measures chlorothalonil, DCPA, dichloran, methoxychlor, and permethrin.

c. EPA Method 614, “The Determination of Organophosphorus Pesticides in Municipal and Industrial Wastewater.” This is a GC method used to determine organophosphorus compounds in industrial and municipal discharges. This method measures azinphos methyl, demeton, diazinon, disulfoton, ethion, malathion, parthion methyl, and parathion ethyl.

d. EPA Method 614.1, “The Determination of Organophosphorus Pesticides in Municipal and Industrial Wastewater.” This is a GC method used to determine organophosphorus compounds in industrial and municipal discharges. This method measures dioxathion, EPN, ethion, and terbufos.

e. EPA Method 615, “The Determination of Chlorinated Herbicides in Municipal and Industrial Wastewater.” This is a GC method used to determine chlorinated herbicides compounds in industrial and municipal discharges. 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 is a GC method used to determine organohalide compounds in industrial and municipal discharges. 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 is a GC method used to determine triazine pesticides compounds in industrial and municipal discharges. This method measures ametryn, atraton, atrazine, prometon, prometryn, propazine, sec-bumeton, simetryn, simazine, terbuthylazine, terbutryn.

h. EPA Method 622, “The Determination of Organophosphorus Pesticides in Municipal and Industrial Wastewater.” This is a GC method used to determine organophosphorus pesticides compounds in industrial and municipal discharges. 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 is a GC method used to determine thiophosphate pesticides compounds in municipal and industrial discharges. 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 is a high-performance liquid chromatographic (HPLC) method used to determine carbamate and urea pesticide compounds in industrial and municipal discharges. This method measures aminocarb, barban, carbaryl, carbofuran, chlorpropham, diuron, fenuron, fenuron-TCA, fluometuron, linuron, methiocarb, methomyl, mexacarbate, monuron, neburon, oxamyl, propham, propoxur, siduron, swep.

4. EPA is proposing to add in Table IC EPA 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. These ethers are used in brominated flame retardants. This method uses isotope dilution and internal standard high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). This method allows use of a temperature-programmed injector/vaporizer and a short column to improve recoveries of the octa-, nona-, and decabrominated diphenyl ethers.

5. EPA is proposing to add in Table IC EPA Method 1668C, “Chlorinated Biphenyl Congeners in Water, Soil, Sediment, Biosolids, and Tissue by HRGC/HRMS.” This method determines individual chlorinated biphenyl congeners in environmental samples by isotope dilution and internal standard high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). Current Part 136 methods only measure a mixture of congeners in seven Aroclors—PCB-1016, PCB-1221, PCB-1232, PCB-1242, PCB-1248, PCB-1254, and PCB-1260. EPA Method 1668C can measure the 209 individual PCB congeners in these mixtures. EPA developed Method 1668 for use in wastewater, surface water, soil, sediment, biosolids, and tissue matrices.

EPA first published Method 1668 in 1999 and it is being used in several environmental applications, including

NPDES permits. EPA based today's proposed version, 1668C, on the results of an interlaboratory validation study (EPA 2010a, b), peer reviews (EPA 2010c), and user experiences. In the development and subsequent multi-laboratory validation of this method, EPA has evaluated method performance characteristics, such as selectivity, calibration, bias, precision, quantitation and detection limits. For example, EPA has observed that detection limits and quantitation levels are usually dependent on the level of interferences and laboratory background levels rather than instrumental limitations. Thus, the published minimum levels of quantitation are conservative estimates of the concentrations at which a congener can be measured with laboratory contamination present (EPA 2010d).

EPA recognizes that the performance of this Method may vary among the 209 congeners, and in different matrices. This is typical of multi-analyte methods because not all chemicals respond identically to extraction and clean up techniques, or have identical instrument responses. 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 a 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 PCB method and the polybrominated diphenyl ether (PBDE) Method 1614A are performance-based methods. This means that users have the flexibility to modify the method to adapt to the sometimes unique characteristics of the user's sample. There is flexibility to modify the sample preparation steps to remove substances that interfere with measurement of the PCB congeners. A consequence of this flexibility is that, after customizing a performance-based method for a specific sample or application, the user should continue to use the same customized procedures on these samples or applications to maintain data comparability.

EPA Method 1668C, the interlaboratory study report, and peer reviews are in the docket for today's rule and on EPA's CWA methods Web site at

http://www.epa.gov/waterscience/methods.

EPA lists Method 1668C in Table IC as the parameter, “PCBs 209 Congeners.”

6. EPA is proposing to update in Table IH EPA Method 1622, “Cryptosporidium in Water by Filtration/IMS/FA” and EPA Method 1623, “Cryptosporidium and Giardia in Water by Filtration/IMS/FA” to reflect changes made in the December 2005 versions of these methods. EPA's drinking water program uses the 2005 versions of the methods. The methods allow the flexibility to choose among several types of filters, quality controls, and stains, as well as clarification on measuring sample temperatures, quality control sample requirements and use of quality control sample results, minimizing carry-over debris, analyst verification procedures and sample condition criteria upon receipt. This method substitution necessitates a change in the holding temperature (Table II) for

Cryptosporidium and

Giardia

from 0-8 °C to refrigerate between 1-10 °C.

7. EPA is proposing in Table IH revised versions of EPA Methods 1103.1, 1106.1, 1600 (also in Table IA), 1603, and 1680 to correct technical errors. Specifically, for Methods 1103.1 and 1603, tryptone broth should be tryptone water (section 12.4.3). In addition, in Tables 2 and 3, respectively, of these two methods, the positive control organism for the cytochrome oxidase reagent has been changed to

P. aeruginosa

from

E. faecalis,

and the negative control organism for Simmons citrate agar has been changed to

S. flexneri

from

E. coli

for more definitive results. In section 7.5.2 of Method 1603, the formula for magnesium chloride hexahydrate should have a dot before the waters rather than an alpha sign (MgCl

2

·6H

2

O). In Methods 1106.1 and 1600, in Tables 6 and 7, respectively, the true spiked Enterococci “T (CFU/100 mL)” in the spiked sample based on the lot mean valued provided by the manufacturer should be 32 instead of 11.2. In Method 1680, the lactose for Lauryl Tryptose Broth (LTB) should be 5.0 g, not 25.0 g (section 7.6.1), and the dipotassium hydrogen phosphate for EC medium should be 4.0 g, not 44.0 g (section 7.7.1).

8. EPA is proposing to add Method 1627, “Kinetic Test Method for the Prediction of Mine Drainage Quality.” The method is a standardized simulated weathering test that provides information to predict the quality of mine drainage from coal mining operations or weathering. The method also can be a tool with which to generate data in the design and implementation of best management practices and treatment processes needed by mining operations to meet U.S. EPA discharge requirements at 40 CFR part 434. Other publications have referred to this method generically as the ADTI Weathering Procedure 2 (ADTI-WP2). EPA lists Method 1627 in Table IB as “Acid Mine Drainage.” The method is suitable for determinations of probable hydrologic consequences and to develop cumulative hydrologic impact assessment data to support Surface Mining Control and Reclamation Act (SMCRA) permit application requirements. Although this method is directed toward the coal mining industry and regulatory agencies, the method may be applicable to highway and other construction involving cut and fill of potentially acid-producing rock. This method may be used to predict the water quality characteristics (

e.g.,

pH, acidity, metals) of mine site discharges using observations from sample behavior under simulated and controlled weathering conditions. The method was developed and evaluated in single, multiple and interlaboratory method validation studies in laboratories representing the mining industry, private sector, federal agencies, and academia.

9. EPA proposes to approve EPA Method 624, “Purgeables,” for definitive measurements of acrolein and acrylonitrile in wastewater. Currently this method is approved only to screen samples for the presence of acrolein and acrylonitrile. Footnote 4 to Table IC requires that the analyst confirm occurrences with either EPA Method 603 or 1624 because, when EPA promulgated this method, EPA believed the confirmatory step was necessary. Commenters on a previous proposed rule to amend part 136 (69 FR 18166, April 6, 2004) requested that EPA allow use of Method 624 for definitive determination of acrolein and acrylonitrile in wastewater without a confirmatory step and provided EPA with data. EPA has considered this comment and after reviewing additional data (Test America 1, 2) is proposing to revise the listing of Method 624 in Table IC to remove footnote 4 that requires a confirmatory analysis.

B. Changes to 40 CFR 136.3 To Include New Standard Methods and New Versions of Approved Standard Methods

EPA is proposing to revise how we identify approved methods that are published by the Standard Methods Committee. Currently in the tables at 136.3(a), EPA lists these methods in one or more columns as being in the 18th, 19th, 20th printed compendiums, or in the On-line editions published by the Standard Methods Committee. EPA identifies which versions are approved by the printed edition in which the

method is published or, in the case of the electronic version of the method, by the last two digits of the year in which the method was published by the Standard Methods Committee (

e.g.,

Standard Method 2320 B-97). In some cases, EPA has approved more than one version of a Standard Method. Approval of several versions of the same Standard Method has led to inconsistencies in how laboratories conduct these analyses especially in quality assurance/quality control (QA/QC) practices. For this reason, EPA is proposing to approve only the most recent version of a method published by the Standard Methods Committee with as few exceptions as possible by listing only one version of the method with the year of publication designated by the last four digits in the method number (

e.g.,

Standard Method 2320 B-1997). This change allows use of a specific method in any edition that includes a method with the same method number and year of publication. Previously, a laboratory only could use the method that was published in the edition of

Standard Methods

listed in the tables at 136.3(a). In some cases, EPA used footnotes to designate approved Standard Methods that are no longer published in

Standard Methods.

