The 2015 TNI Standard and Other News of Interest TCEQ May 5, 2015

THE 2009 TNI NELAP STANDARDS Developed by consensus Ensured key elements were retained. Removed redundant language Removed non-essential requirements Considered the following goals: Easy to use and understand; Easy to grow and expand; Easy to revise and implement; and Applicable to all laboratories.

THE 2009 NELAP STANDARDS Four Small Volumes = Four Standards Volume 1: Requirements for Laboratories 7 Modules Volume 2: Requirements for Accreditation Bodies 3 Modules Volume 3: Requirements for PT Providers Volume 4: Requirements for a PT Provider Accreditor

VOLUME 1 Everything a lab needs to know Proficiency testing (Module 1) Personnel requirements (Module 2) Quality systems (Module 2) Technical requirements (Modules 3-7) 3: Asbestos 4: Chemistry 5: Microbiology 6: Radiochemistry 7: Toxicity a short story, not War and Peace For a laboratory doing chemical testing, all of the requirements are in Modules 1, 2 and 4 of Volume 1, a total of 60 pages of text as compared to the 324 pages of the NELAC standard.

Volumes 2, 3 and 4 Interesting reading, for maybe QA Manager Volume 2: Requirements for ABs Includes how to assess PT sample analysis Volume 3: Requirements for PT Providers Includes scoring of PT results Volume 4: Requirements for PT Provider Accreditors

So why do we need a 2015 standard? Elephino (pronounced ‘ell if I know). You should not be spending too much time trying to find the differences. It will drive you crazy and will not be very productive.

Issues with the 2015 Standard PT reporting not acceptable to some ABs Other minor PT issues All of ISO 17025 not included Reference Materials Method Validation DOC language confusing and inconsistent Chemistry module needs improving Microbiology and Radiochemistry modules written by chemists Other minor issues

Standards Development Process Committee develops Working Draft Standard (WDS) Presented to TNI Members and Public for Comment Committee develops Voting Draft Standard (VDS) Presented to TNI Members for Vote Positive, Positive with Comment, Negative with Comment, Abstain Committee must resolve all comments Persuasive, Non-Persuasive, Hold for Next Revision Comment Period for Working Draft Standard - V1M5 (Microbiology) The EL-V1M5 (Microbiology) Working Draft Standard (WDS) was presented by webinar to those stakeholder groups who may subsequently adopt, use, or be accredited to the standard. Pursuant to SOP 2-100, any stakeholder or stakeholder group is invited to submit written comments to the Microbiology Expert Committee Chair Robin Cook (cookr@codb.us) and Program Administrator Ilona Taunton (ilona.taunton@nelac-institute.org), no later than Friday September 5.

Standards Development Process Committee develops Interim Standard (IS) Presented to TNI Members and Public for Comment Response to Comments document also published Committee works with stakeholder groups to resolve any remaining comments and pass a Final Standard Comment Period for Interim Standard - V1M4 (Calibration) The EL-V1M4 (Calibration) Voting Draft Standard (VDS), dated March 2013, was approved by the membership.  Pursuant to SOP 2-100, changes were made to the standard as a result of persuasive comments received from voters.  On June 18, 2014 it was presented by webinar as an Interim Standard (IS) to those stakeholder groups who may subsequently adopt, use, or be accredited to the standard. Any stakeholder or stakeholder group is invited to submit any further comments on the changes.  As a result of this input, the Chemistry Expert Committee may further modify the IS.

Changes to PT Standards Reverse some decisions made in the 2009 standard LOQ reporting Analysis date 5-7 months No QC check sample for chemistry New sections for WET and Protozoa Many changes affecting PT Providers Clarification of role of AB in reviewing PT results

2012 Quality System Standard Revised to include all of ISO/IEC 17025 verbatim Clarified confusing language on method validation in Modules 3-7 Moved general language on method selection and validation to Module 2 New definition for LOD to be consistent with MDL Other minor clarifications

2015 Quality System Standard Correct a note about ISO/IEC 17025 V1M2: Section 5.6.1 Revise temperature calibration (5.5.13.1) Allow single point verification at mandated condition Comments due May 20 Publish Response to Comments Document Finalize a revised standard

