1. DoD PFAS Sampling and Analysis Requirements ASTSWMO Annual Meeting Arlington, VA October 26, 2017
Janice L. Willey
Senior Chemist
NAVSEA 04X6 Laboratory Quality & Accreditation Office (LQAO)
Environmental Data Quality Workgroup (EDQW) Representative
10/26/2017

2. EDQW Overview Responsibilities
- Recommend sampling, testing and quality system policy
- Develop quality systems guidance documents
- Provide support on analytical issues to the DoD Chemical and Material Risk Management Directorate
- Provide QA/QC report to SERDP/ESTCP
- Represent DoD on public and governmental workgroups
- Chaired by Navy, Principals from Air Force, Army, and DLA
Ensure environmental data are of the type and quality necessary to support their intended uses
10/26/2017

3. PFAS Sampling and Analysis Procedures
Drinking Water
- EPA 537.1, Rev. 1.1 (Technical Advisory, September 2016)
- ISO 25101:2009(E)
Other Media
- EPA-821-R , Draft, December 2011
- ASTM D
- ASTM D
Methods Not Published
- Modified EPA Method 537
10/26/2017

4. EDQW PFAS Activities
Issued “Bottle Selection and other Sampling Considerations When Sampling for Per- and Polyfluoroalkyl Substances (PFAS)”, July
Co-chair ITRC PFAS Site Characterization, Sampling Procedures, and Analytical Methods Workgroup
Laboratory Outreach: On-site Analytical Workshops (ESTCP Project 15 T2-045)
10/26/2017

5. EDQW PFAS Activities
Developed sample preparation and analysis requirements for DoD ELAP accredited laboratories for media other than DW, DoD Quality Systems Manual for Environmental Laboratories, Version 5.1, Appendix B, Table B-15
Worked with vendors to offer Proficiency Test Studies
for DW, SW/GW, and Soils and standards that are a more cost effective option for isotope dilution/internal standard methods
10/26/2017

6. Table B-15: General Information
Released 01/06/17
Applicable to all media except DW
Created due to lack of published method and to address inconsistencies in data resulting from a wide array of modifications to EPA Method 537
Based on input from researchers, instrument manufacturers, EPA laboratories, commercial vendors, standards and PT providers
Performance-based approach
10/26/2017

7. Table B-15: General Information
Include requirements that would enable the most accurate, precise, and defensible data possible is acquired
Modified methods that meet requirements are listed under the method “PFAS by LCMSMS Compliant with QSM 5.1 Table B-15” in DENIX
10/26/2017

8. DoD ELAP Laboratories Status (As of 10/20/17)
Drinking Water by EPA Method 537, Rev. 1.1
- Search under method “EPA 537”
- 11 accredited laboratories
Other media
- Search under method “PFAS by LCMSMS Compliant with QSM 5.1 Table B-15”
- 6 accredited laboratories
- 7 currently under review for accreditation
10/26/2017

9. Questions?
Janice L. Willey Work # : (843) Cell # : (843)
10/26/2017

10. Table B-15: Sample Preparation
Aqueous:
- SPE of entire sample and bottle rinse routine samples
- ENVI-CarbTM Clean-up or equivalent on routine samples and all associated QC samples (except AFFF formulations)
- Serial dilution for non-routine samples (known high concentration samples) with documented project approval
Solid:
- Entire sample received by laboratory must be homogenized prior to subsampling
- ENVI-CarbTM Clean-up or equivalent on all samples
and associated QC samples
10/26/2017

11. Table B-15: Batch Quality Control Samples
Method Blank (MB)
- No analytes detected >½ LOQ or > 1/10 the amount measured in any sample or 1/10 the regulatory limit, whichever is greater
Laboratory Control Sample (LCS)
- Spike concentration ≥ LOQ and ≤ the mid-level calibration concentration
10/26/2017

12. Table B-15: Batch Quality Control Samples
Matrix Spike (MS)
- Not required for aqueous samples prepared by serial dilution instead of SPE
- Spike concentration ≥ LOQ and ≤ the mid-level calibration concentration
- Use in-house LCS limits if project limits are not specified
- Corrective action
Corrective action - Examine the project-specific requirements. Contact client as to additional measures to be taken
10/26/2017

13. Table B-15: Batch Quality Control Samples
Matrix Spike Duplicate (MSD) or Matrix Duplicate (MD)
- MD required for aqueous samples prepared by serial dilution instead of SPE
- MSD spike concentration ≥ LOQ and ≤ the mid-level calibration concentration
- MSD - Use in-house LCS limits if project limits are not specified
- RPD ≤ 30% (between MS and MSD or sample and MD)
- Corrective action
Corrective action - Examine the project-specific requirements. Contact client as to additional measures to be taken
10/26/2017