In addition, EPA is proposing to approve new Standard Methods, SM, new versions of currently approved SM, and the use of an already approved SM for a chemical that is not currently listed in Table IB. The new versions of currently approved SM have been revised to clarify or improve the instructions in the method, improve the quality control (QC) instructions, or make editorial corrections. The proposed new SM and new versions of SM are described in the following paragraphs.

1. EPA is proposing to add SM 5520 B-2001 and SM 5520 F-2001 for Oil and Grease determinations. These methods measure hexane extractable material (HEM). EPA is proposing these methods because they use n-hexane as the extraction solvent. EPA is not proposing SM 5520 G-2001 because it allows use of a co-solvent, such as acetone. In the preceding description of EPA's proposed Method 1664B, EPA explained that oil and grease is a measurement defined by the solvent, in this case n-hexane, used to extract oil and grease from the sample. Thus, use of any other solvent system, such as a co-solvent is precluded.

2. EPA is proposing to add SM 4500-NH

3

G-1997, Ammonia (as N) and TKN, Phenate Method, which is an automated version of the previous version of a previously approved SM 4500-NH

3

F-1997.

3. EPA is proposing to add SM 4500-B B-2000, Boron, Curcumin Method, which uses the same chemistry and instruments as Method I-3112-85.

4. EPA is proposing to add SM 4140-1997, Inorganic Ions (Bromide, Chloride, Fluoride, Orthophosphate, and Sulfate), Capillary Ion Electrophoresis with Indirect UV Detection, which uses the same technology as the EPA approved ASTM Method D6508-00.

5. EPA is proposing to add SM 3114 C-2009, Arsenic and Selenium by Continuous Hydride Generation/Atomic Absorption Spectrometry, which is an automated version of the approved manual method, and uses the same technology as Method I-2062-85.

6. EPA is proposing to add SM 3111 E-1999 for determinations of aluminum and beryllium. The method uses the same instrumental techniques as SM 3111D with an additional chelation concentration step for increased sensitivity.

7. EPA is proposing to add SM 5220 B-1997 for Chemical Oxygen Demand which is similar to EPA Method 410.3.

8. EPA is proposing to add SM 4500 N

ORG

D-1997 for determinations of Kjeldahl Nitrogen—Total, which has a similar chemical and instrument setup as in EPA Method 351.2 in Table IB. The same chemical reaction is measured in both of these methods.

9. EPA is proposing to add SM 4500 P G-1999 and SM 4500 P H-1999, Phosphorus. Both of these methods use separate flow injection instrumentation that is the same as EPA Method 365.1.

10. EPA is proposing to add SM 4500 P E-1999 and SM 4500 P F-1999, Phosphorus. These methods, 4500 P E-1999 Manual Single Reagent and F-1999 Automated Ascorbic Acid, have been approved for drinking water analyses (73 FR 31616, June 3, 2008).

11. EPA is proposing to add SM 4500 O B, D, E and F-2001, Oxygen, Iodometric Methods. EPA is proposing these methods because Standard Methods has broken down the Winkler titration method into several sections. Sections 4500 O B, D, E and F have been added to provide a more detailed Winkler titration. Section B contains information on how to collect the sample and what pretreatment may be needed for just the Winkler titrations. Sections D, E, and F contain specific sample pretreatment for interferences. Section D (see Item 12) is for ferrous iron interferences. Section E (

see

Item 13) is for samples with a high concentration of Total Suspended Solids. Section F is for samples with large concentrations of biological solids. These sections are similar to the instructions in ASTM D888, AOAC 973.45, and USGS I-1575-78.

12. EPA is proposing to add SM 4500 O D-2001, Oxygen, Permanganate Modification. This method for determinations of dissolved oxygen contains the same permanganate pretreatment step that is specified in ASTM D 888 and AOAC 973.45.

13. EPA is proposing to add SM 4500 O E-2001, Oxygen, Alum Flocculation Modification. This method for dissolved oxygen describes a pretreatment step that removes high concentrations of suspended solids.

14. EPA is proposing to add SM 3500 K C-1997, Potassium, Selective Electrode Method. This method uses the same electrochemical procedure to measure Potassium that is used in the Standard Methods for ammonia, chloride, cyanide, and nitrate. Only the electrode construction is different.

15. EPA is proposing to add SM 2540 E-1997 for determinations of Residues—Volatile. This fixed and volatile solids method uses the same equipment and procedures to measure this method defined parameter as approved EPA Method 160.4.

16. EPA is proposing to add SM 4500 SiO

2

E-1997 and SM 4500 SiO

2

F-1997, Silica. These methods have the same instrument setup and molybdate color reagent as USGS Method I-2700, but utilize different reducing agents to produce molybdenum blue color. There are slight modifications in the chemical reaction, but the molybdenum blue final analyte is the same.

17. EPA is proposing to add SM 4500 SO

4

C-1997, D-1997, E-1997, F-1997 and G-1997, Sulfate. EPA is proposing to approve the online version of these methods because they are identical to the approved versions published in the 18th, 19th and 20th edition of Standard Methods. EPA approved the online versions for drinking water use (73 FR 31616, June 3, 2008).

18. EPA is proposing to add SM 4500 S

2

−B-2000 and C-2000, Sulfide. These approved methods have been revised to describe more completely the sample collection, transportation and analysis steps.

C. Changes to 40 CFR 136.3 To Include New ASTM Methods and New Versions of Previously Approved ASTM Methods

EPA is proposing to add to the list of approved testing procedures new ASTM methods for existing pollutants in Table IB, such as cyanide, and methods for new pollutants, such as the nonylphenols in Table IC. EPA also is

proposing new versions of previously approved ASTM methods.

1. EPA is proposing to add ASTM D2036-09 Standard Test Methods for Cyanides in Water, Test Method A Total Cyanide after Distillation. In 2009, ASTM revised the version of this method currently listed in part 136. The method measures cyanides that are free, and strong-metal-cyanide complexes (

e.g.

iron cyanides) that dissociate and release free cyanide when refluxed under strongly acidic conditions. The cyanide in some cyano complexes of transition metals, for example, cobalt, gold, platinum, etc., is not determined. Samples are digested with sulfuric acid in the presence of magnesium chloride in a distillation reaction vessel that consists of a 1-L round bottom flask, with provision for an inlet tube and a condenser connected to a vacuum-type absorber. The flask is heated with an electric heater. Smaller distillation tubes such as 50-mL midi tubes or 6-mL MicroDist

TM

tubes described in D7284-08 can be used if the quality control requirements in D2036-09 are satisfied. After distillation, the cyanide concentration can be determined with titration, ion chromatography, colorimetric procedure (spectrophotometric), selective ion electrode, or flow injection analysis with gas diffusion separation and amperometric detection. The inclusion of ion chromatography and gas diffusion separation with amperometric detection as determinative steps (D2036-09, sections 16.5 and 16.6) will give users additional options to measure cyanide after distillation. Furthermore, these determinative steps can be used to mitigate interferences that have been associated with conventional colorimetric test methods.

2. EPA is proposing to add ASTM D6888-09 Standard Test Method for Available Cyanide with Ligand Displacement and Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and Amperometric Detection. This method is used to determine the concentration of available inorganic cyanide in an aqueous wastewater or effluent. The method detects the cyanides that are free and metal-cyanide complexes that are easily dissociated into free cyanide ions. The method does not detect the less toxic strong metal-cyanide complexes, cyanides that are not “amenable to chlorination.” Total cyanide can be determined for samples that have been distilled as described in Test Methods D2036-09, Test Method A, Total Cyanides after Distillation. Complex cyanides bound with nickel or mercury are released by ligand displacement with the addition of a ligand displacement agent prior to analysis. Other available cyanide species do not require ligand displacement under the test conditions. If samples are distilled for total cyanide, ligand exchange reagents are not required since the cyanide complexes are dissociated and absorbed into the sodium hydroxide capture solution during distillation. The treated or distilled sample is introduced into a flow injection analysis (FIA) system where it is acidified to form hydrogen cyanide. The hydrogen cyanide gas diffuses through a hydrophobic gas diffusion membrane, from the acidic donor stream into an alkaline acceptor stream. Up to 50-mg/L sulfide is removed during flow injection to mitigate sulfide interference. The captured cyanide is sent to an amperometric flow cell detector with a silver-working electrode. In the presence of cyanide, silver in the working electrode is oxidized at the applied potential. The anodic current measured is proportional to the concentration of cyanide in the standard or sample injected.

3. EPA is proposing to add ASTM D7284-08 Standard Test Method for Total Cyanide in Water by Micro Distillation followed by Flow Injection Analysis with Gas Diffusion Separation and Amperometric Detection. This method determines the concentration of total cyanide in wastewater, and detects the cyanides that are free and strong-metal-cyanide complexes (

e.g.,

iron cyanides) that dissociate and release free cyanide when refluxed under strongly acidic conditions. This method has a range of approximately 2 to 400 μg/L (parts per billion) total cyanide. Higher concentrations can be measured with sample dilution or lower injection volume. The determinative step of this method utilizes flow injection with amperometric detection based on ASTM D6888-09. Sample distillation is based on Lachat QuikChem Method 10-204-00-1-X. Prior to analysis, samples must be distilled with a micro-distillation apparatus described in the test method or with a suitable cyanide distillation apparatus specified in Test Methods D 2036-09. The samples are distilled with a strong acid in the presence of magnesium chloride catalyst and captured in sodium hydroxide absorber solution. The absorber solution from the distillation is introduced into a flow injection analysis (FIA) system where it is acidified to form hydrogen cyanide. The hydrogen cyanide gas diffuses through a hydrophobic gas diffusion membrane, from the acidic donor stream into an alkaline acceptor stream. The captured cyanide is sent to an amperometric flow cell detector with a silver-working electrode. In the presence of cyanide, silver in the working electrode is oxidized at the applied potential. The anodic current measured is proportional to the concentration of cyanide. This method has been shown to be less susceptible to interferences compared to conventional spectrophotometric determinations for total cyanide.

