2010 Proposed Methods Update Rule

1. 2010 Proposed Methods Update Rule Changes to 40 CFR Proposed in the September 23, 2010 Federal Register NRTC September 23, 2011

2. A Note on Reading the FR It is a newspaper of activities by all federal agencies It contains proposed rules, final rules, decisions, and notices It comes out every day that any federal agency has some item Is found on the web NRTC September 23, 2011

3. A Proposed or Final Rule Begins with a Preamble section Follows with the proposed or final changes to federal regulations – but only the changes not the full regulation The Preamble is where reasons for changes, examples, affected entities, and some federal “housekeeping” are provided NRTC September 23, 2011

4. A Warning on the Preamble All discussions, examples, and intentions are just that. They are not the actual rule The Preamble provides attorneys and others with the line of thinking that went into the changes It is not enforceable NRTC September 23, 2011

5. If it isn’t in the RegulationThen it doesn’t count! NRTC September 23, 2011

6. Affected Regulations 40CFR Part 136.1 through .7 Appendices A, C, and D 40CFR Parts 423, 430, and 435 40CFR Part 260 (RCRA) NRTC September 23, 2011

7. Changes to Part 136 Added missing EPA methods Changed how Standard Methods cited 250 new analytes Changes to Table II Changes to ATP process in 136.4 and 136.5 Changes to allowed methods modifications in 136.6 New section 136.7 on minimum QC Removed Appendices A and C Revise Appendix D (Precision/Accuracy) NRTC September 23, 2011

8. New EPA Methods Table IB 200.5 Trace Elements by Axially Viewed ICP-AES 1627 Prediction of Mine Drainage Quality Table IC 1614A Polybrominated Diphenyl Ethers (PBDE) by HRGC/HRMS. 1668C Polychlorinated Biphenyl Congeners (PCB) by HRGC/HRMS. Table IG 525.2, 608.1, 608.2, 614, 614.1, 617, 619, 622, 622.1, 632 NRTC September 23, 2011

9. Metals added to ICP & ICP/MS ICP/MS Gold, Iridium, Magnesium, Mercury, Palladium, Platinum, Potassium, Rhodium, Rhodium, Silica (Silicon), Sodium, Tin, and Titanium ICP/AES Mercury and Phosphorous NRTC September 23, 2011

10. Standard Methods Only most recent version approved Approved method cited by year approved by Standard Methods Example 9223-B-2004 for E. coli by enzyme substrate NRTC September 23, 2011

11. New Standard Methods 5520 B-2001 and 5520 F-2001 Oil and Grease. 5520 G-2001 not approved because it allows use of a co-solvent SM 3125-2009 ICP/MS for 24 metals NRTC September 23, 2011

12. Citation Changes = Problem Most hold print versions of Standard Methods and are use to finding methods by edition number Proposed citation best for the on-line version with costs an issue. Some methods not in any print edition Oldest method from 1990 while youngest from 2009 NRTC September 23, 2011

13. BOD 5210B - 2001 NRTC September 23, 2011

14. The Solution will be an Equivalency Table Table would equate approved version with first appearance in a print edition NRTC September 23, 2011

15. New Alternate Test Procedures Hach Method 10360 Luminescence Measurement of Dissolved Oxygen (LDO®), In-Situ Incorporated’s Method 1002-8 Dissolved Oxygen (DO), 1003-8 BOD, and 1004-8 CBOD NRTC September 23, 2011

16. Preservation and Hold Times Required unless approval of an alternative to the Table II instructions. The nature, timing and extent of the required documentation are left to the discretion of the permitting authority (State Agency or EPA Region) May rely on instructions, such as those provided for method modifications in 136.6. NRTC September 23, 2011

17. Holding Times and Sample Preservation Bacteria - change from 6+2 hours to 8 hours Cyanide - Footnotes 5 and 6 now reference ASTM Methods and allow flexibility WETT - No need to meet temperature if analyzed on day of collection NRTC September 23, 2011

18. Method Modifications: 136.6 Extensively rewritten with more examples 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 NRTC September 23, 2011

19. Examples Changes between manual method, flow analyzer and discrete instrumentation. Changes between automated and manual sample preparation. Use of interference reduction for ICP-MS. (Collision and Reaction cell technologies) Using a different acid to adjust pH in colorimetric methods. NRTC September 23, 2011

20. More Examples Changes in calibration model and the use of Relative Standard Error (RSE). Use of prepackaged reagents. Use of Selected Ion Monitoring (SIM). Changes in purge-and-trap sample volumes or operating conditions. Combine base/neutral and acid fractions for Method 625. NRTC September 23, 2011

21. There is a Warning! • Notify permitting authority and/or certification authority/accreditation body of the intent to use modified method • Notification in the form ‘‘Method xxx has been modified within the flexibility allowed in 40 CFR Part 136.6” • If performance in the wastewater matrix does not meet the QC acceptance criteria, the method modification may not be used. NRTC September 23, 2011

22. Uniform Quality Assurance Addition of section 136.7 and 12 Essential Elements NRTC September 23, 2011

23. Elements 1 - 4 • Demonstration of Capability (DOC); • Method Detection Limit (MDL); • Laboratory reagent blank (LRB), also referred to as method blank; • Laboratory fortified blank (LFB), also referred to as a spiked blank, or laboratory control sample (LCS); NRTC September 23, 2011

24. Elements 5 - 7 • Matrix spike, matrix spike duplicate, or laboratory fortified blank duplicate (LFBD) for suspected difficult matrices; • Internal standards, surrogate standards (for organic analysis) or tracers (for radiochemistry); • Calibration (initial and continuing), initial and continuing performance (ICP) solution also referred to as initial calibration verification (ICV) and continuing calibration verification (CCV); NRTC September 23, 2011

25. Elements 8 - 12 • Control charts (or other trend analyses of quality control results); • Corrective action (root cause analyses); • QC acceptance criteria; • Definitions of a batch (preparation and analytical); and • Specify a minimum frequency for conducting these QC checks. NRTC September 23, 2011

26. What Labs Must Do • These twelve quality control checks must be clearly documented in the written method along with a performance specification or description for each of the twelve quality control checks. NRTC September 23, 2011

27. Why is EPA Doing This? EPA proposing “essential” quality control with an approved method and when insufficient instructions are contained in the approved method Regardless of source of an analytical method analysts must use suitable QA/QC procedures. EPA expects that an analyst using these methods for reporting will also comply with the quality assurance and quality control requirements listed in the appropriate sections. NRTC September 23, 2011

28. What EPA Did Not Do Stipulate the source for missing elements listed in section 136.7.a Set any criteria or standards for any quality system function if not stated in the selected source Set any allowed exceptions or how to determine if an element in 136.7.a does not apply. NRTC September 23, 2011

29. Methods Update Rule The bottom line

30. The Important Changes • Changes how Standard Methods… methods are cited • Adds and enhances allowed alteration procedures for both methods and holding times • Adds a uniform framework for quality assurance/quality control for methods NRTC September 23, 2011

31. Important Things for You • Go over all methods you use that are from Standard Methods… and verify the approval date – Update as necessary • Begin rewriting your method SOPs and incorporate the 12 QA elements from 136.7 NRTC September 23, 2011

32. Need a Copy of the Proposed Rule? E-mail bray@waterboards.ca.gov Put MUR2 in the subject line

33. Bill RayQuality Assurance Program ManagerState Water Resources Control Board bray@waterboards.ca.gov