EPA/RVIPA 31st ANNUAL PRETREATMENT WORKSHOP Method Update Rule and Sufficiently Sensitive Methods Rule: What You Need to Know 6 August 2015 Fort Worth, TX Dr. Paul N. Boothe Senior Scientist Albion Environmental Bryan, TX
PRESENTATION OUTLINE Analytical Method Compliance- Why should you care? New R6 & States MALs ups the ante Sufficiently Sensitive Test Methods (SSTM) Rule 2015 Methods Update Rule (MUR) Conclusions
Importance of Method Compliance DMR Certification: CERTIFY UNDER PENALTY OF LAW THAT THE INFORMATION SUBMITTED IS, TO THE BEST OF MY KNOWLEDGE AND BELIEF, TRUE, ACCURATE, AND COMPLETE. Responsibility for analytical method compliance: it is the discharger s responsibility to make sure that the requirements in EPA Method 1631 are followed, that all QC is performed, and that all QC acceptance criteria are met Guidance for Implementation and Use of EPA Method 1631 for the Determination of Low-Level Mercury (40 CFR part 136). EPA 821-R-01-023. March 2001. Pg 5-12
Importance of Method Compliance The importance of QA and following QA and requiring labs to follow QA is a compliance requirement in the permit standard conditions under NPDES regs 40 CFR 122.41(e) so each NPDES permit requires it as a permit condition (e) Proper operation and maintenance. Proper operation and maintenance also includes adequate laboratory controls and appropriate quality assurance procedures.
Importance of Method Compliance NELAP Accreditation is NO GUARANTEE of Method Compliance Misinterpretation of method requirements including QC by labs and assessors NELAP standards NOT specifically require lab to follow a method Method flexibility 40 CFR 136 (MUR 2012) Naïve to assume NELAP accreditation means it is safe to blindly accept lab data without any knowledge of method QA/QC requirements How many permittees validate data submitted?
Importance of Method Compliance Want accurate (defensible) data can rely on Non-compliant data increases likelihood of inaccurate, non-representative, indefensible data Bad data wastes resources (e.g. re-sampling) and can lead to costly erroneous decisions Spend money on problems that don t really exist Knowledge of the methods and compliance with method requirements is the best way to get the most accurate and usable data Validate, validate, validate
Importance of Method Compliance AVOID treating test data as a commodity Per sample cost alone often NOT a good metric Especially for newer methods where labs have limited experience such as working at new MALs RFQ versus RFP Best approach- Use TESTING AGREEMENT TEMPLATES for lab services procurement Make you an instant expert on method reqs. Specify all sampling, analysis & reporting reqs. Allow apples to apples comparisons of labs Insure obtain data you need & can validate
R6 & States Reporting Limits (ppb) ELEMENT R6 MQL TX MAL OK RL NM MQL LA RL AR RL Ag 0.5 0.5 2 0.5 0.5 0.5 Al 2.5 2.5 2.5 As 0.5 0.5 10 0.5 5 0.5 Be 0.5 0.5 5 0.5 0.5 0.5 Cd 1 1 1 1 1 0.5 Cr 3 3 10 10 10 10 Cu 0.5 2 10 0.5 3 0.5 Hg 0.005 / 0.0005 0.005/0.0005 0.2 0.0005 0.005 0.005 Ni 0.5 2 40 0.5 5 0.5 Pb 0.5 0.5 5 0.5 2 0.12 Sb 5 5 60 60 60 60 Se 5 5 5 5 5 5 Tl 0.5 0.5 10 0.5 0.5 0.5 Zn 5 5 20 20 20 20
EPA Sufficiently Sensitive Test Method (SSTM) Rule- What is it? Considered minor amendment to CWA Codify that NPDES permittees must use sufficiently sensitive analytical test methods: For data submitted with NPDES permit application For NPDES permit required monitoring Chemical-specific methods only (not WET) Expansion of existing guidance for clean Hg Final rule effective 9-18-2014 FR 79(160):49001-13
EPA SSTM Rule (con t) Permitting Authorities implementation timeline One (1) year to revise as necessary their NPDES regulations to adopt SSTM requirements Deadline 9-18-2015 Two (2) years if statutory changes are needed As per 40CFR 123.62 Deadline 9-18-2016 Many conflicts with R6 MQLs
EPA SSTM Rule Background EPA generally approves multiple methods for the same pollutant Some approved methods more sensitive (lower minimum level, ML) than others EPA historically expect permittees select method sufficiently sensitive to quantify pollutant Data must be quantified at meaningful levels to support decision-making (permit) process Reasonable potential determinations Patterned after EPA 1631E Hanlon memo 2007
EPA SSTM Rule Definitions Reporting limit has many names: ML= MQL= MAL= RL= LOQ, etc. Sufficiently sensitive method: Method ML is at or below applicable Water Quality Criterion (WQC) or permit limit Method ML > WQC but discharge pollutant concentration is > ML Method has lowest ML of any EPA-approved analytical method SSTM Rule NOT apply where no EPA-approved method exists