4. EPA is proposing to add ASTM D7511-09e2 Standard Test Method for Total Cyanide by Segmented Flow Injection Analysis, In-Line Ultraviolet Digestion and Amperometric Detection. This method determines the concentration of total cyanide in drinking and surface waters, as well as domestic and industrial wastes. Cyanide ion (CN-), hydrogen cyanide in water (HCN(aq)), and the cyano-complexes of zinc, copper, cadmium, mercury, nickel, silver, and iron may be determined by this method. Cyanide ions from Au(I), Co(III), Pd(II), and Ru(II) complexes are only partially determined. The applicable range of the method is 3 to 500 μg/L cyanide using a 200-μL sample loop. The range can be extended to analyze higher concentrations by sample dilution or by changing the sample loop volume. ASTM D7511-09e2 decomposes complex cyanides by narrow band, low watt UV irradiation in a continuously flowing acidic stream at room temperature. Reducing and complexing reagents, combined with the room temperature narrow band low watt UV, minimize interferences. The hydrogen cyanide generated passes through a hydrophobic membrane into a basic carrier stream. The cyanide concentration is determined by amperometry. This method operates similarly to available cyanide methods OIA1677 and ASTM D6888-09. The available cyanide methods employ a preliminary ligand addition to liberate cyanide ion from weak to moderate metal cyanide complexes. These available cyanide methods were developed because they overcome significant interferences caused by the preliminary chlorination and/or distillation processes. Instead of ligands, ASTM D7511-09e2 irradiates the sample causing strong metal cyanide complexes plus all complexes measured by the available cyanide methods to liberate cyanide and generate hydrogen cyanide. Once the sample solution passes from the UV irradiation, the measurement principle is equivalent to OIA1677 and/or ASTM D6888-09.

5. Because there were no EPA-approved methods for free cyanide when water quality criteria were

established for free cyanide EPA recommended measurement of cyanide after a “total” distillation. Analytical methods for free cyanide have been developed, and in today's rule EPA is proposing to add free cyanide as a parameter (24A in Table IB.) For determinations of this parameter, EPA is proposing to allow use of the approved available cyanide method, OIA 1677-09, and two ASTM methods (D4282-02 and D7237-10.) ASTM D4282-02 Standard Test Method for Determination of Free Cyanide in Water and Wastewater by Microdiffusion determines free cyanide as the cyanide that diffuses into a sodium hydroxide solution from a solution at pH 6. It is not applicable to cyanide complexes that resist dissociation, such as hexacyanoferrates and gold cyanide, and it does not include thiocyanate and cyanohydrin. ASTM D7237-10 Standard Test Method for Free Cyanide with Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and Amperometric Detection determines free cyanide with the same instrumentation and technology as approved methods, ASTM D6888-09 and OIA 1677-09, but under milder (less acidic) conditions and without use of ligand replacement reagents.

6. EPA is proposing to add ASTM D888-09 Standard Test Method for Dissolved Oxygen in Water. This method determines dissolved oxygen concentrations in water using the titrimetric (Part A), polarographic (Part B) and luminescence-based (Part C) detection methods. This standard test method is applicable to the determination of dissolved oxygen between 0.05-20 ppm in influent, effluent or ambient water testing. ASTM recently updated Part C of this method to include a detailed description of the technology and to update calibration procedures to include a two-point calibration and an air saturated water calibration in addition to a water saturated air calibration. This method may be used for Biological Oxygen Demand (BOD) and Carbonaceous Oxygen Demand (CBOD.)

7. EPA is proposing to add ASTM D7573-09 Standard Test Method for Total Carbon and Organic Carbon in Water by High Temperature Catalytic Combustion and Infrared Detection. This Method has the same chemical and instrument setup as approved SM 5310 B-2000.

8. EPA is proposing to add in Table IC ASTM D7065-06: Standard Test Method for Determination of five chemicals: Nonylphenol (NP), Bisphenol A (BPA), p-tert-Octylphenol (OP), Nonylphenol Monoethoxylate (NP1EO), and Nonylphenol Diethoxylate (NP2EO) in Environmental Waters by Gas Chromatography Mass Spectrometry. These five chemicals are partitioned into an organic solvent, separated using gas chromatography and detected with mass selective detection. These chemicals or isomer mixtures are qualitatively and quantitatively determined. Although this method adheres to selected ion monitoring mass spectrometry, full scan mass spectrometry has also been shown to work well under these conditions. This method has been multi-laboratory validated for use with surface water and waste treatment effluent samples and is applicable to these matrices. It has not been investigated for use with salt water or solid sample matrices. The reporting limit for nonylphenol is 5 μg/L (ppb); the chronic Freshwater Aquatic Life Ambient Water Quality Criterion is 6.6 ppb.

9. EPA is proposing to add in Table IC ASTM D7574-09: Standard Test Method for Determination of BPA in Environmental Waters by Liquid Chromatography/Tandem Mass Spectrometry. BPA is an organic chemical produced in large quantities. BPA is soluble in water and undergoes degradation in the environment. The reporting limit for BPA is 20 ng/L which is fifty times less than the limit in D7065-06 (see preceding Item 8). The method is based on a solid phase extraction (SPE) followed by separation with liquid chromatography and tandem mass spectrometry (LC/MS/MS), which reduces the amount of sample required, solvents, the analysis time, and the reporting limits. The method has been tested in effluents from secondary and tertiary publicly owned treatment works (POTW), and fresh surface and ground water.

10. EPA is proposing to add in Table IC ASTM D7485-09: Standard Test Method for Determination of NP, OP, NP1EO, and NP2EO in Environmental Waters by Liquid Chromatography/Tandem Mass Spectrometry. The method extracts these four chemicals from water with SPE followed by LC/MS/MS separation and detection. These chemicals are qualitatively and quantitatively determined by this method. This method uses single reaction monitoring (SRM) mass spectrometry. Environmental waters tested using this method were sewage treatment plant effluent, river water, seawater, and a modified ASTM D5905 artificial wastewater. The reporting limit for nonylphenol is 100 ng/L, ppt. The Freshwater and Saltwater Aquatic Life Ambient acute criterion is 7.0 ppb, and the chronic criterion is 1.7 ppb.

11. EPA is not proposing to include in Table IB two ASTM oil and grease methods, D7066-04 and D7575-10 because neither method uses n-hexane to determine oil and grease as hexane extractable material (HEM). As previously explained in the discussion of Method 1664B, HEM is a measurement defined by the solvent (n-hexane) used to extract oil and grease from the sample. D7066-04 employs a proprietary solvent, S-316, a dimer/trimer of chlorotrifluoroethylene to measure S-316-extractable substances from an acidified sample. Method D7066 may be useful for determinations of total petroleum hydrocarbons (TPH). Although TPH has been measured in some applications, EPA has never included it as a Part 136 pollutant nor received any convincing evidence that it should do so. Although S-316 is not the same solvent as the fluorocarbon, Freon®, it is a fluorochlorohydrocarbon.

Instead of n-hexane, ASTM D7575-10 uses a different extracting process, an extracting membrane, followed by infrared measurement of the materials in the sample that can pass through the membrane. Several other steps in D7575-10 significantly differ from 1664 including: Use of 10-mL sample aliquot from sample bottle vs. entire contents of 1-L sample; homogenization of samples; and the challenge of pushing solid oil and grease samples through a membrane. The results of a multi-laboratory study (OSS 2009) that the developer conducted as part of ASTM's evaluation of D7575 are in the docket.

D. Changes to 40 CFR 136.3 To Include Alternate Test Procedures

To promote method innovation, EPA maintains a program whereby method developers may apply for an EPA review and potentially for approval of alternate test procedures. This Alternate Test Procedure (ATP) program is described for Clean Water Act applications at Parts 136.4 and 136.5. EPA has reviewed and is proposing for nationwide use eight alternate test procedures. These proposed new methods include: Hach Company's Method 10360 Luminescence Measurement of Dissolved Oxygen (LDO®) in Water, In-Situ Incorporated's Method 1002-8-2009 Dissolved Oxygen (DO) Measurement by Optical Probe, Method 1003-8-2009 Biochemical Oxygen Demand (BOD) Measurement by Optical Probe, and Method 1004-8-2009 Carbonaceous Biochemical Oxygen Demand (CBOD) Measurement by Optical Probe August 2009, Mitchell Method M5271 and M5331 for measuring turbidity in wastewater; Thermo Scientific's Orion Method

AQ4500 for measuring turbidity in wastewater; and Systea Scientific, LLC's Systea Easy (1-Reagent) Nitrate Method. Descriptions of these new methods included for approval are as follows:

1. EPA is proposing to approve Hach Company's Method 10360 Luminescence Measurement of Dissolved Oxygen (LDO®) in wastewater, Revision 1.1 dated January 4, 2006. EPA has reviewed this method and the data generated in a multi-laboratory validation study performed by Hach Company and is proposing to approve it for use in measuring dissolved oxygen. EPA is also proposing to approve the Hach method 10360 to be used for Dissolved Oxygen (DO) when determining BOD and CBOD.

This method uses an optical probe to measure the light emission characteristics from a luminescence-based reaction that takes place at the sensor-water interface. A light emitting diode (LED) provides incident light required to excite the luminophore substrate. In the presence of dissolved oxygen, the reaction is suppressed. The resulting dynamic lifetime of the excited luminophore is evaluated and equated to DO concentration.

The method involves the following steps:

• Calibration of the probe using water-saturated air, and

• Measurement of the dissolved oxygen in the sample using the probe.

