Office of Water Changes to Water Regulations Methods Update Rule Meghan Hessenauer Office 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

Office of Water Summary of Final Rule

Office of Water MUR Timeline March 12, 2007 Final Rule August 18, 2003 Proposed Rule April 6, 2004 Proposed Rule February 16, 2005 NODA

Office of Water 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of currently approved methods  Revisions to method modification and analytical requirements  Withdrawal of certain outdated methods  Changes to sample collection, preservation, and holding time requirements

Office of Water 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

Office of Water MUR Summary  This Rule will provide:  More choices of methods  More flexible methods  Easier to modify methods without prior approval

Office of Water MUR Information How do I get more information? Docket ID EPA-HQ-OW HQ Water Docket Center

Office of Water MUR - Applicability Who has to comply with these regulations?  Entities with NPDES permits  Entities that analyze water in accordance with the SDWA

Office of Water MUR Information Summary of 40 CFR Part 122 Changes NPDES Program

Office of Water 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

Office of Water MUR Information Summary of 40 CFR Part 136 Changes CWA Program

Office of Water MUR – Summary of 40 CFR Part 136 Changes  EPA approved three new chemical methods submitted as Alternative Test Procedures (ATPs)  Waters Corporation Method D6508 for determination of anions by capillary ion electrophoresis  Lachat QuikChem Method X for determination of total cyanide using MICRODIST  Kelada-01 method for determination of total and available cyanide using UV-digestion, flash distillation and colorimetry

Office of Water MUR – Summary of 40 CFR Part 136 Changes  Approves a broad digestion procedure for total recoverable elements  EPA Method (Revision 2.8, 1994) for use with ICP-AES, ICP-MS, STGFAA, and FLAA  Approves three new multi-element test procedures EPA Method (Revision 5.4, 1994)  AOAC Method (16 th Edition)  ASTM D for determination of elements by ICP- MS

Office of Water MUR – Summary of 40 CFR Part 136 Changes  Approves a new multi-element test procedure  EPA Method (Revision 2.2, 1994) for determination of elements by STGFAA.  Approves four new methods for determination of hexavalent chromium by ion chromatography  EPA Method  AOAC Method (16 th Edition)  ASTM D  SM 3500-Cr C (20 th Edition) and SM 3500-Cr E (18 th and 19 th Editions)

Office of Water MUR – Summary of 40 CFR Part 136 Changes  Approves five new methods for determination of anions by ion chromatography  EPA Method (Revision 2.1, 1993)  EPA Method (Revision 1.0, 1997)  AOAC Method (16 th Edition)  ASTM D4327  SM 4110 B (18 th, 19 th, and 20 th Editions)  Approves automated cadmium reduction methods to determine nitrate and nitrite individually, as well as in combination  EPA Method (Revision 2.0, 1993)  ASTM D A and B  SM NO 3 – E and F (18 th, 19 th, and 20 th Editions)  SM 4500-NO 3 – E and F (2000)  USGS Method I

Office of Water MUR – Summary of 40 CFR Part 136 Changes  Approves a new method for determination of chlorine by low level amperometry – SM 4500-Cl E (18 th, 19 th, 20 th Editions) and SM 4500-Cl E (2000)  Approves a new method for determination of cations by ion chromatography, ASTM D  Approves a new method for determination of chloride by potentiometry, SM 4500-Cl - D (18 th, 19 th, 20 th Editions) and SM 4500-Cl - D(2000)  Approves a new method for determination of chloride by ion selective electrode, ASTM D (1999)

Office of Water MUR – Summary of 40 CFR Part 136 Changes  Approves EPA Method 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 as an alternative to EPA Method 1631  Both methods use CVAFS and allow for trace analysis of mercury; however, EPA Method 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%

Office of Water MUR – Summary of 40 CFR Part 136 Changes  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

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods retained in Table IB Alkalinity310.2 Ammonia350.1 (Rev. 2.0 Aug 93) Arsenic206.5 COD410.3, Gold231.2 Total Hardness130.1 Iridium235.2 TKN351.1, (Rev. 2.0) Mercury245.1 (Rev. 3.0), Nitrate (as N)352.1

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods retained in Table IB Nitrate-Nitrite (as N)353.2 (Rev. 2.0 Aug 93) Orthophosphate (as P)365.1 (Rev. 2.0), Osmium252.2 Palladium253.2 Phenols420.1, (Rev. 1.0) Total Phosphorus365.1, 365.3, Platinum255.2 Rhodium265.2 Specific Conductance120.1 Sulfate375.2 (Rev. 2.0)

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods retained in Table IB Thallium279.2 Titanium283.2 Turbidity180.1 (Rev. 2.0, Aug. 93) Zinc289.2

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods withdrawn in Table IB Acidity305.1Boron212.3 Alkalinity310.1Bromide320.1 Aluminum202.1, 202.2Cadmium213.1, Ammonia350.2, 350.3Calcium215.1, Arsenic206.2, 206.3, 206.4COD410.1, Barium208.1, 208.2Chloride325.1, 325.2, Beryllium210.1, 210.2Chlorine330.1, 330.2, 330.3, 330.4, BOD405.1Chromium VI 218.4

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods withdrawn in Table IB Chromium Total 218.1, 218.2, 218.3Gold231.1 Cobalt219.1, 219.2Hardness130.2 Color110.1, 110.2, 110.3Hydrogen ion (pH) Copper220.1, 220.2Iridium235.1 Cyanide335.2, 335.3Iron236.1, Available Cyanide 335.1Kjeldahl nitrogen (TKN) 351.3, Fluoride340.1, 340.2, 340.3Lead239.1, 239.2