Chemistry: Module 4 Accomplishments Plans VDS for Calibration passed. Response to Comments completed. Interim standard published, Response to Comments for IS completed. Modified the EPA MDL procedure; published on the website, presented to EPA MDL Procedure published in the February 19 MUR Plans Finalize Calibration Standard Start work on detection and quantitation WDS, incorporating the modified MDL procedure

Revised Calibration Section Removal of calibration points Number of standards required Relative Error / Relative Standard Error Corrective action for CCV Many other minor changes

Microbiology: M5 Accomplishments Plans Published WDS for V1M5 Clarified definition of source water Revised Method Selection and Validation Revised chlorine residual check Plans Complete standards development cycle for V1M5

Radiochemistry: M6 Accomplishments Summary of Changes Published a Voting Draft Standard for V1M6 Comments due May 15 Summary of Changes Many new terms Major rewrite

The 2015 Standard Changes to PT, Quality Systems, Chemistry, Microbiology and Radiochemistry Also changes to Volumes 2, 3, and 4 Expected to be adopted by CSDP in August 2015. Will need review by LASEC for suitability Will need adoption by NELAP for implementation NELAP implementation will be for a specific date, likely 2017

Implementation of 2015 Standard 2-3 year process Extensive training will be provided to labs and lab assessors New checklists will be developed Quality Manual template will likely be revised Half-day webinar planned for July 15 in conjunction with TNI’s summer meeting

Exploring the Future of National Environmental Laboratory Accreditation

Background • ELAB letter to FEM, FEM response • TNI Board assigned action to Advocacy Committee • Advocacy committee proposed outreach to stakeholders

Discussion Original assumptions How do we move forward? EPA would direct the program All states would participate May not be valid assumptions today How do we move forward?

Objective Get input on the state of national accreditation from stakeholders to learn what is and is not working in the current program Ask participants to identify barriers to state and federal participation in the current program in order to determine how to best move national accreditation forward

Direction from Louisville Meeting Conduct interviews of non-NELAP states Hold a webinar for other stakeholders Conduct a face to face workshop session in DC in August 2014

Issues Identified Technical Issues EPA/State Issues Method vs Quality System Audits 1 vs 2 PT samples Harmonization with EPA Cert Manual Simplify TNI Standard and Accreditation Process EPA/State Issues Recognition of NELAP accreditation by other states Encourage more EPA involvement Consistency among NELAP states Accreditation of State labs Communications and Outreach Help for small labs Outreach to Non-NELAP states Technical resources

Technical Issues Misperception that these two approaches are not already integrated. TNI should better publicize how the quality systems approach supports a method based approach. Open to change PT only if there was a guarantee that non-participating states would join. Look at all the compromises that went into the 2 PTs per year decision. TNI standard is more than DW. Don’t want to force all labs into DW requirements. If incorporate into the TNI standard, need to make DW a consensus standard. Generic application. Guidance to help labs with process- mentors, tools. Surveillance assessments. Better use of tools and technology for ABs to manage programs

EPA/State Issues Work at the grass roots level with lab associations. Assign a TNI ambassador to every non-NELAP state. Re-visit the crosswalk with TNI standard and DW certification manual. Develop an bi-annual “State of National Accreditation” report and offer briefings to EPA Increase management oversight of assessments Promote assessor calls and assessor forum to disseminate information. Encourage state labs to use non-governmental accreditation bodies (NGABs). Promote EPA lab competency policy.

Communication and Outreach Explore website changes. Consider a “tool box” format with flow charts, diagrams, templates, examples and other graphics to make information more readily available. Establish a mentoring group for small labs and FSMOs. Consistently have a seminar at NEMC to introduce new labs to TNI. Develop a free webinar to introduce TNI and highlight the benefits of accreditation.

