1. Clean Water Act Methods Overview of EPA’s CWA Method Activities
August 2018• Adrian Hanley, U.S. EPA

2. CWA Analytical Methods Program
Many industries and municipalities are permitted to discharge pollutants under the CWA NPDES
They use analytical methods to analyze the chemical, physical, and biological components of wastewater and other environmental samples for monitoring compliance
CWA requires EPA, through rulemaking, to establish test procedures to measure pollutants for CWA programs
EPA promulgates test procedures in 40 CFR Part 136

3. Method Update Rule (MUR)
2017 Clean Water Act Methods Update Rule for the Analysis of Effluent
Proposed February 19, 2015
175 sets of comments received
Final rule published August 28, 2017
Effective September 27, 2017

4. 2017 MUR Summary
Proposed ~100 method revisions from ASTM International and Standard Methods
6 Alternate Test Procedures (ATPs)
1 USGS Method (based off of an ATP)
Whole Effluent Toxicity Manual Erratta
Revisions to Methods 608, 624, and 625
Method Detection Limit (MDL) Revision
The method revisions are minor changes/updates to methods that are already in 40 CFR 136.  They usually are wording changes and small additions or clarifications to the method.  They do not contain any significant procedural changes or changes to the QC requirements.  For instance, ASTM Standard D will likely be changed to the more updated version D0516 – 2011.
Alternate testing procedures are typically submitted by vendors who would like to approve a new technology to be used as part of a method already in 40 CFR 136.  These applications are throughly reviewed by my division’s Alternate Testing Procedure Program.  The applications usually require that the technology is tested in 9 matrices at 9 different laboratories before they are approved (less testing is required for technologies that are only applying for use in one industry). 
The revision to the Method Detection Limit (Appendix B of 40 CFR 136) was submitted by the NELAC institute.  It has already been reviewed and revised extensively by my office, and a few hundred other people from EPA, laboratory organizations, states, and industry.  It is a small addition to the current procedure that adds a step to account for laboratory contamination.

5. Future MURs
Plan to propose and finalize Method Update Rules more frequently
Smaller rules
Less wait time for revisions, ATPs, corrections
A “Routine MUR” every 1-2 years
Routine MURs will contain non-controversial items
Non-routine MURs will contain more contentious items and be proposed separately and less frequently

6. 2018 Routine MUR Next routine MUR proposal - late 2018 Will include
Voluntary Consensus Standard Body (VCSB) method revisions and submittals
Alternate Test Procedures (ATPs)
Corrections and clarifications
Data was due May 30th

7. CWA Microbiology Method Activities
Coliphage culture methods
Male-specific and somatic coliphage
Validated in recreational waters and wastewater
Methods and study report finalized
Anticipate web posting soon
Coliphage = bacterial virus
The coliphage method includes male specific and somatic.

8. CWA Microbiology Method Activities
Microbial source tracking molecular methods
OW and ORD collaboration
Rapid Methods
Human specific targets
Completed multi-laboratory validation study for recreational waters (fresh and marine)
Methods and study report forthcoming
Coliphage = bacterial virus
The coliphage method includes male specific and somatic.

9. CWA Chemistry Method Activities
Peracetic acid and hydrogen peroxide methods
Continuous monitoring – total residual chlorine
PCB congener method
ATP reviews
Update QC Criteria for Methods 608.3, 624.1, and 625.1

10. Peracetic Acid and H2O2 Alternative antimicrobial
Almost no residual – unlike chlorine
Byproducts: hydrogen peroxide and acetic acid
Already in use at some POTWs
Method must be performed onsite
Degrades quickly
Halted EPA efforts after reviewing Standard Methods Draft Methods
Currently Collaborating with the Standard Methods Joint Editorial Board
Multi-lab validation in progress

11. Continuous Monitoring
Total residual chlorine pilot study
Based on EPA Drinking Water Method 334.0
Recruited POTWs to generate side-by-side data for monitors and an onsite lab
One POTW currently compiling data packages
Next steps may include a multi-utility study

12. PCB Congener Method Single-laboratory validation goals:
Identifies and quantifies PCB contamination using individual congeners
Improves sensitivity over Method 608, less sensitive to typical laboratory background
Implementable at a typical mid-sized full-service environmental laboratory
Single-laboratory testing completed
Study report finalized, draft method revised

