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

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

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 https://www.epa.gov/cwa-methods/methods-update-rule-2017

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 D0516 - 2007 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.

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

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 https://www.epa.gov/cwa-methods/methods-update-rule-2018

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 https://www.epa.gov/cwa-methods Coliphage = bacterial virus The coliphage method includes male specific and somatic.

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.

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

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

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

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

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)

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-105+127 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.

PCB Congener Method cont. Aqueous Mean Matrix Spike Recovery

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

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!

ATP Reviews Alternate test procedures (ATPs) for nationwide use are submitted to EPA HQ for review Codified at 40 CFR 136.4 and 136.5 Protocols for EPA review of alternate test procedures and new methods are available at: https://www.epa.gov/cwa-methods/alternate-test-procedures Deadline for 2018 MUR was May, 30 2018 Next MUR likely 2020 The Clean Water Act Alternate Test Procedure (ATP) program is described at 40 CFR 136.4 and 136.5. 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 136.6 (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.

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

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

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: 202-564-1564 E-Mail: hanley.adrian@epa.gov 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.