Bob Beimer Bill Telliard Bruce Colby Larry Keith Somebody from Texas

2015 Methods Update Rule Proposed on February 19, 2015 Updated EPA Methods 608.3, 624.1, 625.1 New and Updated Standard Methods, ASTM methods and methods from other sources Changes to sample preservation and holding times for microbiology Revised MDL Procedure Other “Technical Corrections” Methods 1600. 1603. 1680. 1682 WET methods manuals Footnotes 2,2’-oxybis(1-chloropropane) Many more details in TNI webcast

Footnotes Table 1B Table 1A Adds 1999 errata sheet to Method 300.1, cover sheet is not on EPA methods page, but can be found by searching. Method is shown as 300.1-1 Clarifying analyst role in meeting criteria when modifying methods Correctly typo LRB to LFB Clarifying reporting data qualifiers for failed QC Added footnote 30 for 9222D: The verification frequency is at least five typical and five atypical colonies per sampling site on the day of sample collection and analysis. Table 1A

Table 1C: Dichlorobenzenes 2007 MUR removed approval of dichlorobenzenes from Method 625 “significant losses of these volatiles can occur using the prescribed sample collection procedures in the LLE methods, resulting in relatively low recovery of these compounds” Method 624 approved for all three isomers 2015 proposed rule list 624.1 for two isomers (1,3 and 1,4) and 625.1 for one (1,2)

Method Modifications: 136.6 Deleted some language that has been added to Methods 608.3, 624.1 and 625.1, e.g. alternate extraction, concentration, and cleanup procedures, changes in column and type of mass spectrometer Added new section on Method Modifications The permittee must notify their permitting authority of the intent to use a modified method. Such notification should be of the form “Method xxx has been modified within the flexibility allowed in 40 CFR 136.6.” The permittee may indicate the specific paragraph of 136.6 allowing the method modification. Specific details of the modification need not be provided, but must be documented in the Standard Operating Procedure (SOP) and maintained by the analytical laboratory that performs the analysis.

600 Series Methods Developed in the 1970s and reflected the best practice at the time, e.g. Analytes = priority pollutants Liquid-liquid extraction Packed columns Separate base/neutral and acid fractions because of special column needed for phenols 3-point calibration Methods were inter-laboratory validated

Since 1979 Other EPA Programs used these methods as a basis Contract Laboratory Program SOWs Drinking Water: 508, 524, 525 SW-846: 8080, 8081, 8082, 8240, 8250, 8260, 8270 Expanded analyte lists New technology Capillary columns Solid Phase Extraction (SPE) Selected Ion Monitoring (SIM) Hydrogen carrier gas Additional QC

Summary of Changes Expanded to include additional analytes Table 1 = “Analytes of Interest” Table 2 = Expanded Analytes (Table 3 for 625.1) Added Reporting Limits (Minimum Level or ML) Much more flexibility in the procedure More QC and more requirements for reporting Some inconsistencies Some interesting new concepts Some interest new identification techniques

Analytes of Interest 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. MDLs and MLs provided for most analytes

Expanded Analytes Very long lists Very little performance data 67 pesticides 105 volatiles 315 semivolatiles Very little performance data Includes some that are likely not measurable Methanol Phthalic anhydride Includes analytes of little or no regulatory concern that may not be measurable May lead some data users to requests tests that are not practicable

Minimum Level EPA Concept that has existed for >20 years ML = MDL x 3.18 3.18 =10/3.14 = Curries LQ Round to the nearest 1, 2 or 5 x 10n So ML Values would be 1, 2, 5, 10, 20, 50, etc MLs published in the method = MDL x 3 If MDL is wrong, 3 x MDL is also wrong

Inconsistencies Storage and replacement of standards Standard traceability 608.3 = to a national standard, when available. 624.1/625.1 = to NIST or other national standard Second Source standard Closing CCV 608.3 = Yes 624.1/625.1 = No Batch definitions 608.3/625.1 = 20 samples 624.1 = 12 hours

Storage of Standards 624.1 Store standard solutions at - 10 to -20°C, protected from light, in fluoropolymer-sealed glass containers with minimal headspace. 625.1 Store at <6 °C and protect from light. Check frequently for degradation or evaporation, especially just prior to preparing calibration standards from them. 608.3 Store neat standards or single analyte standards in the dark at -20 to -10 °C. Store multi-analyte standards at 4°C or per manufacturer’s recommendations. Place a mark on the vial at the level of the solution so that solvent evaporation loss can be detected.