13. PCB Congener Method cont.
Quantification
29 carbon-13 isotope dilution standards
Calibration of 48 congeners
Other 161 congeners quantified indirectly
Extraction
Tested 2 SPE procedures and 1 LLE procedure
Tested Soxhlet extraction for biosolids, sediment, and fish tissue
Sensitivity
Aqueous MDL generally 0.2 to 1.5 ng/L (except mono chloro congeners)

14. Method Detection Limit Study Aqueous Samples
Method detection limits (MDLs) were determined using EPA’s recently revised MDL procedure. Both the MDLb and MDLs were determined.
MDL values varied by congener and extraction technique, but generally ranged from approximately 0.06 to 2.37 ng/L.
For the separatory funnel procedure, none of the method blank aliquots contained any of the congeners and therefore, MDLb could not be calculated.
For the cartridge-based SPE procedure, only PCB was present at a level that allowed the calculation of MDLb.
For the disk-based SPE procedure, 83 of the 167 congeners or groups of coeluting congeners were present in the blanks at levels that allowed the calculation of MDLb. However, in all of those instances, the MDLb value was less than the MDLs value, and the revised MDL procedure instructs the user to select the greater of the two values as the detection limit to be used. Therefore, none of the calculated MDLb values affected the final MDL.
An MDLs could not be determined for certain congeners (PCB-1, PCB-3, PCB-11, PCB-12/13, PCB-14, PCB-81, and PCB-157) due to failing qualitative identification criteria (i.e., ion abundance ratio failures). A higher spiking level may resolve the ion abundance ratio concerns.
By and large, the MDLs values from the separatory funnel extraction are lower than those for either the cartridge-based or disk-based solid-phase extraction.

15. PCB Congener Method cont.
Aqueous Mean Matrix Spike Recovery

16. PCB Congener Method cont.
Aqueous Min/Max Matrix Spike Recovery

17. Completed QAPP and Study Plan Current Efforts:
PCB Multi-Lab Study
Completed QAPP and Study Plan
Current Efforts:
Order mixed standards for multi-laboratory validation
Obtain, homogenize, and test validation matrices
Recruit laboratories, both contracted (paid) and volunteer
Contracting laboratories this fall!

18. ATP Reviews
Alternate test procedures (ATPs) for nationwide use are submitted to EPA HQ for review
Codified at 40 CFR and 136.5
Protocols for EPA review of alternate test procedures and new methods are available at:
Deadline for 2018 MUR was May,
Next MUR likely 2020
The Clean Water Act Alternate Test Procedure (ATP) program is described at 40 CFR and This program provides a mechanism for submission and review of an application for nationwide use or limited use of an ATP for measurement of a pollutant as an alternative to the methods approved at 40 CFR Part 136. An ATP may fall into one of two categories:
A method using a determinative technique (e.g., a pollutant detector) different from that in an existing Part 136 method (for method validation and evaluation purposes this type of method is referred to as a new method), or
A modification to a Part 136 method that falls outside the scope of the modification flexibility described in the Part 136 method, or at 40 CFR (for validation and evaluation purposes this type of method is referred to as an ATP).
A method developer may apply for review of a method modification or a new method through the ATP program.

19. 608.3, 624.1, 625.1
QC Criteria Update
TNI, ACIL, APHL, and WEF have volunteered to provide data to update QC criteria
Initial calibration, MDLs, calibration verification, ongoing precision and recovery, MS/MSD
Secondary Data Collection
Use existing data anonymously
Volunteer laboratories
Perform NPDES compliance monitoring
Have an SOP and formal quality system
Coordinate with laboratory associations

20. QC Criteria Update cont.
Schedule – FY18
Draft and finalize Secondary data collection QAPP and Study Plan
Receive external review
Schedule – FY19 and 20
Review and compile data
EDD and supporting documentation
Include all data, including any that failed current QC criteria
Statistical Analysis
Draft and finalize study report
Rulemaking to update QC criteria

21. For more information or additional feedback, please contact:
Contact Information
For more information or additional feedback, please contact:
Adrian Hanley, US EPA
CWA Method Team Leader Office of Science and Technology Office of Water
Phone:
Does anyone have any questions, comments, or feedback?
If you have additional comments or would like to provide feedback on the issues raised in this presentation, please feel free to contact me.