U.S. Department of Energy Radiological and Environmental Sciences Laboratory

1. U.S. Department of EnergyRadiological and Environmental Sciences Laboratory Anita Bhatt, RESL Director Shane Steidley Steve Bohrer U.S. Department of Energy Idaho Operations Office Sept. 26, 2013

2. 2013 RESL Program Review • Program overview – Anita • MAPEP and analytical issues – Shane • Uncertainties and CRMs - Steve

3. MISSION: A Reference Laboratory for the U.S. Department of Energy • Provide DOE and other federal agencies & programs confidence in laboratory results supporting protection of workers, the public and the environment • Assurance of measurement quality • Traceability • Independence • RESL adds a defensible decision making component to the management and oversight of federal operations • Performance based evaluation of laboratories with real world samples and matrices

4. RESL’s Core Capabilities Expertise in analytical measurements for radiological, inorganic and organic analyses Radiation measurements and calibrations for dosimeters Applied programmatic R&D Development of new Radiological and Inorganic Certified Reference Materials (CRM) New Analytical Methods Technical Assistance Development of DOE and National Standards

5. RESL – Established Quality Systems Accredited to ISO/IEC-17025:2005 ISO Quality Standard for Laboratory Operations & External Dosimetry Accredited to ISO/IEC-17043:2010 General Requirements for Proficiency Testing Accredited to ISO/IEC-G34:2009 General Requirements for Certified Reference Material Provider NIST/RESL Radiological Traceability Program

6. Combined QSM/QSAS document requirements • Section 2.1.2 PT Samples for Initial Accreditation (DoD Only) • MAPEP is required for all laboratories that possess a radioactive materials license for analysis of radiological samples. • Section 3.1.2 PT Samples for Initial Inclusion (DOE Only) • MAPEP is required for all laboratories that possess a radioactive materials license and that perform inorganic, semi-volatile organic, or radiochemical analyses for DOE.

7. www.id.energy.gov/resl/

8. MAPEP Sites General MAPEP Website • http://www.inl.gov/resl/mapep/ • QA concerns criteria, program info, handbook, data reporting • Complete, statistical, & summary reports for all labs Password MAPEP Website • https://mapep.inl.gov/ • Laboratory point of contact • MAPEP Stakeholders • DOCAP Auditors, DOE HQ, DOECAP Site Representatives, DOE Field Office • Access for nonfederal subcontractors upon request

9. Laboratory Enter, view, & obtain study data Laboratory performance Analyte, Study, Flag, and Bias Reports Letters of Concern MAPEP Stakeholder View and obtain study data Multi Laboratory performance Analyte, Study, Flag & Bias Reports Letters of Concern Non-Reporting Labs Concern Reports Query Capability Access for nonfederal subcontractors upon request Password MAPEP Website Website Administration • All of the above • Page contact/Site Feedback: Shane Steidley, steidlsd@id.doe.gov

10. Results for Natural vs. Depleted Uranium Isotopes by Mass Spec

11. Results for Natural vs. Depleted Uranium Isotopes by Alpha Spec

15. Iodine Testing updated RESL identified that Iodine-129 analyses were being performed. However, there was no performance testing • Continued participation has improved performance • Series 28 • Failing Laboratories withdraw • International labs increase participation

16. I-129 Verification • XAW waters are prepared with an independent NIST traceable solution of I-129 • Blind RESL verification results: Std Known (pCi/L) Exp (pCi/L) Ratio I-129- XAW-A 2.56 ± 0.04 E2 2.55 ± 0.04 E2 1.00 ± 0.02 I-129- XAW-B 3.30 ± 0.05 E2 3.36 ± 0.03 E2 1.01 ± 0.02 I-129- XAW-C 1.84 ± 0.03 E2 1.83 ± 0.05 E2 0.99 ± 0.03

17. MAPEP Sr-90 Verification • Internal Blind Test Results • Statistically identical to known • Independent RESL solutions • NIST Intercomparison

18. RESL Sr-90 Analytical Traceability • RTP External Blind NIST Performance Test Results • Cross checked to NIST and independent RESL standards

