office of water changes to water regulations methods update rule meghan hessenauer office of science...

Office of Water

Changes to Water RegulationsMethods Update Rule

Meghan HessenauerOffice of Science and Technology

March 2007

Office of Water

Methods Update Rule (MUR)

Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; National Primary Drinking Water Regulations; and National Secondary Drinking Water Regulations; Analysis and Sampling Procedures

Final Rule

40 CFR Parts 122, 136, 141, 143, 430, 455, and 465

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Summary of Final Rule

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MUR Timeline

March 12, 2007Final Rule

August 18, 2003Proposed Rule

April 6, 2004Proposed Rule

February 16, 2005NODA

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MUR Summary – Changes to CWA

New Vendor developed methods EPA methods Voluntary Consensus Standard Bodies methods (VCSB) Updated versions of currently approved methods Revisions to method modification and analytical

requirements Withdrawal of certain outdated methods Changes to sample collection, preservation, and holding

time requirements

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MUR Summary – Changes to SDWA

Approval of Vendor Developed Methods

New EPA Methods

New VCSB Methods

Approval of a modification to the test kit used with Syngenta Method AG-625

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MUR Summary

This Rule will provide:

More choices of methods

More flexible methods

Easier to modify methods without prior approval

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MUR Information

How do I get more information?

Docket ID

EPA-HQ-OW-2003-0070

http://www.regulations.gov

HQ Water Docket Center

202-566-2426

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MUR - Applicability

Who has to comply with these regulations?

Entities with NPDES permits

Entities that analyze water in accordance with the SDWA

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MUR Information

Summary of 40 CFR Part 122 Changes

NPDES Program

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MUR – Summary of 40 CFR Part 122 Changes

This rule amends the NPDES regulation at 40 CFR Part 122 to clarify use of methods at 40 CFR Part 136

Updates grab and composite sampling requirements

Resolves inconsistencies

Adds E. coli and Enterococci to the list of parameters in the permit program

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MUR Information


CWA Program

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EPA approved three new chemical methods submitted as Alternative Test Procedures (ATPs)Waters Corporation Method D6508 for determination of

anions by capillary ion electrophoresisLachat QuikChem Method 10-204-00-1-X for

determination of total cyanide using MICRODISTKelada-01 method for determination of total and

available cyanide using UV-digestion, flash distillation and colorimetry

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Approves a broad digestion procedure for total recoverable elementsEPA Method 200.2 (Revision 2.8, 1994) for use with

ICP-AES, ICP-MS, STGFAA, and FLAA Approves three new multi-element test procedures EPA

Method 200.8 (Revision 5.4, 1994)AOAC Method 993.14 (16th Edition)ASTM D5673-03 for determination of elements by ICP-

MS

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Approves a new multi-element test procedureEPA Method 200.9 (Revision 2.2, 1994) for

determination of elements by STGFAA. Approves four new methods for determination of

hexavalent chromium by ion chromatographyEPA Method 218.6AOAC Method 993.23 (16th Edition)ASTM D5257-97SM 3500-Cr C (20th Edition) and SM 3500-Cr E

(18th and 19th Editions)

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Approves five new methods for determination of anions by ion chromatography

EPA Method 300.0 (Revision 2.1, 1993)EPA Method 300.1 (Revision 1.0, 1997)AOAC Method 993.30 (16th Edition)ASTM D4327SM 4110 B (18th, 19th, and 20th Editions)

Approves automated cadmium reduction methods to determine nitrate and nitrite individually, as well as in combination

EPA Method 353.2 (Revision 2.0, 1993)ASTM D3867-99 A and BSM 4500- NO3 – E and F (18th, 19th, and 20th Editions)SM 4500-NO3 –E and F (2000)USGS Method I-4545-85

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Approves a new method for determination of chlorine by low level amperometry – SM 4500-Cl E (18th, 19th, 20th Editions) and SM 4500-Cl E (2000)

Approves a new method for determination of cations by ion chromatography, ASTM D6919-03.