Approved methods for measuring dissolved oxygen are listed at 40 CFR 136.3, Table IB. The performance characteristics of the Hach Company Method 10360 were compared to the characteristics of the methods listed at 40 CFR 136.3, Table IB for measurement of dissolved oxygen. Because the Hach Company Method 10360 is equally effective relative to the methods already promulgated in the regulations, EPA is proposing to include this method in the list of methods approved for measuring dissolved oxygen concentrations in wastewater when determining BOD and CBOD.

2. EPA is proposing to approve In-Situ Incorporated's Method 1002-8-2009 Dissolved Oxygen Measurement by Optical Probe. EPA has reviewed this method and the data generated in a multi-laboratory validation study performed by In-Situ Incorporated and is proposing to approve it for use in measuring dissolved oxygen. In-Situ Method 1002-8-2009 uses a new form of electrode based on the luminescence emission of a photoactive chemical compound and the quenching of that emission by oxygen to measure dissolved oxygen concentration.

The method involves the following steps:

• Calibration of the probe using water-saturated air, and

• Measurement of the dissolved oxygen in the sample using the probe.

Approved methods for measuring dissolved oxygen are listed at 40 CFR 136.3, Table IB. The performance characteristics of the In Situ Method 1002-8-2009 were compared to the characteristics of the methods listed at 40 CFR 136.3, Table IB for measurement of dissolved oxygen. Because the In-Situ Method 1002-8-2009 is equally effective relative to the methods already promulgated in the regulations, EPA is proposing In-Situ Method 1002-8-2009 for inclusion in the list of methods approved for measuring dissolved oxygen concentrations in wastewater.

3. EPA is proposing to approve In-Situ Incorporated's Method 1003-8-2009 Biochemical Demand (BOD) Measurement by Optical Probe. EPA has reviewed this method and the data generated in a multi-laboratory validation study performed by In-Situ Incorporated and is proposing to approve it for measuring BOD.

In-Situ Method 1003-8-2009 uses a new form of electrode based on the luminescence emission of a photoactive chemical compound and the quenching of that emission by oxygen to measure dissolved oxygen concentration when performing the 5-day BOD test.

The method involves the following steps:

• Filling a BOD bottle with diluted seeded sample,

• Measuring the dissolved oxygen in the sample using an optical DO probe,

• Sealing and incubating the bottle for five days,

• Measuring the dissolved oxygen with an optical probe after the five day incubation period, and

• Calculating the BOD from the difference between the initial and final dissolved oxygen measurements.

Approved methods for measuring BOD are listed at 40 CFR 136.3, Table IB. The performance characteristics of In-Situ Method 1003-8-2009 were compared to the characteristics of the methods listed at 40 CFR 136.3, Table IB for measurement of BOD. Because In-Situ Method 1003-8-2009 is equally effective relative to the methods already promulgated in the regulations, EPA is proposing In-Situ Method 1003-8-2009 for inclusion in the list of methods approved for measuring BOD.

4. EPA is proposing to approve In-Situ Incorporated's Method 1004-8-2009 Carbonaceous Biochemical Oxygen Demand (CBOD) Measurement by Optical Probe. EPA has reviewed this method and the data generated in a multi-laboratory validation study performed by In-Situ Incorporated and is proposing to approve it for use in measuring carbonaceous biochemical oxygen demand (CBOD). In-Situ Method 1004-8-2009 uses a new form of electrode based on the luminescence emission of a photoactive chemical compound and the quenching of that emission by oxygen to measure dissolved oxygen concentration when performing the CBOD test.

The method involves the following steps:

• Filling a BOD bottle with diluted seeded sample,

• Adding a chemical nitrification inhibitor,

• Measuring the dissolved oxygen in the sample using an optical dissolved oxygen probe,

• Sealing and incubating the bottle for five days,

• Measuring the dissolved oxygen with an optical probe after the five day incubation period, and

• Calculating the CBOD from the difference between the initial and final dissolved oxygen measurements.

Approved methods for measuring CBOD are listed at 40 CFR 136.3, Table IB. The performance characteristics of In Situ-Method 1004-8-2009 were compared to the characteristics of the methods listed for measurement of CBOD. Because In-Situ Method 1004-8-2009 is equally effective relative to the methods already promulgated in the regulations, EPA is proposing In-Situ Method 1004-8-2009 for inclusion in the list of methods approved for measuring CBOD.

5. EPA is proposing to approve the Mitchell Method M5271 dated July 31, 2008. This method uses laser based nephelometry to measure turbidity in drinking water and wastewater. The method involves the following steps for instruments other than on-line continuous models:

• Mixing the sample to thoroughly disperse the solids,

• Waiting until air bubbles disappear,

• Pouring a sample into a turbidimeter tube, and

• Reading turbidity directly from the instrument scale or from the appropriate calibration curve.

Approved methods for turbidity are listed at 40 CFR 136.3 Table 1B. The performance characteristics of Mitchell Method M5271 were compared to the performance characteristics of EPA Method 180.1 listed at 40 CFR 136.3 for measurement of turbidity. Comparisons were based on results obtained from turbidimeters placed in series which took measurements at one minute

intervals over a 20 to 30 hour time period at three different public water supply systems (in one case measurements were taken at 15 minute intervals). Testing included source water from one ground water source and two surface water sources and included at least one natural filter event (back-flush) in lieu of artificially calibrated spikes using a primary standard spiking solution. Additionally, a demonstration of performance at higher turbidities was conducted by making replicate measurements of primary standards at four levels (5 NTU, 10 NTU, 20 NTU and 40 NTU). Results showed excellent correlation between measurements made using a tungsten filament incandescent bulb as specified in EPA Method 180.1 and those made using the laser light source specified in Mitchell Method M5271. Based on the results of these studies, EPA has determined that Mitchell Method M5271 is as effective as the methods already promulgated in the regulations. EPA is proposing to add this method to the list of methods approved for measurement of turbidity in wastewater.

6. EPA is proposing Mitchell Method M5331 dated July 31, 2008. This method uses LED based nephelometry to measure turbidity. The method involves the following steps for instruments other than on-line continuous models:

• Mixing the sample to thoroughly disperse the solids,

• Waiting until air bubbles disappear,

• Pouring the sample into turbidimeter tube, and

• Reading turbidity directly from the instrument scale or from the appropriate calibration curve.

Approved methods for turbidity are listed at 40 CFR 136.1 Table 1B. The performance characteristics of Mitchell Method 5331 were compared to the performance characteristics of EPA Method 180.1 listed at 40 CFR 136.3 for measurement of turbidity. Comparisons were based on results obtained from turbidimeters placed in series, which took measurements at one minute intervals over a 20 to 30 hour time period at three different public water supply systems (in one case measurements were taken at 15 minute intervals). Testing included source water from one ground water source and two surface water sources and included at least one natural filter event (back-flush) in lieu of artificially calibrated spikes using a primary standard spiking solution. Additionally, a demonstration of performance at higher turbidities was conducted by making replicate measurements of primary standards at four levels (5 NTU, 10 NTU, 20 NTU and 40 NTU). Results showed excellent correlation between measurements made using a tungsten filament incandescent bulb as specified in EPA Method 180.1 and the LED light source specified in Mitchell Method M5331. Based on the results of these studies, EPA has determined that Mitchell Method M5331 is equally effective relative to the methods already promulgated in the regulations. EPA is proposing to add this method to the list of methods approved for measurement of turbidity in wastewater.

7. EPA is proposing to approve Thermo Scientific's Orion Method AQ4500 dated March 12, 2009. This method uses LED-based nephelometry to measure turbidity. The method involves the following steps:

• Calibration of the instrument using a primary calibration standard,

• Placing the sample into the sample chamber, and

• Reading the turbidity result displayed on the instrument.

Approved methods for turbidity are listed at 40 CFR 136.3 Table IB. The performance characteristics of Thermo Scientific's Orion Method AQ4500 were compared to the performance characteristics of EPA Method 180.1 listed at 40 CFR 136.3 for measurement of turbidity. Comparisons were based on an ASTM round robin study comparing results from analyses of 28 different samples of various types including formazin standards, styrene divinyl benzene (SDVB) co-polymer bead standards and real world samples ranging from approximately 2 NTU to over 1,000 NTU. These analyses were conducted using turbidimeters with various light sources including tungsten filament incandescent bulbs as specified in EPA Method 180.1 and white LEDs as specified in Thermo Scientific's Orion Method AQ4500. Additionally, a demonstration of performance at lower turbidities was conducted by making 20 replicate measurements of dilute formazin standards at four levels (0.2 NTU, 0.5 NTU, 1 NTU, and 2 NTU) using turbidimeters with tungsten filament incandescent bulbs as specified in EPA Method 180.1 and turbidimeters using white LEDs as specified in Thermo Scientific Orion Method AQ4500. Results showed significant correlation between measurements made using a tungsten filament incandescent bulb as specified in EPA Method 180.1 and those made using the LED light source specified in Thermo Scientific's Orion Method AQ4500. Based on the results of these studies, EPA has determined that Thermo Scientific's Orion Method AQ4500 is as effective as the methods already promulgated in the regulations. EPA is proposing to add this method to the list of methods approved for measurement of turbidity in wastewater.

8. EPA is proposing to approve Systea Scientific, LLC's Systea Easy (1-Reagent) Nitrate Method dated February 4, 2009. This is a method that uses automated discrete analysis, and spectrophotometry to determine concentrations of nitrate and nitrite combined or singly. The method involves the following steps:

• Reduction of nitrate in a sample to nitrite using a non-hazardous proprietary reagent,

• Diazotizing the nitrite originally in the sample plus the reduced nitrate with sulfanilamide followed by coupling with N-(1-napthyl) ethylenediamine dihydrochloride under acidic conditions to form a highly colored azo dye,

• Colorimetric determination in which the absorbance of color at 546 nm is directly proportional to the concentration of the nitrite plus the reduced nitrate in the sample,

• Measurement of nitrite singly, if needed, by analysis of the sample while eliminating the reduction step, and

• Subtraction of the nitrite value from that of the combined nitrate plus nitrite value to measure nitrate singly if needed.