14. Table B-15: Batch Quality Control Samples
Post Spike Sample
- Only applies to aqueous samples prepared by serial dilution instead of SPE that have reported value of “<LOQ” for analytes
- Spike aliquot(s) of sample at the final dilution(s) reported for sample with all analytes that have reported value of “<LOQ” in the final dilution. Spike must be at the LOQ concentration to be reported with the sample (the “<LOQ” value)
10/26/2017

15. Table B-15: Batch Quality Control Samples
Post Spike Sample
- When analyte concentrations are calculated as “<LOQ”, spike must recover within % of its true value
- When analyte concentrations are calculated as “<LOQ” and the spike recovery does not meet the % acceptance criteria, the sample, sample duplicate, and post spike sample must be reanalyzed at consecutively higher dilutions until the criteria is met
10/26/2017

16. Table B-15: Analysis
Mass Calibration
- Entire mass range must be bracketed by calibration range
- Tune Check masses within ± 0.5 amu
- Acquisition Rate is minimum of 10 spectra scans across each peak
Standards
- Must contain branched and linear isomers when commercially available (currently only PFHxS and PFOS)
- If not available, total response of the analyte must be integrated and quantitated off of the linear isomer (e.g., PFOA)
10/26/2017

17. Table B-15: Analysis Ion Transitions
- Derivation of ion transitions used for quantitation and confirmation must be documented
- Two transitions and the ion transition ratio per analyte must be monitored and documented (exceptions are PFBA and PFPeA)
- Specify quantitative transitions fro PFOA, PFOS, PFHxS, PFBS, 4:2 FTS, 6:2 FTS, 8:2 FTS, NetFOSAA, and NMeFOSAA
- S/N Ratio: ≥ 10:1 for all ions used for quantitation
- For analytes having a promulgated standard (e.g., HA for PFOA and PFOS), the qualitative (confirmation) transition ion must have a S/N ratio of ≥ 3:1
10/26/2017

18. Table B-15: Analysis Initial Calibration
- Isotope Dilution Quantitation is required, when standards are commercially available
- When not available Internal Standard Quantitation is required
- %RSD of the RFs for all analytes must be < 20%
- Linear or non-linear calibrations must have a r² ≥ for each analyte
- Analyte concentrations must be within % of their true value for each calibration standard
10/26/2017

19. Table B-15: Analysis Instrument Sensitivity Check (ISC)
- Every 12 hours
- Concentration at the LOQ
- Recover within ± 30% true value
Initial Calibration Verification (ICV)
- Once after each ICAL, prior to sample analysis
- Second source standard
10/26/2017

20. Table B-15: Analysis Continuing Calibration Verification (CCV)
- Prior to sample analysis, after every 10 field samples and at end of analytical sequence
- Concentration must range from LOQ to the mid-level calibration concentration
- Recover within ± 30% true value
- Corrective Action
Instrument Blanks
- Immediately following the highest standard analyzed and daily prior to sample analysis
- Concentration of each analytes must be ≤ ½ the LOQ
- Corrective Actions
Corrective action for failure is immediately analyze 2 additional consecutive CCVs. If both pass, report sample. If one or both fails or 2 additional CCVs could not be analyzed, perform corrective actions(s) and repeat CCV and all associated samples since the last successful CCV. If not, recalibrate and reanalyze
If criteria are not met after the highest calibration standard, calibration must be performed using a lower concentration for the highest standard
If criteria are not met after the highest standard which is not included in the calibration, the standard cannot be used to determine the highest concentration in samples at which carryover does not occur
If acceptance criteria are not met after sample, additional instrument blanks must be analyzed until acceptance criteria are met. Additional samples shall not be analyzed until acceptance criteria are met
10/26/2017

21. Table B-15: Analysis Extracted Internal Standards
- Added to sample prior to extraction
- Aqueous samples prepared by serial dilution instead of SPE, added to samples prior to analysis
- Recover within 50% to 150% of the true value
- If recoveries are acceptable for QC samples but not field samples, the field samples must be reprepped and reanalyzed (greater dilution may be needed)
- If recoveries are unacceptable for QC samples, correct problem and reanalyze all associated failed field samples
10/26/2017

22. Table B-15: Analysis Injection Internal Standards
- Added to aliquot of samples QC samples, standards, and blanks
- Peak areas must be within -50% to +50% of the area measured in the ICAL midpoint standard
- On days when ICAL is not performed, the peak areas must be within -50% to +50% of the peak area measured in the daily initial CCV
- Corrective Actions
If peak areas are unacceptable, analyze a second aliquot of the extract or sample if enough extract remains. If there is not enough extract, reanalyze the first aliquot.
If second analysis meets criteria, report the second analysis. If it fails, either analysis may be reported with the appropriate flags
10/26/2017