Approves a new method for determination of chloride by potentiometry, SM 4500-Cl-D (18th, 19th, 20th Editions) and SM 4500-Cl-D(2000)

Approves a new method for determination of chloride by ion selective electrode, ASTM D512-89 (1999)

Office of Water


Approves EPA Method 245.7 for Mercury, “Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry” (Revision 2.0, 2005)

The Association of Metropolitan Sewerage Agencies (AMSA) petitioned the Agency to approve EPA Method 245.7 as an alternative to EPA Method 1631

Both methods use CVAFS and allow for trace analysis of mercury; however, EPA Method 245.7 uses a lower cost analyte isolation procedure

In response, EPA conducted a multi-laboratory validation of this method in 2001 to assess the method’s performance

A ML of 5 ng/L was achieved. In reagent water, average recoveries ranged between 85% to 105% and

relative standard deviations (RSDs) were below 15% Recoveries in industrial and municipal effluents ranged from 64% to 120%

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Withdrawal of MCAWW Methods

EPA replaced 109 EPA Methods with newer versions and retained 28 of these methods

EPA withdrew Method 413.1, the Freon-based oil and grease method – Hexane-based methods will be used instead

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MCAWW Methods retained in Table IB

Alkalinity 310.2

Ammonia 350.1 (Rev. 2.0 Aug 93)

Arsenic 206.5

COD 410.3, 410.4

Gold 231.2

Total Hardness 130.1

Iridium 235.2

TKN 351.1, 351.2 (Rev. 2.0)

Mercury 245.1 (Rev. 3.0), 245.2

Nitrate (as N) 352.1

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Nitrate-Nitrite (as N) 353.2 (Rev. 2.0 Aug 93)

Orthophosphate (as P) 365.1 (Rev. 2.0), 365.3

Osmium 252.2

Palladium 253.2

Phenols 420.1, 420.4 (Rev. 1.0)

Total Phosphorus 365.1, 365.3, 365.4

Platinum 255.2

Rhodium 265.2

Specific Conductance 120.1

Sulfate 375.2 (Rev. 2.0)

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Thallium 279.2

Titanium 283.2

Turbidity 180.1 (Rev. 2.0, Aug. 93)

Zinc 289.2

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MCAWW Methods withdrawn in Table IB

Acidity 305.1 Boron 212.3

Alkalinity 310.1 Bromide 320.1

Aluminum 202.1, 202.2 Cadmium 213.1, 213.2

Ammonia 350.2, 350.3 Calcium 215.1, 215.2

Arsenic 206.2, 206.3, 206.4 COD 410.1, 410.2

Barium 208.1, 208.2 Chloride 325.1, 325.2, 325.3

Beryllium 210.1, 210.2 Chlorine 330.1, 330.2, 330.3, 330.4, 330.5

BOD 405.1 Chromium VI

218.4

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Chromium Total

218.1, 218.2, 218.3 Gold 231.1

Cobalt 219.1, 219.2 Hardness 130.2

Color 110.1, 110.2, 110.3 Hydrogen ion (pH)

150.1

Copper 220.1, 220.2 Iridium 235.1

Cyanide 335.2, 335.3 Iron 236.1, 236.2

Available Cyanide

335.1 Kjeldahl nitrogen (TKN)

351.3, 351.4

Fluoride 340.1, 340.2, 340.3 Lead 239.1, 239.2

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Magnesium 242.1 TOC 415.1

Manganese 243.1, 243.2 Orthophosphate (as P)

365.2

Molybdenum 246.1, 246.2 Osmium 252.1

Nickel 249.1, 249.2 Oxygen, dissolved

360.1, 360.2

Nitrate-Nitrite (as N)

353.1, 353.3 Palladium 253.1

Nitrite (as N) 354.1 Phenols 420.2

Oil and Grease 413.1 Platinum 255.1

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Phosphorus – Total

365.2 Rhodium 265.1

Potassium 258.1 Ruthenium 267.1

Residue – Total 160.3 Selenium 270.2

Residue – Filterable

160.1 Silica 370.1

Residue – Nonfilterable

160.2 Silver 272.1, 272.2

Residue- settleable

160.5 Sodium 273.1

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Sulfate 375.1, 375.3, 375.4

Titanium 283.1

Surfactants 425.1 Vanadium 286.1, 286.2

Temperature 170.1 Zinc 289.1

Thallium 279.1

Tin 282.1, 282.2

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Approves a new method for determination of available cyanide by ligand exchange followed by flow injection analysis