ELEMENT SSTM COMPARISON MQLs/ MALs Old MQL R6 (ppb) New R6 MQL (ppb) NEW TX MAL (ppb) SSTM TX FW MALs (ppb) SSTM TX SW MALs (ppb) Ag 2 0.5 0.5 0.8 2 Al 30 2.5 2.5 991 NA As 10 0.5 0.5 10 78 Be 5 0.5 0.5 NA NA Cd 1 1 1 0.13-0.4 8.75 Cr 10 3 3 35 131 50 Cu 10 0.5 2 4.3 17.1 3.6 Hg 0.2 0.005 / 0.0005 0.005/0.0005 0.0122 1.1 Ni 10 0.5 2 24 94 13.1 Pb 5 0.5 0.5 0.9 1.2 5.3 Sb 60 5 5 6 NA Se 10 5 5 5 136 Tl 10 0.5 0.5 0.75 NA Zn 5 5 5 54 211 84
SSTM Rule Details Matrix specific minimum level (ML) may be necessary to determine SS method Methods not specifically listing ML Use lowest calibration standard as ML Derive from MDL given in method Technology based requirement such as zero discharge or no detect May justify use of older, less sensitive method to monitor compliance No analytical SAFETY MARGIN in rule (e.g. ML 1/10 of WQC as per 1600 series clean methods)
Impact SSTM on Permittees Only impact on permittees NOT using sufficiently sensitive (SS) methods NPDES permit application incomplete Require re-sampling using SS methods BIG QUESTION: Which MLs will State regulators require/ enforce? R6 MQLs based on analytical sensitivity achievable SSTM Rule MLs based on WQC BEST GUESS: Stay with R6 MQLs for now
2015 EPA MUR-What is it? Method Update Rule (MUR) Periodic update of CWA approved chemical, physical and biological methods for wastewater and environmental samples DRAFT published FR 80(33): 8956-9076 Comment period closed 5-20-2015 Expect FINAL Rule no later than early 2016 Expect considerable push-back from lab community
2015 MUR Who Is Affected? NPDES permit applicants Sampling or other reports required under NPDES Other requests for quantitative or qualitative effluent data under NPDES regulations State CWA 401 certifications, Sludge sampling and testing ( 136.1) Sampling and testing under EPA s pretreatment regulations for existing and new sources of pollution by categorical industries ( 403.12(b)(5)(v)) Refer to applicability language in 122.1, 136.1 and 403.1 Source: TCEQ
2015 MUR Summary Not as dramatic as the 2012 rule Most of 2015 MUR just adds new methods and corrects problems Emphasis on changes to organics methods Updated EPA Methods 608.3, 624.1, 625.1 New 600 Methods a great improvement from a technology perspective but will create enormous hardships if finalized in their current form New and Updated Standard Methods, ASTM, USGS methods and methods from other sources Source: TNI
2015 MUR Summary (con t) Methods incorporated by reference Approval of several national alternative test procedure (ATP) methods Clarifications/Corrections to ATP Procedures in 136.4, 136.5 and Allowed Modifications in 136.6 Revised MDL Procedure Changes to Table II at 136.3(e) to Required Containers, Preservation Techniques, and Holding Times for microbiology Other Technical Corrections Methods 1600. 1603. 1680. 1682 WET methods manuals Footnotes Source TNI/ TCEQ
2015 MUR Summary (con t) Changes to 136.3 to Include New Versions of Approved ASTM Methods Non-substantive changes Table IB: 25 changes Table IC: 1 change Changes to 136.3 to Include New USGS Methods USGS Methods I-2457-11 and I-2548-11 titled Colorimetric Determination of Nitrate Plus Nitrite in Water by Enzymatic Reduction, Automated Discrete Analyzer Methods added to Table 1B for analysis of nitrate, nitrite, and combined nitrate-nitrite. Source TCEQ
2015 MUR Details of Changes Changes to 136.3 to Include ATPs Six new national ATP procedures for the determination of coliform/e. coli (2 methods), inorganic ammonia, nitrate-nitrogen, and organic ammonia (2 methods). Changes to 136.3 to Align with 40 CFR Part 122 Clarifying definition of Director to be the same as in 122.2 Since 122 was recently amended to include a definition of sufficiently sensitive, the words be sufficiently sensitive and will be deleted from 136.6(a)(2). This will avoid confusion since term used in the context of comparing the performance of a modified method versus approved method being modified. Source TCEQ
2015 MUR Details of Changes Corrections to 136 EPA proposed to correct typographical errors, add updates intended to be incorporated with the 2012 MUR, and updates to toxicity methods. Whole effluent toxicity clarifications and corrections to acute and chronic manuals. Add MPN line to Table 1A for Enterococci, SM9230B-2007. Change a hardness entry in Table 1B to clarify calculation of hardness using Ca and Mg approved methods Edit footnote in Table 1B Delete Method 200.5 in Table 1B from cobalt, thallium, and molybdenum entries. Remove reference to costs in 136.3. Remove first occurrence of are in 136.3(e). Source TCEQ
