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Changes to Water Regulations Methods Update Rule

Changes to Water Regulations Methods Update Rule. Meghan Hessenauer Office of Science and Technology March 2007. Methods Update Rule (MUR) .

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Changes to Water Regulations Methods Update Rule

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  1. Changes to Water RegulationsMethods Update Rule Meghan Hessenauer Office of Science and Technology March 2007

  2. 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

  3. Summary of Final Rule

  4. MUR Timeline

  5. 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of currently approved methods • Revisions to method modification and analytical requirements • Withdrawal of certain outdated methods • Changes to sample collection, preservation, and holding time requirements

  6. 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

  7. MUR Summary • This Rule will provide: • More choices of methods • More flexible methods • Easier to modify methods without prior approval

  8. 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

  9. MUR - Applicability Who has to comply with these regulations? • Entities with NPDES permits • Entities that analyze water in accordance with the SDWA

  10. MUR Information Summary of 40 CFR Part 122 Changes NPDES Program

  11. 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

  12. MUR Information Summary of 40 CFR Part 136 Changes CWA Program

  13. 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 10-204-00-1-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

  14. MUR – Summary of 40 CFR Part 136 Changes • Approves a broad digestion procedure for total recoverable elements • EPA 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

  15. MUR – Summary of 40 CFR Part 136 Changes • Approves a new multi-element test procedure • EPA Method 200.9 (Revision 2.2, 1994) for determination of elements by STGFAA. • Approves four new methods for determination of hexavalent chromium by ion chromatography • EPA Method 218.6 • AOAC Method 993.23 (16th Edition) • ASTM D5257-97 • SM 3500-Cr C (20th Edition) and SM 3500-Cr E (18th and 19th Editions)

  16. MUR – Summary of 40 CFR Part 136 Changes • 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 D4327 • SM 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 B • SM 4500- NO3– E and F (18th, 19th, and 20th Editions) • SM 4500-NO3–E and F (2000) • USGS Method I-4545-85

  17. MUR – Summary of 40 CFR Part 136 Changes • 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)

  18. MUR – Summary of 40 CFR Part 136 Changes • 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%

  19. 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

  20. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods retained in Table IB

  21. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods retained in Table IB

  22. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods retained in Table IB

  23. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods withdrawn in Table IB

  24. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods withdrawn in Table IB

  25. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods withdrawn in Table IB

  26. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods withdrawn in Table IB

  27. MUR – Summary of 40 CFR Part 136 Changes • MCAWW Methods withdrawn in Table IB

  28. 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 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

  29. MUR – Summary of 40 CFR Part 136 Changes • 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)

  30. 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

  31. 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

  32. MUR – Summary of 40 CFR Part 136 Changes • 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

  33. 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

  34. 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 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

  35. 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

  36. MUR Information Summary of 40 CFR Part 141 and 143 Changes SDWA Program

  37. 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

  38. 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 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

  39. MUR – 40 CFR Part 141 and 143 Changes • 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”

  40. 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 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

  41. MUR – 40 CFR Part 141 and 143 Changes • 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

  42. 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

  43. MUR Summary of 40 CFR Part 430 Changes Effluent Guideline

  44. 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

  45. MUR Summary of 40 CFR Part 455 Changes Effluent Guideline

  46. MUR – Summary of 40 CFR Part 455 Changes • 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

  47. MUR Summary of 40 CFR Part 465 Changes Effluent Guideline

  48. 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

  49. 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” • Ammonia • added a footnote to Table IB allowing analysts to omit EDTA from EPA Method 350.1

  50. 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 D6888-04 • Contains a new online sulfide removal procedure

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