ASTM 6888-04

Approves new methods for determination of total cyanide by ion selective electrode

SM 4500-CN- F (18th, 19th, and 20th editions) SM 4500-CN- F (2000) ASTM D2036-98 A

Office of Water


Approves new methods for determination of sulfide by ion selective electrode

SM 4500 – S2-G (18th, 19th, and 20th Editions)

ASTM D4658-03 (1996)

Approves a new method for determination of nitrate by ion selective electrode

SM 4500 – NO3- (18th, 19th, and 20th Editions)

SM 4500 – NO3- (2000)

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Approves the use of newer versions of 74 methods published by ASTM International

Approves the use of newer versions of 88 methods published by the Standard Methods Committee and adopts a new numbering system to track the approved methods

Approves the use of newer versions of 19 methods published by AOAC-International

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Approves the replacement of the mercuric sulfate catalyst with copper sulfate in methods approved for TKN

Approves the use of styrene divinyl benzene beads and stabilized formazin standard for determination of turbidity

Withdraws liquid-liquid extraction (LLE) methods including EPA method 612 and 625 for determination of 1,2-dichlorobenzene, 1,3- dichlorobenzene, and 1,4- di-chlorobenze

Office of Water


Adopting a new 136.6 to introduce greater flexibility in the use of approved methods

Approved methods may be modified by analysts without prior EPA approval provide that: The analyte measure is not “method-defined” The chemistry of the method or the determinative

techniques are not changed The performance meets specified performance

requirements and is documented

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Method Flexibility for Wastewater (continued) Potentially allowable changes include:

– Changes between automated and manual discrete instrumentation

– Changes in the calibration range (provided that the modified range covers any relevant regulatory limit)

– Changes in equipment, such as using similar equipment from a vendor other than that mentioned in the method

– Changes in equipment operating parameters, such as changing the monitoring wavelength of a colorimeter

– Increases in purge-and trap sample volumes– Use of salts and inert surfactants to improve recovery

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Revises Table II (Required Containers, Preservation Techniques, and Holding Times)

Updates to grab and composite sampling requirements to resolve inconsistencies

Raises the maximum holding temperature from 4o C to 6o C Revises preservation procedures for Cr(VI) and extends the

holding time from 24 hours to 28 days Suggests preserving metal samples in the lab Removes requirement for icing metal samples for shipment Updates holding time requirements based on new studies

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Revised Footnote 6 to Table II by adding text that describes procedures that are recommended for removal or suppression of cyanide interferences, including interferences from:

Sulfur Sulfide Sulfite Thiocyanate Aldehydes Carbonates Chlorine and Hypochlorite

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MUR Information

Summary of 40 CFR Part 141 and 143 Changes

SDWA Program

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MUR – 40 CFR Part 141 and 143 Changes

Allows the use of 66 methods in Standard Methods Online

Allows the use of 28 newer versions of methods published by ASTM international

Approves a new ATP for the determination of common anions – chloride, fluoride, nitrate, nitrite, orthophosphate, and sulfate

Waters Corporation Method D6508

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Approves two new methods for determination of available cyanide, “Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry”

Method OIA-1677 ASTM D6888-04

Approves the use of EPA method 300.1 (Rev. 1.0, 97) for compliance determinations of chloride, fluoride, nitrate, nitrite, orthophosphate, and sulfate

Office of Water


Approves the use of EPA Method 552.3 (Rev. 1.0, 03) for compliance determinations of dalapon

Adds a new method for determination of radium-226 and radium-228

Georgia Institute of Technology’s method for “The Determinaton of Radium-226 and Radium-228 in Drinking Water by Gamma-ray Spectrometry Using HPGE or Ge(Li) Detectors”

Office of Water


Allows States the option of approving ITS Free Chlorine Test Strips as a test kit for the measurement of free chlorine using free chlorine test strips

ITS Method D99-003 (Rev. 3.0, Nov 21, 2003)

Approves EPA Method 327.0 (Rev. 1.0, 2005) for measurement of chlorine dioxide residuals

Approves the use of styrene divinyl benzene beads and stabilized formazin as alternatives to the presently approved formazin standard for determination of turbidity