Replacement of Standards 608.3 Stock standard solutions must be replaced after 12 months or sooner if comparison with quality control check standards indicates a change in concentration. Analyze all standard solutions within 48 hours of preparation. Replace purchased certified stock standard solutions per the expiration date. Replace stock standard solutions prepared by the laboratory or mixed with purchased solutions after one year, or sooner 624.1 Replace after one month, or sooner if the concentration changes by more than 10 percent. 625.1 Replace purchased certified stock standard solutions per the expiration date. Replace stock standard solutions after one year, or sooner if comparison with QC check samples indicates a problem.

Second Source Standard 624.1 Not listed in Reagents Not used to check ICAL = LCS Criteria = Table 7 May run 2 consecutive LCS 625.1 = CCV Criteria = Table 6 May run 2 consecutive 608.3 different manufacturer or different certified lot verify the accuracy of the initial calibration concentrations must be within 20% difference of the true value

Calibration Curves 624.1/625.1 608.3 External Standard At least three levels (5 recommended, 6 for quadratic) Low point must be below published ML External Standard If the RSD is less than 20%, linearity can be assumed If curve, must be inversely weighted to concentration Must have R2 of 0.99 or RSE of 20% Internal Standard If the RSD is less than 15%, linearity can be assumed Must have R2 of 0.99 or RSE of 15% 624.1/625.1 At least five levels (6 for quadratic) Average RF may be used if RSD < 35% If curve, must be inversely weighted to concentration Must have R2 of 0.92 or RSE of 35% Low point must be below published ML ML can be rounded, but may not be above published level; i.e., ML of 4.8 cannot be rounded to 5

Correlation Coefficients for Evaluation of Calibration Anal. Chem. 1981 (C.L. Grant) One practice which should be discouraged is the use of the correlation coefficient as a means off evaluating goodness of fit of linear models. Thorough statistical analysis of analytical calibration data should be used to provide optimal evaluation of results. The correlation coefficient is not an effective statistic for this purpose.

Calibration Verification 608.3 Verified at the beginning and end of each 24-hour shift Criteria published in Table 4, e.g. Aldrin =75-125 Dieldrin = 48-125 Table 4 criteria includes all sample processing steps 624.1 = LCS Criteria in Table 7, e.g. Bromoform = 70-130 Bromomethane = 15-185 625.1 20% difference changed to Table 6 (Q?) Values can be as high as 13-200% This is the same as 624 608 was once per day and 15%

Quality Control Old Methods New Methods DOC per analyst Blank 10% MS 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)

IDC/DOC MDL Study 4 replicate QC Check samples Concentration at or below mid-point Compare results to QC criteria (Tables 4, 6, or 7) For analytes with no criteria, use 136.6 Criteria from an “equivalent” method Default criteria (e.g., 60-140%) MDL Study As described in Appendix B MDLs must be equal to or lower than those in the method, OR 1/3 the regulatory level

MS/MSD Spike at least 5% of samples from each site Data user to identify samples and analytes If direction cannot be obtained, the laboratory must spike at least one sample in duplicate per batch. Spiked sample results should be reported only to the data user whose sample was spiked. If recovery falls outside the designated range, the result for the analyte in the sample is suspect and may not be reported or used for permitting or regulatory compliance.

Statements of Accuracy Calculate the average recovery and sd from MS/MSD (for each discharge?) Calculate interval X ± 2sd Update on a regular basis What would this be used for? This was in the 1984 versions of these methods

QC Limits for MS/MSD Calculate new limits after 20 MS/MSD Update every two years 80% of limits better than QC Table QC Table are the maximum limits

LCS One LCS per batch of 20 or less Use criteria in QC Table (Table 4, 6 or 7) Repeat the test for those analytes that failed to meet the criteria. If these analytes now pass, system performance is acceptable and analysis of samples may proceed. If this occurs, repeat the test using a fresh LCS, or perform and document system repair. Update criteria using same procedure as MS/MSD