19. RESL, Reference Laboratory Example • Radiological and Environmental Sciences Laboratory provided the reference values for 89Sr and 239Pu analyses for MFPII PT study. • Sr-89 Determined using Strontium Separation Chemistry • ICP-Emission Spectrometry was used to determine the recovery of Strontium. • RESL determined the Pu-239 reference value • RESL identified and quantified Np-237

20. Uncertainty Flags • Current uncertainty flags and criteria • > 20% relative uncertainty – H • < 3% relative uncertainty – L • MAPEP will be changing the uncertainty flags to align with the reported value flags A, W, N • Uncertainty flags will be for information purposes only at this time, no letters of concern • Will not apply to False Positive or Sensitivity Evaluation tests

21. Uncertainty Flags Rationale • MAPEP levels are sufficiently high to provide at least 5-10% relative uncertainty due to counting statistics at routine sample sizes. • Most labs are reporting “reasonable” uncertainties • Some labs report >50% or <1% relative uncertainties • Statistical zeros • Unjustifiable precision (Implies precision that may or may not be applicable to routine sample counting)

22. Uncertainty Flags Rationale, Cont. • High relative uncertainties can come from: • Very small sample size • Low recovery • Short count times, etc. • Low relative uncertainties can come from: • Failure to include all sources of uncertainty in calculations • Unreasonably small estimates of uncertainty components • All of these potential issues should be of concern to laboratory personnel

23. New MAPEP Uncertainty formula

24. Uncertainty for Inorganic Results(ASP 2011) • A Result is not an absolute, the uncertainty characterizes the range about the result within which the true value is expected lie (result +/- uncertainty) • 19 years MAPEP has encouraged reporting a result with uncertainty • ISO 17025 requires analytical results with uncertainty • NIST recommends reporting a result with uncertainty • The international laboratory community routinely reports analytical result with uncertainty • MAPEP will require inorganic uncertainty reporting beginning with Session 30 • Inorganic results and associated uncertainties will be used in evaluating False Positive tests

25. ISO Accreditations • ISO/IEC 17025:2005 General requirements for the competence of testing and calibration laboratories • ISO/IEC 17043:2010 General requirements for proficiency testing • 17025 + specific requirements for PT • Verification of reference values, homogeneity, stability • ISO/IEC Guide 34:2009 General requirements for the competence of reference material producers • 17025 + 17043 + additional rigor • ISO 30, 31, 35

26. RESL’s ISO Guide 34 Accreditation • Purpose of CRM accreditation: To ensure that valid methods are established to assign values to properties of a reference material, including the evaluation of their associated uncertainty, and establish their metrological traceabliity. • Reference material that undergo all steps described in ISO Guide 34 are usually accompanied by a certificate and are called certified reference materials (CRM).

27. How is PT different than CRM? • PT is used for the purpose of evaluating laboratory methods, performance, etc. • Generally provided by outside organization – single/double blind • Reference value is not known by analysts • Evaluation methods and criteria are defined • CRM may be used as PT, or by a laboratory for validating methods, internal QC, etc. • CRMs come with a certificate indicating reference values, expiration dates, intended uses, etc.

28. PT vs. CRM Requirements MAPEP

29. RESL CRMs • Reference values are directly calculated from dilution of a traceable standardwith very few exceptions (e.g. U) • Homogeneity • Within Bottle For Subdivision • Between Bottle • Batch Produced • Batch Produced (Individuals) • “Single Shot” • Stability • Transportation • Shelf-Life