Office of Water


Revised footnote 17 to the table at 40 CFR 141.23 to allow the use of a 450-W UV lamp in the Kelada Method-01 for determination of cyanide

Allows the use of Syngenta Method AG-625, with the modified immunoassay testing product manufactured by Beacon Analytical Systems, for the measurement of atrazine under certain conditions

Only used by systems that do not use chlorine dioxide for drinking water treatment

The results of the analysis with concentrations more than one half the atrazine MCL must be confirmed using another approved method

Office of Water


Revised footnote 8 to the table in paragraph (a)(1) to correct a long-standing discrepancy between the footnote and the specifications in SM 9221 E Fecal Coliform monitoring

Corrects the holding time for the A-1 broth to match the 7-day holding time specified in the method

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MUR


Effluent Guideline

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MUR – Summary of 40 CFR 430 Changes

Amends the Effluent Limitations Guidelines for the pulp, paper, and paperboard point source category

Approves a new method for determination of chlorinated phenolics in wastewaters

Method CP-86.07 “Chlorinated Phenolics in Water by In situ Acetylation and GC/MS Determination” developed by the National Council for Air and Stream Improvement (NCASI)

Alternative to Method 1653

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MUR


Effluent Guideline

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Amends the regulations at 40 CFR Part 455 by moving Table 7 to 40 CFR Part 136.3 (a) as a new Table IG

There were requests to have the pesticide active ingredients methods in same place as other analytical methods

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MUR


Effluent Guideline

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Amends the Effluent Limitations for the coil coating point source category

The analytical method required for determination of petroleum hydrocarbons (non-polar material) is given under the listing for “oil and grease” at 40 CFR 136.3(a), Table IB, EPA Method 1664 A

Office of Water

Changes between the Proposed Rule and the Final Rule Silver

added footnote to Table IB on how to keep silver in solution, but is still withdrawing EPA Method 272.1

Approves an updated version of ASTM Method D5673-02 “Standard Test Method for Elements in Water by Inductively Coupled Plasma-Mass Spectrometry”

Ammoniaadded a footnote to Table IB allowing analysts to omit

EDTA from EPA Method 350.1

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Changes between the Proposed Rule and the Final Rule Cyanide

Problem with ligand exchange amperometric detection methods for samples with significant solids

added a footnote with suggestions for sample filtration and for limiting the time between addition reagents for samples with a lot of solids

Revised version of ASTM Method D6888-04Contains a new online sulfide removal procedure

Office of Water

Changes between the Proposed Rule and the Final Rule Kelada-01 Method for Determination of Available

Cyanide and Total CyanideAdded a footnote to allow the use of 450-W UV lamp

instead of the 550-W lamp specified in the method

Mandatory replacement of mercuric sulfate with copper sulfate in methods for the determination of TKNThe Agency has decided that it will continue to allow

the use of mercury sulfate in TKN analysis based on public comment

Office of Water

Changes between the Proposed Rule and the Final Rule Approval of Additional Standards for Turbidity

Determinations Replaced turbidity standard trade names with more generic

names in Table IB Added a footnote for turbidity in drinking water 40 CFR 141.74

Explicitly noted that the use of Capillary Columns may be used in EPA Methods 601-613, 624, 625, and 1624B

Allows the use of capillary columns in place of packed columns provided that all QC tests are met.

Clarifies retention times will change with the switch

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Changes between the Proposed Rule and the Final Rule Changes to Sampling Requirements at 40 CFR Part 122,

136, and 403 Based on comments, the Agency clarified language with respect

to grab and composite sampling requirements Added E. coli and Enterococci to the parameters listed at 122.21

Approval Status of Total Elements Digestion Based on comments, the Agency clarified language in Table IB

to specifiy Section 4.1.3 of MCAWW as the approved digestion procedure for use with non-platform graphite furnace atomic absorption determiantions

Office of Water

Changes between the Proposed Rule and the Final Rule EPA Method 245.7 for Determination of Mercury

Revised the method, Rev. 2.0, 2005Changes include:

–a discussion of the gas-liquid separator, – reduce the amount of HCl used during sample digestion,