Approved methods for nitrate, nitrite and combined nitrate/nitrite are listed at 40 CFR 136.3, Table 1B. The performance characteristics of the Systea Easy (1-Reagent) Nitrate Method were compared to the characteristics of the methods listed at 40 CFR 136.3 for nitrate and nitrite. Based on the results of the comparative studies, EPA has determined that the Systea Easy (1-Reagent) Nitrate Method is as effective as the methods already promulgated in the regulations for use in determining concentrations of nitrate and nitrite and combined nitrate/nitrite. The method is a “green” alternative to other approved methods that use cadmium, a known carcinogen, for the reduction of nitrate to nitrite. The performance of Systea Easy (1-Reagent) Nitrate Method is equivalent to other methods already approved for measurement of nitrate, nitrite and combined nitrate/nitrite in wastewater.

E. Clarifications and Corrections to Previously Approved Methods in 40 CFR 136.3

EPA is proposing a clarification to procedures for measuring orthophosphate, and is proposing to correct typographical or other citation errors in part 136.

1. EPA is clarifying the purpose of the immediate filtration requirement in

orthophosphate measurements, which is to assess the dissolved or bio-available form of orthophosphorus (

i.e.,

that which passes through a 0.45 micron filter), hence the requirement to filter the sample immediately upon collection. This filtration excludes any particulate forms of phosphorus that might hydrolyze into orthophosphorus in a slightly acidic sample during the allowed 48 hour holding time. Each grab sample must be filtered within 15 minutes of collection to prevent orthophosphate formation. Specifically, filtration may not be delayed until the final grab sample is collected; each grab sample must be filtered upon collection. However, the filtered grab samples may be held for compositing up to the 48-hour holding time.

2. EPA is proposing to correct missing citations to the table of microbiological methods for ambient water monitoring which are specified in Table IH at 40 CFR 136.3. Stakeholders asked EPA to separately specify the microbiological methods that EPA has approved for wastewater (Table IA) from those for ambient water. On August 15, 2005 (70 FR 48256), EPA proposed to move microbial (bacterial and protozoan) methods which were applicable to ambient water to a new table, Table IH. However, in the final rule of March 26, 2007 (72 FR 14220), EPA inadvertently omitted fecal coliform, total coliform, and fecal streptococcus methods from the table. EPA is proposing to add these methods to Table IH.

3. EPA is proposing to correct several other typographical or minor citation errors, such as incomplete or incorrect method citations.

F. Proposed Revisions in Table II at 40 CFR 136.3(e) to Required Containers, Preservation Techniques, and Holding Times

EPA is proposing revisions to Table II at 136.3(e) to clarify how to resolve conflicts between instructions in this table and instructions in an approved method or other source, and to amend some of the current requirements in Table II.

1. The introductory text to Table II at 136.3(e) specifies that the instructions in the table take precedence over other sources of this information. EPA publishes holding time and related instructions in Table II to provide a consistent set of instructions, and for other reasons. Not all methods contain complete instructions, and some otherwise equivalent methods (or methods for the same parameter) have conflicting instructions. For example, Table II instructions specify the 48 hour BOD holding time while some Part 136 methods recommend 24 hours. In this instance Table II instructions take precedence. EPA recognizes that there may be cases where new technologies or advancements in current technologies may produce approved methods with instructions for a specific parameter that differ from Table II instructions, and provide better results. Cyanide determinations and some automated methods may fall into this category. Therefore, EPA is proposing to revise the text at 136.3(e) to allow a party to submit documentation to their permitting or other authority that supports use of an alternative approach. EPA is proposing to revise the introductory text to the table to read as follows: “Information in this table takes precedence over instructions provided in specific methods or elsewhere unless a party documents the acceptability of an alternative to the Table II instructions. The nature, timing and extent of the required documentation (

i.e.

how to apply and review as well as the amount of supporting data) are left to the discretion of the permitting authority (State Agency or EPA Region) or other authority and may rely on instructions, such as those provided for method modifications at 136.6.” Thus, an alternate sample container, preservation and/or holding time may be considered at the discretion of the permitting authority or other authority.

2. Some stakeholders have asked EPA to extend the holding time for

Escherichia coli

and

Enterococcus.

In 2006, EPA conducted a nationwide holding time study (EPA 2006) for fresh and marine ambient waters and concluded that, on a nationwide basis, the Agency was unable to justify extending the holding time for

Escherichia coli

or

Enterococcus

in these water matrices. However, EPA is proposing to provide some relief by revising footnote 22 to Table II, which applies to bacterial tests. This footnote currently reads as follows: “Sample analysis should begin immediately, preferably within 2 hours of collection. The maximum transport time to the laboratory is 6 hours, and samples should be processed (in incubator) within 2 hours of receipt at the laboratory.”

Stakeholders have commented that laboratories must meet the two-hour analysis start time, even if they receive the samples early enough that they could start after two hours and still meet the overall six-hour time limit. EPA is proposing to revise the footnote 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.”

3. EPA is proposing to revise 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. This practice advises analysts to add a reducing agent only if an oxidant is present, and use of the reducing agents sodium thiosulfate (Na

2

S

2

O

3

), ascorbic acid, sodium arsenite (NaAsO

2

), or sodium borohydride (NaBH

4

).

4. EPA is proposing to revise 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. EPA proposes to allow 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.

5. EPA is proposing to revise footnote 16 of Table II instructions for handling Whole Effluent Toxicity (WET) samples to be consistent with the November 19, 2002 (67 FR 69951) “Guidelines for Establishing Test Procedures for the Analysis of Pollutants; Whole Effluent Toxicity Test Methods; Final Rule,” as well as the three toxicity methods (Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms (5th Edition, October 2002), Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms (4th Edition, October 2002), and Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms (3rd Edition, October 2002). In the 2002 final rule, EPA established the acceptable range for the current sampling holding temperature for aquatic toxicity tests as 0 to 6 °C based on current National Environmental Laboratory Accreditation Conference (NELAC) standards. EPA also clarified in the final rule that hand-delivered samples used on the day of collection do not need to be cooled to 0 to 6 °C prior to test initiation. Section 8.5.1 of all three WET methods listed previously states, “Unless the samples are used in an on-site toxicity test the day of collection (or hand delivered to the testing laboratory for use on the day of collection) it is recommended that they be held at 0 to 6 °C until used to inhibit microbial degradation, chemical transformation, and loss of highly volatile toxic substances.” EPA is proposing to add two sentences to the

end of Footnote 16 of Table II based on this information. The two sentences are “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.” 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.)

6. EPA is proposing to add a sentence to footnote 4 of Table II to clarify the sample holding time for the Whole Effluent Toxicity (WET) samples for the three toxicity methods (Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms (5th Edition, October 2002), Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms (4th Edition, October 2002), and Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms (3rd Edition, October 2002) to indicate that one sample of the minimum of three required samples may be used for the renewal of the test solutions and that the sample holding time refers to first use of each sample collected for the toxicity test. The sentence to be added is, “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.”

G. Proposed Revisions to 40 CFR 136.4 and 136.5

EPA is proposing to revise §§ 136.4 and 136.5 to describe the procedures for obtaining review and EPA approval for the use of alternate test procedures (alternate methods or ATPs). The proposed changes would revise 40 CFR 136.4 to establish the procedures for obtaining approval for nationwide use of an ATP. The proposed changes would modify 40 CFR 136.5 to establish the procedures for obtaining approval for use of an ATP in a State within a particular EPA Region. It should be noted that in its ATP program, EPA considers for review only those methods for which EPA has published an ATP protocol. Presently, EPA has published protocols for chemistry, radiochemical, and culture microbiological methods. EPA does not have ATP protocols for Whole Effluent Toxicity (WET) methods or genetic methods.

In today's rule, EPA proposes to clarify that the intent of the limited use authority is to allow limited use of an alternate method for a specific application at a facility or type of discharge without requiring the same level of supporting test data that would be required for approval for nationwide use. Thus, limited use authority is not intended to be used as a means of avoiding the full examination of comparability that is required when EPA considers a method for nationwide use and decides to amend its list of approved CWA methods at 40 CFR part 136 to include alternative test procedures. In the event that EPA decides not to approve an application for approval of an alternate method for nationwide use, the Regional Alternate Test Procedures Coordinator may choose to reconsider any previous limited use approvals of the alternate method. Based on this reconsideration, the Regional Coordinator will notify the user, if the limited use approval is withdrawn.

H. Proposed Revisions to Method Modification Provisions at 40 CFR 136.6

EPA encourages regulatory authorities to allow analysts the flexibility to modify CWA methods without prior approval provided the user has documented equivalent or better performance of the method in the matrix type to which the user will apply the modified method. EPA recognizes that addressing specific matrix interferences may require modifications to approved methods that do not require the extensive review and approval process specified for an alternate test procedure at 136.4 and 136.5. Based on users' experiences with 136.6, since it was promulgated on March 12, 2007 (72 FR 11199), EPA proposes to revise this section 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 employed in methods currently approved in 40 CFR part 136. Analysts may use the examples in this section to assess and document that their modification is acceptable and does not depart substantially from the chemical principles in the method being modified. EPA specifically invites comment on the examples of flexibility specified at 136.6 and the documentation that a method modifier must have to demonstrate the equivalency of the modified method. In particular, EPA is interested in public comment on what additional controls, if any, should be applied when changing pH, purge times, buffers, or applying the relative standard error calibration alternative.