30. Pu-239 Homogeneity Test Data Target Conc. 2.100 0.06 (based on 3% target S.D.) (a-b) a+b Sample Result 1(a) Result 2(b) D^2=(a-b)^2 1 2.1 2.0 0.11 4.09 0.01 2 2.1 2.1 0.07 4.21 0.00 3 2.0 2.0 -0.03 3.97 0.00 4 2.1 2.2 -0.05 4.25 0.00 5 2.1 2.2 -0.11 4.33 0.01 6 2.0 2.1 -0.16 4.12 0.03 7 2.0 2.0 0.00 4.04 0.00 8 2.1 2.1 0.03 4.19 0.00 9 2.2 2.0 0.23 4.21 0.05 10 2.1 2.0 0.08 4.16 0.01 Sum D^2 0.12 Average 2.1 Cochran's Test 0.447 No Evidence for Outliers Std. Dev 0.1 Analytical Variance (San^2) 0.006 %RSD 3.6% S^2 (sam) 0.000 BIAS -1.0% Target Sample Variance (Sall^2) 0.000 Critical Value 0.006 Sufficiently Homogeneous at the 95% confidence interval 2.3 2.3 2.2 2.2 2.1 Result 1(a) Result 2(b) 2.1 Target Conc 2.0 +/ - 95% 2.0 1.9 1.9 1.8 0 1 2 3 4 5 6 7 8 9 10 11 RESL’s Approach to Homogeneity (Soil)

31. Long Term Process Stability Test - Pu-238 RATIO Uncertainty Time (Years) EXP'L/KNOWN RATIO MAW14 7.06 0.94 0.04 Stable MAW16 6.06 0.99 0.05 Stable MAW18 MAW20 3.55 1.01 0.05 Stable MAW22 2.39 0.98 0.04 Stable MAW24 1.47 0.99 0.05 Stable (Uncertainties reported with a coverage factor k=1) Number of Data Points 5 b Slope of Line 0.09 1 b Intercept of Line 0.60 0 2 s Std Dev of Points 0.51 s(b ) Unc of Slope 0.10 1 t Student t-factor * 3.18 0.95,n-2 * (* The Student's t-factor for n-2 degrees of freedom and p=0.95 (95% level of confidence) Abs. Value of b |b | 0.09 1 1 t *s(b ) 0.33 Slope is insignificant 0.95,n-2 1 If |b |<t *s(b ) then the slope is insignificant indicating stability. 1 0.95,n-2 1 MAPEP Water process stability test indicates that Pu-238 in RESL prepared reference water is stable for at least 7 years. Reference: ISO G35:2006 (E) Section 8.3 ANSI N42.22 RESL’s Approach to long-term stability (Shelf-Life)

32. RESL CRM History • RESL has prepared custom standards for many years • Kelp, bone, fish for Amchitka Island project • Air filters for emergency exercises, IAEA • Egg powder, vegetation for FERN • Various DOE sites and federal agencies – radionuclides in vegetation, food, soil, water, biological material. • Refractory Pu • RESL standard philosophy • Blank natural matrices spiked with known quantities of NIST traceable standards with calculated reference values • Standard materials are tailored to specific purposes and include multiple nuclides as varying activity levels to realistically test capability

33. RESL CRMs • Over the years RESL has received a number of requests for higher levels of activity in a variety of environmental matrices (SSPEP) • Needs have been identified in the homeland security/consequence management area • RESL is already preparing a variety of real-world matrix standards • RESL now has the ISO 34 accreditation to produce CRMs

34. New RESL/NE Certified Reference Materials Radiological & Inorganic CRMs • Soil • Water Radiological CRMs • Cement – (Surface Contamination) • Cement – (Homogeneous) • Vegetation • Filters • Sludge • Nasal Swabs • Powdered Eggs/Milk • Food Stuffs

36. Specialized Proficiency Testing Proficiency Testing with new CRMs • Customer & RESL determine acceptance criteria • Single blind or double blind PT samples • RESL ships PT samples to field or participants • Secure web site reporting of results • Web accessible performance evaluation reports Addresses the need of Integrated Consortium of Laboratory Networks (ICLN)

37. RESL Contacts • Anita Bhatt, RESL Director – bhattar@id.doe.gov • Shane Steidley, MAPEP Database – steidlsd@id.doe.gov • Steve Bohrer, Radiochemist – bohrerse@id.doe.gov • Guy Marlette, MAPEP Coordinator – marletgm@id.doe.gov Talk Topic