–adds HCl to the standard solutions, –clarifies procedures for handling difficult matrices, – revises procedures for preparing reagent blanks to remove stannous chloride

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Changes between the Proposed Rule and the Final Rule Clarification of Reporting Requirements

EPA proposed to add 136.7 to clarify that a QC failure does not relieve a permittee to report results

Based on comments, EPA agrees that the section was not needed and revised the text at 136.3

Corrections to 40 CFR Part 136 Table IA to IF and footnotesAgency is correcting errors that were published in the

proposed tables

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Changes between the Proposed Rule and the Final Rule Revisions to 40 CFR Part 136 Table II

Revised footnote 1 to distinguish between polyethylene (P), fluoropolymer (FP), glass (G), and low-density polyethylene (LDPE)

Revised footnotes 2 and 7 to add language to make more clear that preservation must be within 15 minutes after collection of a grab sample, a composite sample, or an aliquot split

Revised footnote 4 to clarify the start of holding times Revised footnote 6 for cyanide interferences Clarified footnote 17 sampling for mercury Clarified footnote 18 to indicate the number of significant figures Deleted footnote 19, now included in footnote 5

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Changes between the Proposed Rule and the Final Rule Revisions to 40 CFR Part 136 Table II (continued)

Clarified that preservation is not required for soil and sediment Revised preservation requirements for acrolein, acrylonitrile,

and purgeable aromatics to remove inconsistencies Revised requirements for collection of samples to be tested for

Cryptosporidium and Giardia Corrected formatting and typographic errors

Corrections to Tables 40 CFR Part 141.23, 141.24, 141.25, and 141.74 and footnotes

Corrects errors and revised the wording of several entries for cyanide methods

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Changes between the Proposed Rule and the Final Rule Retention of Syngenta Method AG-625 for Determination

of Atrazine Agency proposed to withdraw this method, based on public

comment, EPA has decided to retain it with certain restrictions Requires confirmation of any compliance monitoring results for

atrazine that are greater than one half of the MCL Not authorized for public water systems that use chlorine

dioxide for drinking water treatment

Deferral of Action on Microtox® 1010 EPA is continuing to evaluate public comment and the data

supporting the use of this test procedure

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MUR – Response to Comments

EPA received over 100 comments on the proposal from: Wastewater and drinking water utilities Academics Industry or trade groups Method developers VCSBs State regulatory agencies Citizens

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MUR – Response to Comments

Significant areas of concern were: Cyanide distillation methods, particulate cyanides, and

interferences “Total recoverable” digestion for metals Withdrawal of older MCAWW methods Proposed use of Microtox EPA’s approach to approving modified methods Default QC and reporting requirements for new or revised

methods Withdrawal of Syngenta Method AG-625

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MUR – Frequently Asked Questions

What if I have a withdrawn method in my NPDES permit?

The primacy authority should allow use of methods in the permit for the life of the permit unless the authority exercises permits reopener procedures. This final rule does not withdraw any ATP approval that is tied to one of the withdrawn methods. The withdrawn methods have equivalent Part 136 methods published by VCSBs.

When will the wastewater –biosolids methods final rule be published?

This rule was signed on 9/28/06 and will be published within the next month.

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What is the deal with Cyanide? There have been a number of recommendations regarding

interferences and Cyanide determination. These interferences do not apply to all matrices and therefore you are not required to do the procedures outlined in Table IB, footnote 6. ASTM is currently writing a practice to deal with cyanide interferences.

What method am I suppose to use to determine Oil and Grease?

EPA Method 1664, Revision A: 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 is approved as part of EPA's effort to reduce dependency on use of chlorofluorocarbons (CFCs).

Office of Water


What does Method Flexibility mean? Allows the use of automatic discrete analyzers

Where can I get copies of these methods? There are references in the final rule for each of the methods EPA plans to post the methods on our website this year

If I found errors, what can I do? Send an email to us at [email protected]

Office of Water

MUR

Who can I contact if I have further questions?

Branch Chief – Dick Reding, [email protected] Inorganics – Lem Walker, [email protected] Organics- Brian Englert, [email protected] Biologicals – Robin Oshiro, [email protected] Rule Writer – Marion Kelly, [email protected] Rule Writer- Meghan Hessenauer,

[email protected]

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