Blanks One blank per batch Re-extract if blank result is: Greater than MDL, or Greater than 1/3 compliance limit, or Greater than 1/10 sample concentration If re-testing of blanks results in repeated failures, the laboratory should document the failures and report the problem and failures with the data. NELAP: the concentration is at or above the reporting limit, AND greater than 1/10 of the amount measured in the sample

Surrogates Must be spiked in every sample Laboratory develops limits; 60-140% can be used as interim limits Any failure, re-analyze sample if available Surrogate recoveries from the blank and LCS may be used as pass/fail criteria by the laboratory or as required by a regulatory authority, or may be used to diagnose problems with the analytical system.

Blank Subtraction When subtracting two measurements, the uncertainty in the final measurement is equal to the sum of the uncertainties in the original measurements: (A ± s) - (B ± s) = (A - B) ± (sA + sB) Dieldrin: MDL = 6; ML = 18; s = 42% C = (18 -6) ± (7.5+2.5) = 2 - 22 http://physicsed.buffalostate.edu/pubs/MeasurementAnalysis/MA1_9ed.pdf

Specific Method Issues

608.3 Second Column Confirmation If values from two columns are in agreement within a factor of 2, analyte is present If not within factor of 2 If interferent is detected on second column, report result and advise data user of interference If no interferent is detected, report ND at the lower concentration

624.2 Mass Spectrometer Scan rate changed to 7 scans/second Mass range = 35-260 with suggestion to go to 25-260 for: Acrolein (m/z 56, 55, 58) Acrylonitrile (m/z 53, 52, 51) Choloromethane (m/z 50, 52) Vinyl chloride (m/z 62, 64) Interferences below m/z 35 Methanol (m/z 29, 31, 32) Nitrogen (m/z 28) Oxygen (m/z 32) Argon (m/z 40)

624.1 GC resolution Valley between 1,2-dibromoethane and chlorobenzene must not exceed 25% 1,2-dibromoethane is not listed as an analyte The two compounds have very different spectra 1,2-dibromoethane 107 (109, 188) chlorobenzene 112 (77, 114)

GC/MS Identification Retention time: ±30 seconds changed to 0.06 RRT Relative intensities changed from ±20% to 50% to 200% New: “m/z’s present in the acquired mass spectrum for the sample that are not present in the reference mass spectrum must be accounted for by contaminant or background m/z’s.” Isomers must have peak resolution of 50% compared to 25% in Method 624/625 (and methods 524/525)

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. 624 allowed QC check to override MS failure; no criteria for blanks

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.

Reporting Caveat (1.7.1) EPA has promulgated this method at 40 CFR Part 136 for use in wastewater compliance monitoring under the National Pollutant Discharge Elimination System (NPDES). The data reporting practices described in Section 15.2 are focused on such monitoring needs and may not be relevant to other uses of the method.

600s: Summary of Technical Updated technology to current practice Much more flexibility Additional analytes Some inconsistencies between the methods

Summary: QC and Reporting New concepts may be troublesome Making data user select samples to be spiked Establishing accuracy/precision per site/discharge Reporting rules for 608.3 Revised identification criteria for 624.1 and 625.1 Blank subtraction Daily calibration checks are problematic Not consistent with current industry practice Will greatly increase error QC section is problematic Cannot realistically be done Will increase laboratory fraud The caveats help, but not enough

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

Summary of Procedure One procedure, start with 7 spikes and 7 blanks MDLS = tSs (Std Dev of spikes) MDLB = X + tSb (Std Dev of blanks) Use whichever is highest as the MDL Requires ongoing spikes

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 Much more tomorrow: Richard Burrows

SUMMARY Not as dramatic as the 2010 rule Most of this just adds new methods and corrects problems New 600 Methods a great improvement from a technology perspective but will create enormous hardships if finalized in their current form MDL is a incredible improvement! Send in your comments! Deadline extended to May 20 www.regulations.gov Docket ID: EPA–HQ–OW–2014–0797

Contact TNI Jerry Parr, Executive Director www.nelac-institute.org jerry.parr@nelac-institute.org 817-598-1624