Overview CWA Methods Update Rule Method 608.3 August 2017 • Adrian Hanley, U.S. EPA

Methods Update Rule (MUR) CWA MUR every 3-5 years Previous CWA MUR finalized in 2012 Current CWA MUR Proposed February 19, 2015 175 sets of comments received OMB Found the rule not significant under Executive Order 12866 on April 13, 2016 Originally signed on December 15, 2016 Withdrawn from the FR, being reconsidered Not significant means neither financially significant nor controversial

Action Development Process for the MUR Rule proposed and comments received Respond to comments Modifications for final rule may occur Internal Review of Final Rule Multi-office EPA workgroup including Office of General Counsel and Office of Policy Rule finalized, signed by Administrator Becomes effective upon publication Important Note: When finalizing a rule, items from the proposed rule are generally accepted, rejected, or modified. New items outside of the scope of the proposed rule are generally not added to the final rule. Followed the Action Development Process (ADP).

Methods 608.3, 624.1, and 625.1 Pesticides and PCBs, volatile and semivolatile organic compounds Revision – made limited changes: Updated technology Capillary columns, updated references Method Flexibility Allows more changes with internal documentation (no ATP required) Follow 40 CFR Part 136.6 Method Harmonization Enhances consistency among EPA method programs: drinking water, solid-waste, superfund Three revised EPA Methods: 624 and 625 (volatile and semivolatile organic compounds) and 608 (Pesticides and PCBs) Have not been revised since promulgation in 1984 Laboratory stakeholders asked for a long overdue revision of these methods. Revisions reflect collaboration with other EPA program offices, EPA regions, technology vendors, states, and laboratory organizations in a multi-year process via workgroup before proposal Revisions incorporate: Technology updates that have occurred in the more than thirty years since these were originally promulgated Harmonization with similar methods in other EPA offices (e.g., frequency of QC testing, calibration criteria, etc…) in order to reduce the workload at laboratories that run methods for multiple EPA programs Primary comments: (1) Comments in support of the overall revisions, (2) Many highly varied comments regarding minor technical details – some resulted in minor revisions, (3) Many requests to tighten published QC limits and lower published detection limits, which would require a multi-laboratory study

Method 608 to 608.3 Underwent 2 rounds of review before proposal EPA Regions then select reviewers Proposed Rule in 2015 Received 210 pages of tabulated comments Resulted in many minor revisions Current Version of 608.3 Pre-publication available at: https://www.epa.gov/cwa-methods/methods-update-rule-2016

Disclaimer The following slides are only a summary of the changes made from Method 608 to Method 608.3. The slides do not contain every single change, just the changes that this presenter believes are most significant.

Additional Analytes Table 2: Additional Analytes New analytes not approved under 40 CFR part 136 Intended for analytes of interest (see 1.4) Cost savings for dischargers Initial Demonstration of Capability required Default MS/MSD recovery of 60-140% and RPD of 30%, unless tighter in house criteria are available (see 8.1.2.1.2) Aroclors and Toxaphene Moved to Table 2 Not required for QC tests (see 1.5) 1.4 The large number of analytes in Tables 1 and 2 makes testing difficult if all analytes are determined simultaneously. Therefore, it is necessary to determine and perform quality control (QC) tests for the “analytes of interest” only. The analytes of interest are those required to be determined by a regulatory/control authority or in a permit, or by a client. If a list of analytes is not specified, the analytes in Table 1 must be determined, at a minimum, and QC testing must be performed for these analytes. The analytes in Table 1 and some of the analytes in Table 2 have been identified as Toxic Pollutants (40 CFR 401.15), expanded to a list of Priority Pollutants (40 CFR part 423, appendix A). 1.5 … Toxaphene and the PCBs have been moved from Table 1 to Table 2 (Additional Analytes) to distinguish these analytes from the analytes required in quality control tests (Table 1). QC acceptance criteria for Toxaphene and the PCBs have been retained in Table 4 and may continue to be applied if desired, or if these analytes are requested or required by a regulatory/control authority or in a permit. …

Calibration Recommend 5 standards for single component analytes (minimum of 3 standards) Calibration curve can be used Consistent with 40 CFR part 136.6 6 standards are required for curve fits and relative standard error calculations Aroclors Minimum of 3 standards containing both Aroclor 1016 and 1260 Single midpoint standards of the other 5 Aroclors Toxaphene Minimum of 3 standards

QC Changes Can repeat failed QC tests for failed analytes Only when many analytes are analyzed, and 80% of the analytes pass No maintenance or adjustments in between Calibration Verification Standards (see 6.8.4) Prepared using standards obtained from a second source Note: Second source standards are optional for MS/MSD and LCS samples (see 6.8.3)

QC Changes (cont.) Surrogates are required Examples: dibutyl chlorendate (DBC), tetrachloro-m-xylene (TCMX), 4,4'-dibromobiphenyl, or decachlorobiphenyl Alternative surrogates and concentrations allowed Blanks are reported to the MDL GC resolution criteria added (see 13.4) Valley height 40% of the shorter peak DDT and Endrin decomposition criteria added Breakdown <20% (see 13.5)

Extraction/Cleanup Additional procedures for continuous liquid-liquid extraction (CLLE) and disk based solid phase extraction (SPE) CLLE is essentially an automated liquid-liquid extraction, which is allowed under 40 CFR part 136.6 Disk based SPE is based on an approved alternate test procedure (60 FR 39585, August 2, 1995) More cleanup procedures are provided Always have been allowed under method flexibility Contained within “Solutions to Analytical Chemistry Problems with Clean Water Act Methods”

New Allowed Modifications New materials can be vendor certified by one laboratory (see 8.1.2.1.1) Most relevant to solid phase extraction Requires an Initial Demonstration of Capability Requires testing in specified 9 matrix types (see 8.1.2.1.2) Must meet Table 4 MS/MSD criteria Default criteria if no Table 4 data available 60 to 140% recovery and 30% RPD Full data packages must be made available, and kept by the laboratories using the new materials (see 8.1.2.2)

Common Comments Remove 5% MS/MSD frequency requirement for each discharge site Not a significant change, 608 requires 10% frequency Reviewed and approved by the Science Advisory Board during original promulgation in 1984 Proposed MDLs are invalid MDL were changed back to original values Do not reference unapproved methods Only referenced in the context of analytical trouble shooting

Common Comments (cont.) Require 5 calibration standards Change “Fill in the blank” criteria Need a multi-lab validation Criteria were taken from a different EPA method program, so it is fostering method harmonization EPA should not allow reporting to the MDL That is the decision of the permitting authority

For more information or additional feedback, please contact: Contact Information For more information or additional feedback, please contact: Adrian Hanley, US EPA Office of Water Office of Science and Technology 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.