2015 MUR Details of Changes Changes to Table II at 136.3(e) to Required Containers, Preservation Techniques, and Holding Times. EPA proposed to amend some of the requirements in Table II. Specify holding times for total/fecal coliform and fecal streptococci in Table 1H. Change sodium thiosulfate concentrations for bacteria tests. Reinsert language in footnote 5 RE: treatment options (cyanide) vs. dechlorination procedures (bacteria analysis) for samples containing. EPA seeks comments on the best way for EPA and/or State permitting authorities to approve variances for sample preservation, containers or holding times. The 2012 MUR allowed parallel approval by states and EPA which resulted in contradictory answers. EPA is also seeking comments on what data should be submitted to support requests and demonstrate that the variance does not compromise the analytical results. Source TCEQ
2015 MUR Details of Changes Clarifications/Corrections to ATP Procedures in 136.4, 136.5 and Allowed Modifications in 136.6 EPA to clarify that only EPA approves limited ATPs. In the 2012 MUR, EPA inadvertently inserted a phrase that allowed a State permitting authority to approve limited use ATPs within the State. EPA will also clarify the procedure for national ATP approval and the Regional ATP Coordinator s role. EPA plans to add language to 136.6(b)(1) for method users to contact the Regional ATP Coordinator or State to determine if a method modification is allowed Source TCEQ
Update 600 Series Methods Major methods updates 608.3 Pesticides & PCB s in wastewater (67 analytes) 624 Volatile (Purgable) organics in water (105) 625 Semi-volatile organics by solid phase extraction and GC/MS (315 analytes) Updated technology to current practice Much more flexibility Additional analytes Added reporting limits (MLs) Some inconsistencies between the methods Source: TNI
Quality Control Old Methods DOC per analyst Precision and accuracy One time Blank 10% MS 10% QC Check Statements of accuracy New Methods DOC per laboratory Precision, accuracy and MDL Initial and annually (should) Blank 5% MS; 5% MSD LCS per batch Surrogates Internal standard areas (50-200%) Statements of accuracy PT Samples (recommended) Source: TNI
QC Failures If continued re-testing results in repeated failures, the laboratory should document the failures (e.g., as qualifiers on results) and either avoid reporting results for analytes that failed or report the problem and failures with the data. Failure to report does not relieve a discharger or permittee of reporting timely results. Results for regulatory compliance must be accompanied by QC results that meet all acceptance criteria. Source TNI
Reporting Report quantitative data to ML to 3 significant figures Report the lower of two results from 608.3 Report results less than ML as < ML, or as required by the regulatory authority or permit Allows for blank subtraction if requested or required Results from tests performed with an analytical system that is not in control must not be reported or otherwise used for permitting or regulatory compliance purposes, but do not relieve a discharger or permittee of reporting timely results. Source: TNI
Changes to Appendix B Revised MDL Procedure Developed by TNI s Chemistry Committee Addresses issues with current procedure Blanks not centered around 0 Short term variance does not equal long term variance Lack of guarantee of actual detectability Source: TNI
Summary of Procedure One procedure, start with 7 spikes and 7 blanks MDL S = ts s (Std Dev of spikes) MDL B = X + ts b (Std Dev of blanks) Use whichever is highest as the MDL Requires ongoing spikes Source: TNI
Details Requires spreading the initial 7 replicates across at least 3 batches Includes instructions for multiple instruments with the same assigned MDL Requires that spike results meet qualitative ID criteria Requires ongoing (quarterly) spikes Recalculate (but do not redo) every year Includes instructions for determination of a MDL in a specific matrix Source TNI
CONCLUSIONS Know more about the method requirements for data reported under NPDES permits RFQ versus RFP options if available Testing agreement templates best way to proceed New, lower MALs emphasize need for permittee to know more about methods used to report data SSTM Rule impact on analyte by analyte basis Regulators face confusing situation Regulators likely not back away from lower R6 MQLs 2015 MUR Organics analyses centric- 600 series methods Many new methods added Changes to MDL if adopted a significant change Bookkeeping changes to minimize confusion/ conflicts
QUESTIONS? Dr. Paul N. Boothe ALBION ENVIRONMENTAL 4505 Boyett Street Bryan, TX 77801-4614 (979) 268-2677 pboothe@albionenv.com