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods withdrawn in Table IB Magnesium242.1TOC415.1 Manganese243.1, 243.2Orthophosphate (as P) Molybdenum246.1, 246.2Osmium252.1 Nickel249.1, 249.2Oxygen, dissolved 360.1, Nitrate-Nitrite (as N) 353.1, 353.3Palladium253.1 Nitrite (as N)354.1Phenols420.2 Oil and Grease413.1Platinum255.1

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods withdrawn in Table IB Phosphorus – Total 365.2Rhodium265.1 Potassium258.1Ruthenium267.1 Residue – Total160.3Selenium270.2 Residue – Filterable 160.1Silica370.1 Residue – Nonfilterable 160.2Silver272.1, Residue- settleable 160.5Sodium273.1

Office of Water MUR – Summary of 40 CFR Part 136 Changes  MCAWW Methods withdrawn in Table IB Sulfate375.1, 375.3, Titanium283.1 Surfactants425.1Vanadium286.1, Temperature170.1Zinc289.1 Thallium279.1 Tin282.1, 282.2

Office of Water MUR – Summary of 40 CFR Part 136 Changes  Approves a new method for determination of available cyanide by ligand exchange followed by flow injection analysis  ASTM  Approves new methods for determination of total cyanide by ion selective electrode  SM 4500-CN - F (18 th, 19 th, and 20 th editions)  SM 4500-CN - F (2000)  ASTM D A

Office of Water MUR – Summary of 40 CFR Part 136 Changes  Approves new methods for determination of sulfide by ion selective electrode  SM 4500 – S 2 - G (18 th, 19 th, and 20 th Editions)  ASTM D (1996)  Approves a new method for determination of nitrate by ion selective electrode  SM 4500 – NO 3 - (18 th, 19 th, and 20 th Editions)  SM 4500 – NO 3 - (2000)

Office of Water MUR – Summary of 40 CFR Part 136 Changes  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

Office of Water MUR – Summary of 40 CFR Part 136 Changes  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 MUR – Summary of 40 CFR Part 136 Changes  Adopting a new 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

Office of Water MUR – Summary of 40 CFR Part 136 Changes  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

Office of Water MUR – Summary of 40 CFR Part 136 Changes  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 4 o C to 6 o 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

Office of Water MUR – Summary of 40 CFR Part 136 Changes  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

Office of Water MUR Information Summary of 40 CFR Part 141 and 143 Changes SDWA Program

Office of Water 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

Office of Water MUR – 40 CFR Part 141 and 143 Changes  Approves two new methods for determination of available cyanide, “Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry”  Method OIA-1677  ASTM D  Approves the use of EPA method (Rev. 1.0, 97) for compliance determinations of chloride, fluoride, nitrate, nitrite, orthophosphate, and sulfate

Office of Water MUR – 40 CFR Part 141 and 143 Changes  Approves the use of EPA Method (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 MUR – 40 CFR Part 141 and 143 Changes  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 D (Rev. 3.0, Nov 21, 2003)  Approves EPA Method (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 MUR – 40 CFR Part 141 and 143 Changes  Revised footnote 17 to the table at 40 CFR 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 MUR – 40 CFR Part 141 and 143 Changes  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

Office of Water MUR Summary of 40 CFR Part 430 Changes Effluent Guideline

Office of Water 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 “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

Office of Water MUR Summary of 40 CFR Part 455 Changes Effluent Guideline

Office of Water MUR – Summary of 40 CFR Part 455 Changes  Amends the regulations at 40 CFR Part 455 by moving Table 7 to 40 CFR Part (a) as a new Table IG  There were requests to have the pesticide active ingredients methods in same place as other analytical methods

Office of Water MUR Summary of 40 CFR Part 465 Changes Effluent Guideline

Office of Water MUR – Summary of 40 CFR Part 465 Changes  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  Approves an updated version of ASTM Method D “Standard Test Method for Elements in Water by Inductively Coupled Plasma-Mass Spectrometry”  Ammonia  added a footnote to Table IB allowing analysts to omit EDTA from EPA Method 350.1

Office of Water 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 D  Contains 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 Cyanide  Added 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 TKN  The 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  Explicitly noted that the use of Capillary Columns may be used in EPA Methods , 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

Office of Water 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  Approval Status of Total Elements Digestion  Based on comments, the Agency clarified language in Table IB to specifiy Section 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 for Determination of Mercury  Revised the method, Rev. 2.0, 2005  Changes 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

Office of Water Changes between the Proposed Rule and the Final Rule  Clarification of Reporting Requirements  EPA proposed to add 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  Corrections to 40 CFR Part 136 Table IA to IF and footnotes  Agency is correcting errors that were published in the proposed tables

Office of Water 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

Office of Water 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 , , , and and footnotes  Corrects errors and revised the wording of several entries for cyanide methods

Office of Water 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

Office of Water 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

Office of Water 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

Office of Water 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.

Office of Water MUR – Frequently Asked Questions  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 MUR – Frequently Asked Questions  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 to us at

Office of Water MUR  Who can I contact if I have further questions?  Branch Chief – Dick Reding,  Inorganics – Lem Walker,  Organics- Brian Englert,  Biologicals – Robin Oshiro,  Rule Writer – Marion Kelly,  Rule Writer- Meghan Hessenauer,