I. Proposed New Quality Assurance and Quality Control Language at 40 CFR 136.7

EPA is proposing to specify “essential” quality control at § 136.7 for use in conducting an analysis with an approved method and when insufficient instructions are contained in an approved method. Auditors, co-regulators, laboratory personnel, and the regulated community have noted the different amounts and types of quality assurance (QA) and quality control (QC) procedures practiced by laboratories that use 40 CFR part 136 methods. Some of these methods are published by voluntary consensus standards bodies, such as the Standard Methods Committee, and ASTM International. ASTM and Standard Methods are contained in printed compendium volumes, electronic compendium volumes, or as individual online files. Each organization has its 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. For example, the publisher of

Standard Methods for the Examination of Water and Wastewater

consolidates the general quality assurance and quality control requirements for all methods. Each specific Part and section can contain additional QA and QC requirements (for example, see part 2020, 3020, 6020, and 9020). ASTM specifies QA and QC requirements in the analyte method's Referenced Documents section and in the analyte method. Both organizations require the analyst to reference this additional information within the respective compendiums to achieve the QA and QC expected for valid results.

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 specific part 136 method, or referenced these procedures by other means. Consequently, EPA

expects that an analyst using these consensus body methods for reporting under the CWA will also comply with the quality assurance and quality control requirements listed in the appropriate sections in the consensus 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 would 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 have insufficient QA/QC requirements, analysts could refer to and follow the QC published in several public sources. Examples of these sources include the instructions in an equivalent approved EPA method or standards published by the National Environmental Laboratory Accreditation Conference (cf. Chapter 5 of the compendium published in 2003.)

In addition to and regardless of the source of the laboratory's QA and QC instructions, EPA is proposing at 136.7 to specify twelve essential quality control checks that must be in the laboratory's documented quality system unless a written rationale is provided to explain why these controls are inappropriate for a specific analytical method or application. This written rationale will be included in the laboratory's Standard Operating Procedure (SOP) for each method to which specific controls do not apply (

e.g.,

internal standards, surrogate standards or tracers do not apply to analyses of inorganic parameters) as well as being included with the monitoring data produced using each method. 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.

J. Proposed Withdrawal of Appendices at 40 CFR 136

EPA is proposing to incorporate by reference all of the methods printed in 40 CFR part 136 appendices A and C, and to remove most of the information in Appendix D. EPA is proposing to remove EPA Method numbers 601 through 613, 624, 625, 1613B, 1624B and 1625B from Appendix A. All of these methods are readily accessible from a variety of sources including EPA's CWA methods Web site

http://www.epa.gov/waterscience/methods/.

Removing this appendix would decrease the resources associated with the annual publication of 40 CFR part 136 regulations. EPA would incorporate these methods by reference in Tables IC and ID at 136.3(a).

EPA is proposing to remove Appendix C—Method 200.7 Inductively Couple Plasma—Atomic Emission Spectrometric Method for Trace Element Analysis of Water and Waste Method because this method has been superseded by Rev. 5.4 of Method 200.7, which is incorporated by reference in Table IB.

Finally, EPA is proposing to remove from Appendix D the data for all EPA methods that are no longer approved. This would result in Appendix D containing Precision and Recovery Statements only for EPA Method 279.2 for thallium and EPA Method 289.2 for zinc. EPA will correct any typographical errors in the Appendix, such as the misspelling of thallium. EPA requests comment on whether to publish and make available, at least temporarily, the current version of Appendix D online at the CWA methods Web site for historical purposes.

K. Proposed Revisions at 40 CFR 423

EPA is proposing two changes to part 423, Steam Electric Power Generating Point Source Category. First, EPA proposes to revise the definitions for

total residual chlorine

and

free available chlorine

at §§ 423.11(a) and 423.11(l), respectively. The current definitions restrict the permittee to the use of the specific amperometric titration method cited in the definitions. The revised definitions will allow the permittee flexibility to use additional approved methods. EPA proposes to revise the definitions as follows:

a. The term

total residual chlorine

(or total residual oxidants for intake water with bromides) means the value obtained using any of the “chlorine—total residual” methods in Table IB 136.3(a), or other methods approved by the permitting authority.

b. The term

free available chlorine

means the value obtained using any of the “chlorine—free available” methods in Table IB 136.3(a) where the method has the capability of measuring free available chlorine, or other methods approved by the permitting authority.

Second, EPA is proposing to move the current citations of methods from Part 423 and reference a new parameter, “chlorine-free available”, in Table IB at 136.3(a). Under this parameter, EPA will list any Part 136 methods for total residual chlorine that also provide instructions for determining free chlorine. The tables at 136.3 are well known as the source of most methods that are approved for CWA programs. For this reason EPA is proposing to move the citations of specific methods from part 423 to Table IB, and as described in the following sections, also for Parts 430 and 435.

L. Proposed Revisions at 40 CFR 430

EPA is proposing several editorial changes to 40 CFR part 430, The Pulp, Paper, and Paperboard Point Source Category. Currently the complete text of EPA Methods 1650 and 1653 are published in Appendix A of part 430. EPA is proposing to cite these two methods in Table IC, at § 136.3, and to incorporate by reference the full text of these methods. EPA will list these two methods in Table IC—List of Approved Test Procedures for Non-Pesticide Organic Compounds, under adsorbable organic halides (AOX) by Method 1650 and chlorinated phenolics by Method 1653. This action would remove Appendix A at 40 CFR part 430, and organize the analytical methods for the Pulp, Paper, and Paperboard category into one part, the Part 136 CWA methods tables, of the CFR.

To help users more readily identify approved compliance monitoring methods, EPA is proposing to cite at part 430 the Part 136 methods that are approved for these pollutants: Chloroform, 2,3,7,8- tetrachlorodibenzo-p-dioxin (TCDD), and 2,3,7,8- tetrachlorodibenzo-p-furan (TCDF).

M. Proposed Revisions at 40 CFR 435

EPA is proposing several changes to Part 435, Oil and Gas Extraction Point Source Category. EPA is proposing to move, and in two cases revise, the methods 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-09-013), which is included in the record for this rulemaking. This proposed 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 proposes to move from Part 435 to the cited document, EPA-821-R-09-013.

EPA Method Numbers for Oil and Gas Extraction Point Source Category Analytical Methods and Prior CFR References

Analytical/test method

EPA method number

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.

EPA is also proposing to incorporate additional quality assurance procedures in the marine anaerobic biodegradation analytic method (Appendix 4 of Subpart A of Part 435) and to correct some erroneous references and omissions in the method for identification of crude oil contamination (Appendix 5 of Subpart A of Part 435). EPA is proposing to include these revisions in the EPA document (EPA-821-R-09-013).

EPA promulgated the use of the marine anaerobic biodegradation analytic method (closed bottle test, ISO 11734:1995 as clarified by Appendix 4 to Subpart A of Part 435) 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 analytic 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.

Additionally, EPA is proposing to correct some erroneous references and omissions in the method for identification of crude oil contamination (Appendix 5 of Subpart A of Part 435). Specifically, EPA is proposing to:

a. Add a schematic flow for qualitative identification of crude oil, which was erroneously omitted in Appendix 5 to Subpart A of Part 435,

b. Correct erroneous citations in sections 9.5, 9.6, 11.3, and 11.3.1 of Appendix 5, and

c. Add a missing “<” 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.”

As previously noted, EPA is proposing to include these revisions to these two methods in the EPA document (EPA-821-R-09-013), which is included in the record for this rulemaking.

III. Statutory and Executive Order Reviews

A. Executive Order 12866: Regulatory Planning and 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 the EO.

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 updated 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 proposed 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 updated 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. In some cases, analytical costs may increase slightly due to the additional QC requirements included in the methods that are being approved to replace older EPA methods. However, most laboratories that analyze samples

for EPA compliance monitoring have already instituted QC requirements as part of their laboratory practices.

We continue to be interested in the potential impacts of the proposed rule on small entities and welcome comments on issues related to such impacts.

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 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 updated versions of testing procedures. Thus, the proposed rule is not subject to the requirements of Section 203 of UMRA.

E. Executive Order 13132: Federalism

This proposed rule does not have federalism implications. It will not have substantial direct effects on the States, on the relationship between the national government and the States, or on the distribution of power and responsibilities among the various levels of government, as specified in Executive Order 13132 (64 FR 43255, Aug. 10, 1999). This proposed rule merely approves new and updated versions of testing procedures. The costs to State and local governments will be minimal (in fact, governments may see a cost savings), 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 solicits comment on this proposed action from State and local officials.

F. Executive Order 13175: Consultation and Coordination With Indian Tribal Governments

This proposed rule does not have tribal implications, as specified in Executive Order 13175, (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 updated versions of testing procedures. The costs to Tribal governments will be minimal (in fact, governments may see a cost savings), and the rule does not preempt State law. 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 solicits comment on this proposed action from tribal officials.

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 action proposes to approve new and updated versions of testing procedures.

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 proposed rulemaking involves technical standards. As described throughout this document, EPA is proposing many standards developed by the Standard Methods Committee, and ASTM International. In Sections IIB, IIC of this preamble, and the tables at § 136.3, EPA specifies these proposed methods, provides information on how to obtain copies of these methods, and describes the rationale for employing these methods. EPA welcomes comments on this aspect of the proposed rulemaking and, specifically, invites the public to identify potentially applicable voluntary consensus standards and to explain why EPA should include such standards in future revisions to Part 136.

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 proposed 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 proposes to approve new and updated versions of testing procedures to measure pollutants in water.

IV. References

EPA 2006, “Assessment of the Effects of Holding Time on Enterococci Concentrations in Fresh and Marine Recreational Waters and

Escherichia coli

Concentrations in Fresh Recreational Waters” (EPA-821-R-06-019, December 2006)

EPA 2010a, “Method 1668A Interlaboratory Validation Study Report” (EPA-820-R-10-004, March 2010)

EPA 2010b, “Addendum to the Method 1668A Interlaboratory Validation Study Report” (EPA-820-R-10-003, March 2010)

EPA 2010c, “Peer Review of the Method 1668A Interlaboratory Validation Study” (EPA 820-R-10-007, April 2010)

EPA 2010d, “Development of Pooled Method Detection Limits (MDLs) and Minimum Levels of Quantitation (MLs) for EPA Method 1668C (May 2010)

EPA 2010e, Errata for “Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms” (4th edition, October 2002) manual.

OSS 2009, ASTM D7575 “Inter-Laboratory Study to Establish Precision Statements for ASTM WK23240—Standard Test Method for Solvent-Free Membrane Recoverable Oil and Grease by Infrared Determination”

Passaic River 2010 “Summary of Passaic River Split Sample Results”, EPA, April 2010

Test America 1 “Acrolein Acrylonitrile Stability Study”

Test America 2 “Acrolein Acrylonitrile Control Charts”

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: August 6, 2010.

Lisa P. Jackson,

Administrator.

For the reasons set out in the preamble, title 40, chapter I of the Code of Federal Regulations, is proposed to be amended as follows:

PART 136—GUIDELINES ESTABLISHING TEST PROCEDURES FOR THE ANALYSIS OF POLLUTANTS

1. The authority citation for part 136 continues to read as follows:

Authority:

Secs. 301, 304(h), 307, and 501(a) Pub. L. 95-217, 91 Stat. 1566,

et seq

. (33 U.S.C. 1251,

et seq.

) (The Federal Water Pollution Control Act Amendments of 1972 as amended by the Clean Water Act of 1977.)

2. Section 136.1 is amended by revising paragraph (a) to read as follows:

§ 136.1

Applicability.

(a) The procedures prescribed herein shall, except as noted in §§ 136.4, 136.5, and 136.6, be used to perform the measurements indicated whenever the waste constituent specified is required to be measured for:

(1) An application submitted to the 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;

b. In paragraph (a), revise Table IA, IB, IC, ID, IG, and IH;

c. By revising paragraphs (b)(1), (b)(54), (b)(55), (b)(56), (b)(59), (b)(60), (b)(61), (b)(70), and adding paragraph (b)(73);

d. By revising paragraph (e) introductory text;

e. In Table II to paragraph (e), by revising entries “Table IA—Bacterial Tests”, “Table IA—Aquatic Toxicity Tests”, “Table IH—Bacterial Tests”, and “Table IH—Protozoan Tests, and footnote 6”.

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. 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 incorporation by reference of these documents, as specified in paragraph (b) of this section, was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the documents may be obtained from the sources listed in paragraph (b) of this section. Documents may be inspected at EPA's Water Docket, EPA West, 1301 Constitution Avenue, NW., Room 3334, Washington, DC (Telephone: 202-566-2426); or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to:

http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html.

These test procedures are incorporated as they exist on the day of approval and a notice of any change in these test procedures will be published in the

Federal Register

. The 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. Under certain circumstances paragraph (c) of this section, § 136.5 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

,

13

1681

11

,

18

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

p. 124

3

9222 D-1997

3. Coliform (total), number per 100 mL

MPN, 5 tube, 3 dilution, or

p. 114

3

9221 B-2006

MF

2

, single step or two step

p. 108

3

9222 B-1997

B-0025-85.

4

4. Coliform (total), in presence of chlorine, number per 100 mL

MPN, 5 tube, 3 dilution, or

p. 114

3

9221 B-2006

MF

2

with enrichment

p. 111

3

9222 (B+B.5c)−1997

5. E. coli, number

per 100 mL.

19

MPN

6

,

8

,

14

multiple tube/multiple well

9223 B-2004

12

991.15

10

Colilert®

12

,

16

Colilert-18®.

12

,

15

,

16

MF

2

,

5

,

6

,

7

,

8

single step

1603

20

mColiBlue-24®.

17

6. Fecal streptococci, number per 100 mL

MPN, 5 tube, 3 dilution,

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.

19

MPN

6

8

, multiple tube/multiple well

D6503-99

9

Enterolert®.

12

22

MF

2

5

6

7

8

single step

1600.

23

8. Salmonella, number per gram dry

weight.

11

MPN multiple tube

1682.

21

Aquatic Toxicity:

9. Toxicity, acute, fresh water organisms, LC

50

, percent effluent

Ceriodaphnia dubia

acute

2002.0.

24

Daphnia puplex

and

Daphnia magna

acute

2021.0.

24

Fathead minnow,

Pimephales promelas,

and Bannerfin shiner,

Cyprinella leedsi,

acute

2000.0.

24

Rainbow Trout,

Oncorhynchus mykiss,

and brook trout,

Salvelinus fontinalis,

acute

2019.0.

24

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.

24

Sheepshead Minnow,

Cyprinodon variegatus,

acute

2004.0.

24

Silverside,

Menidia beryllina, Menidia menidia,

and

Menidia peninsulae,

acute

2006.0.

24

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

25

, percent effluent

Fathead minnow,

Pimephales promelas,

larval survival and growth

1000.0.

25

Fathead minnow,

Pimephales promelas,

embryo-larval survival and teratogenicity

1001.0.

25

Daphnia,

Ceriodaphnia dubia,

survival and reproduction

1002.0.

25

Green alga,

Selenastrum capricornutum,

growth

1003.0.

25

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.

26

Sheepshead minnow,

Cyprinodon variegatus,

embryo-larval survival and teratogenicity

1005.0.

26

Inland silverside,

Menidia beryllina,

larval survival and growth

1006.0.

26

Mysid,

Mysidopsis bahia,

survival, growth, and fecundity

1007.0.

26

Sea urchin,

Arbacia punctulata,

fertilization

1008.0.

26

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

USEPA. 1978. Microbiological Methods for Monitoring the Environment, Water, and Wastes. Environmental Monitoring and Support Laboratory, U.S. Environmental Protection Agency, Cincinnati, OH, EPA/600/8-78/017.

4

USGS. 1989. 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, U.S. Geological Survey, U.S. Department of the Interior, Reston, VA.

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

ASTM. 2000, 1999, 1996. Annual Book of ASTM Standards—Water and Environmental Technology. Section 11.02. ASTM International. 100 Barr Harbor Drive, West Conshohocken, PA 19428.

10

AOAC. 1995. Official Methods of Analysis of AOAC International, 16th Edition, Volume I, Chapter 17. Association of Official Analytical Chemists International. 481 North Frederick Avenue, Suite 500, Gaithersburg, MD 20877-2417.

11

Recommended for enumeration of target organism in sewage sludge.

12

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

.

13

USEPA. April 2010. Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation Using Lauryl-Tryptose Broth (LTB) and EC Medium. U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA-821-R-10-003.

14

Samples shall be enumerated by the multiple-tube or multiple-well procedure. Using multiple-tube procedures, employ an appropriate tube and dilution configuration of the sample as needed and report the Most Probable Number (MPN). Samples tested with Colilert® may be enumerated with the multiple-well procedures, Quanti-Tray®, Quanti-Tray®/2000, and the MPN calculated from the table provided by the manufacturer.

15

Colilert-18® is an optimized formulation of the Colilert® for the determination of total coliforms and

E. coli

that provides results within 18 h of incubation at 35 °C rather than the 24 h required for the Colilert® test and is recommended for marine water samples.

16

Descriptions of the Colilert®, Colilert-18®, Quanti-Tray®, and Quanti-Tray®/2000 may be obtained from IDEXX Laboratories, Inc. 1 IDEXX Drive, Westbrook, ME 04092.

17

A description of the mColiBlue24® test, is available from Hach Company. 100 Dayton Ave., Ames, IA 50010.

18

USEPA. July 2006. Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation using A-1 Medium. U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA-821-R-06-013.

19

Recommended for enumeration of target organism in wastewater effluent.

20

USEPA. December 2009. Method 1603:

Escherichia coli

(

E. coli

) in Water by Membrane Filtration Using Modified membrane-Thermotolerant

Escherichia coli

Agar (modified mTEC). U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA-821-R-09-007.

21

USEPA. July 2006. Method 1682:

Salmonella

in Sewage Sludge (Biosolids) by Modified Semisolid Rappaport-Vassiliadis (MSRV) Medium. U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA-821-R-06-014.

22

A description of the Enterolert® test may be obtained from IDEXX Laboratories, Inc., 1 IDEXX Drive, Westbrook, ME 04092.

23

USEPA. December 2009. Method 1600: Enterococci in Water by Membrane Filtration Using membrane-

Enterococcus

Indoxyl-β-D-Glucoside Agar (mEI). U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA-821-R-09-016.

24

USEPA. October 2002. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms. Fifth Edition. U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA/821/R-02/012.

25

USEPA. October 2002. Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms. Fourth Edition, U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA/821/R-02/013.

26

USEPA. October 2002. Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms. Third Edition. U.S. Environmental Protection Agency, Office of Water, Washington, DC, EPA/821/R-02/014.

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 E-1999

I-3051-85.

2

AA furnace

3113-2004

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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

See footnote 7.

Ion Chromatography

D6919-09

5. Antimony—Total,

4

mg/L

Digestion

4

followed by any of the following:

AA direct aspiration

36

3111 B-1999

AA furnace

3113-2004

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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 C-2009

D2972-08 (B)

I-3062-85.

2

AA furnace

3113-2004

D2972-08 (C)

I-4063-98.

49

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05.

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

3113-2004

D4382-02(07).

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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 E-1999

D3645-08 (A)

I-3095-85.

2

AA furnace

3113-2004

D3645-08 (B)

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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

D888-09

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); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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, Rev. 1.0 (1997)

4110 B-2000, C-2000, D-2000

D4327-03

993.30.

3

CIE/UV

4140-1997

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 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

3113-1999

D3557-02(07) (D)

I-4138-89.

51

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-1472-85

2

or

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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); 200.7, Rev. 4.4 (1994)

3120-1999

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14.

3

DCP

See footnote.

34

Titrimetric (EDTA)

3500-Ca-1997

D511-08(A)

Ion Chromatography

D6919-09

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

12

Dissolved Oxygen Depletion with nitrification inhibitor

5210 B-2001

D888-09

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, Rev. 1.0 (1997)

4110 B-2000 or C-2000

D4327-03

993.30,

3

I-2057-90.

51

CIE/UV

4140-1997

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 chela tion-extraction

3111 C-1999

AA furnace

3113-1999

D1687-02(07)(C)

I-3233-93.

46

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05.

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 C-1999

D3558-08 (A or B)

p. 37,

9

I-3239-85.

2

AA furnace

3113-2004

D3558-08 (C)

I-4243-89.

51

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05.

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 C-1999

D1688-07 (A or B)

974.27

3

p. 37

9

I-3270-85

2

or

I-3271-85.

2

AA furnace

3113-2004

D1688-07 (C)

I-4274-89.

51

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05

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

D7511-09e2

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, Rev. 1.0 (1997)

4110 B-2000 or C-2000

D4327-03

993.30.

3

CIE/UV

4140-1997

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 (Rev. 1978)

1

3113-2004

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14.

3

DCP

See footnote.

34

27. Hardness—Total, as CaCO3, mg/L

Automated colorimetric,

130.1 (Issued 1971)

1

Titrimetric (EDTA)

2340 C-1997

D1126-02(07)

973.5 2B,

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

+

-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

3125-2009

30. Iron—Total,

4

mg/L

Digestion

4

followed by any of the following:

AA direct aspiration

36

3111 B-1999 or C-1999

D1068-05 (A or B)

974.27,

3

I-3381-85.

2

AA furnace

3113-1999

D1068-05(C)

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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-Norg 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-Norg D-1997

D3590-02(06) (B)

I-4515-91.

45

Block digester, followed by Auto distillation and Titration

See footnote.

39

Block digester, followed by Auto distillation and Nesslerization.

See footnote.

40

Block Digester, followed by Flow injection gas diffusion (distillation not required)

See footnote.

41

32. Lead—Total,

4

mg/L

Digestion

4

followed by any of the following:

AA direct aspiration.

36

3111 B-1999 or C-1999

D3559-08(A or B)

974.27,

3

I-3399-85.

2

AA furnace

3113-1999

D3559-08(D)

I-4403-89.

51

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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

3113-2004

D858-07(C)

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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)

3112-2009

D3223-07

977.22,

3

I-3462-85.

2

Cold vapor, Automated

245.2 (Issued 1974)

Cold vapor atomic fluorescence spectrometry (CVAFS)

245.7, Rev. 2.0 (2005)

17

I-4464-01.

Purge and Trap CVAFS

1631E.

43

ICP/AES

36

200.7, Rev. 4.4 (1994)

3120-1999

I-4471-97.

50

ICP/MS

3125-2009

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

3113-2004

I-3492-96.

47

ICP/AES

200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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 C-1999

D1886-08(A or B)

I-3499-85.

2

AA furnace

3113-2004

D1886-08(C)

I-4503-89.

51

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05.

DCP

36

D4190-08

See footnote.

34

38. Nitrate (as N), mg/L

Ion Chromatography

300.0, Rev. 2.1 (1993) and 300.1, Rev. 1.0 (1997)

4110 B-2000 or C-2000

D4327-03

993.30.

3

CIE/UV

4140-1997

D6508-00(05)

D6508, Rev. 2.

54

Ion Selective Electrode

4500-NO

3

−

D-2000

Colorimetric (Brucine sulfate)

352.1

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.

2

Automated hydrazine

4500-NO

3

−

H-2000

Reduction/Colorimetric

See footnote.

62

Ion Chromatography

300.0, Rev. 2.1 (1993) and 300.1, Rev. 1.0 (1997)

4110 B-2000 or C-2000

D4327-03

993.30.

3

CIE/UV

4140-1997

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, Rev. 1.0 (1997)

4110 B-2000 or C-2000

D4327-03

993.30.

3

CIE/UV

4140-1997

D6508-00(05)

D6508, Rev.2.

54

41. Oil and grease—Total recoverable, mg/L

Hexane extractable material (HEM): n-Hexane extraction and gravimetry

1664B

42

5520 B-2001.

38

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

1664B

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. Orthophosphate (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, Rev. 1.0 (1997)

4110 B-2000 or C-2000

D4327-03

993.30.

3

CIE/UV

4140-1997

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

68

(C)

See footnote

63

68

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

3125-2009

DCP

See footnote.

34

48. Phenols, mg/L

Manual distillation

26

followed by any of the following:

420.1

1

(Rev. 1978)

5530B-2005

D1783-01

Colorimetric (4AAP) manual

420.1

1

(Rev. 1978)

5530D-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

Persulfate 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)

3120-1999

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.

1

ICP/MS

3125-2009

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)

3120-1999

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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

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.

1

ICP/MS

3125-2009

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

3125-2009

60. Selenium—Total,

4

mg/L

Digestion

4

followed by any of the following:

AA furnace

3113-2004

D3859-08 (B)

I-4668-98.

49

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

36

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05

AA gaseous hydride

3114 B-2009, or 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); 200.7, Rev. 4.4 (1994)

3120-1999

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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 C-1999

974.27,

3

p. 37,

9

I-3720-85.

2

AA furnace

3113 -1999

I-4724-89.

51

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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); 200.7, Rev. 4.4 (1994)

3120-1999

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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 -1997

D1125-99 (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, Rev. 1.0 (1997)

4110 B-2000 or C-2000

D4327-03

993.30,

3

I-4020-05.

CIE/UV

4140-1997

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)

3113-2004

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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

3113-2004

STGFAA

200.9, Rev. 2.2 (1994)

ICP/AES

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

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)

DCP

See footnote.

34

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14.

3

73. Turbidity, NTU

53

Nephelometric

180.1, Rev. 2.0 (1993)

2130-2001

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

3113-2004

D3373-03(07)

ICP/AES

200.5, Rev. 4.2 (2003); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05.

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 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); 200.7, Rev. 4.4 (1994)

3120-1999

D1976-07

I-4471-97.

50

ICP/MS

200.8, Rev. 5.4 (1994)

3125-2009

D5673-05

993.14,

3

I-4020-05.

DCP

36

D4190-08

See footnote.

34

Colorimetric (Dithizone)

(Zincon)

3500-Zn-1997

See footnote.

33

76. Acid Mine Drainage

1627

Table 1B Notes:

1

“Methods for Chemical Analysis of Water and Wastes,” Environmental Protection Agency, Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI), EPA-600/4-79-020 (NTIS PB 84-128677), Revised March 1983 and 1979 where applicable.

2

Fishman, M. J.,

et al.

“Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments,” U.S. Department of the Interior, Techniques of Water-Resource Investigations of the U.S. Geological Survey, Denver, CO, Revised 1989, unless otherwise stated.

3

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

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

Ammonia, Automated Electrode Method, Industrial Method Number 379-75 WE, dated February 19, 1976, Bran & Luebbe (Technicon) Auto Analyzer II, Bran & Luebbe Analyzing Technologies, Inc., Elmsford, NY 10523.

8

The approved method is that cited in “Methods for Determination of Inorganic Substances in Water and Fluvial Sediments”, USGS TWRI, Book 5, Chapter A1 (1979).

9

American National Standard on Photographic Processing Effluents, April 2, 1975. Available from ANSI, 25 West 43rd St., New York, NY 10036.

10

In-Situ Method 1003-8-2009, “Biochemical Oxygen Demand (BOD) Measurement by Optical Probe”. Available from In-Situ, Incorporated, 221 E. Lincoln Avenue, Ft. Collins, CO 80524, Telephone: 970-498-1500.

11

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

12

Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test method which measures “total BOD.” The addition of the nitrification inhibitor is not a procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit requires reporting the traditional BOD5 may not use a nitrification inhibitor in the procedure for reporting the results. Only when a discharger's permit specifically states CBOD5 is required can the permittee report data using a nitrification inhibitor.

13

OIC Chemical Oxygen Demand Method, Oceanography International Corporation, 1978, 151 Graham Road, P.O. Box 9010, College Station, TX 77842.

14

Chemical Oxygen Demand, Method 8000, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.

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, 840 Memorial Drive, Cambridge, MA 02138. 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, Rev. 2.0, “Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry,” February 2005, EPA-821-R-05-001, available from the U.S. EPA Sample Control Center (operated by CSC), 6101 Stevenson Avenue, Alexandria, VA 22304,

Telephone:

703-461-2100, Fax: 703-461-8056.

18

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

19

Copper, Biocinchoinate Method, Method 8506, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.

20

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

21

Hydrogen ion (pH) Automated Electrode Method, Industrial Method Number 378-75WA, October 1976, Bran & Luebbe (Technicon) Autoanalyzer II. Bran & Luebbe Analyzing Technologies, Inc., Elmsford, NY 10523.

22

Iron, 1,10-Phenanthroline Method, Method 8008, 1980, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.

23

Manganese, Periodate Oxidation Method, Method 8034, Hach Handbook of Wastewater Analysis, 1979, pages

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