RADIOACTIVITY PROFICIENCY TEST PROVIDER WORKSHOP AT RRMC

Transcription

1 RADIOACTIVITY PROFICIENCY TEST PROVIDER WORKSHOP AT RRMC 2015 Organised by: Carolyn Wong (LLNL, USA) Simon Jerome (NPL, UK) Proficiency testing is an important external measure of a laboratory s capabilities in their particular field of work and this is especially so in radioactivity measurement, given continued public interest in, and concern with, human use of nuclear technology. This year s PT workshop will provide a platform for proficiency test providers in the USA and beyond to describe their PT schemes and how these inform regulators, customers and the public about laboratory performance and the implications for confidence in measurement capabilities for the determination of radioactivity. In addition, current developments in ANSI national standards and ISO international standards will be presented and how such standards interface with laboratory quality requirements. As is usual with the RRMC PT provider workshops, the emphasis will be on open discussion from the attendees around the topics for presentation described above, with particular interest in: Quality control and quality assurance issues arising from PT exercises, Lessons learned over the past 12 months, Accreditation to ISO and ISO 17025, Traceability of measurement, Access to PT programs, Rapid radioactivity measurements, Announcements and information, and Topics for the RRMC 2016 PT workshop. Anyone with an interest in radioactivity measurement proficiency testing is encouraged to attend, whether they are providers of a PT scheme or a participant in such PT schemes. Please contact the organisers of the workshop if you wish to make a brief presentation on any of the topics mentioned above. A splendid time is guaranteed for all!

2 Proficiency Test Providers Workshop Bureau International des Poids et Measures comparisons of NMIs Simon Jerome National Physical Laboratory, UK RRMC Workshop for PT Providers Sheraton Hotel, Iowa City, 27 th October 2015

3 The BIPM Ultimate reference point for all measurements - Sited in Paris on international territory - Set up as part of the metre convention (1875) Sub text Radioactivity? - Policed through Comité Consultatif des Rayonnements Ionisants section 2 - Organisation of international comparisons

4 Why? Sets the scene for global metrology infrastructure - Comparisons of key radionuclides Eg 3 H, 55 Fe, 60 Co, 99m Tc, 137 Cs, 152 Eu, 238 Pu, 241 Am. How? - CCRI(II) meetings set the programmes for: Key comparisons (above) Supplementary comparisons: Completed 137 Cs in rice Planning 231 Pa, 234 Th

5 Standard protocol

6 Outcome

7 Outcomes

8 Outcomes

9 and in reality Participation is not mandatory Outcomes of key comparisons are a KPI for most NMIs Equivalence between measurement systems is essential for international trade, manufacturing &c Open reporting is a given Access to key comparison reports illustrates quality of measurement in a particular country also trading areas, such as the EU Underpins metrology around the planet.

10 Thank you. Any questions?

11 The Intercomparison Studies Program At Oak Ridge National Laboratory An Overview G. Payne, N. Bores, J. Rankin ORNL is managed by UT-Battelle for the US Department of Energy

12 Intercomparison Studies Program Natural urine samples Artificial fecal samples Whole body count samples Single or double-blind (urine) submission Quarterly report

13 Programs Urine Matrix: natural urine Fecal Matrix: synthetic fecal material Whole Body Matrix: acid solutions (phantom provided to program participants)

14 Available Radionuclides In-vitro Am-241, Cm-244, Pu-238, Pu-239, Np-237, Th-nat, U-nat, Bq/kg (0-15 dpm/kg) Sr-90, Co-60, Cs-137, Tc Bq/kg ( dpm/kg) H Bq/kg (0-500 dpm/g) In-vivo Ba-133, Co-57, Co-60, Cs-137, Y kbq/nuclide/sample (0-500 nci/nuclide/sample)

15 Standards Preparation NIST SRM dilution dilution factor verification NPL standards at working concentration Internal stability testing

16 Sample Preparation Urine from employees/retirees with no exposure and no known body burden Urine pooled and added to appropriate containers Gravimetric material transfer

17 Reported Results vs Nuclide 250 Number of Reported Results vs Nuclide 200 Number of Results U-nat Am-241 Pu-239 Pu-238 H-3 Sr-90 Th-nat Cm-244 Co-60 Cs-137 Np-237 Tc-99 Nuclide

18 Custom Samples 239 Pu µbq/sample (low level) and µbq/sample (high level) 238 Pu µbq/sample ( ) Pu µbq/sample

19 Performance Review Continuous, independent 3 rd party monitoring Complete bioassay program testing Performance relative to ISP values Performance relative to participant values Trending

20 Contact Ged Payne (865) Janice Rankin (865)

21 Unbroken Chain, an ISO Requirement Larry Jassin Eckert & Ziegler Isotope Products (EZIP) October 27, 2015 PT Provider Workshop-RRMC

22 3 ISO17025 Accredited Calibration Laboratories Valencia/Burbank, USA Braunschweig, Germany Atlanta, USA

23 Definition PE- performance evaluation, PT- proficiency testing evaluation of participant performance against preestablished criteria by means of interlaboratory comparisons EZIP operates a number of PT programs also known as cross-check programs

24 Current PT-Programs Radiochemical Cross-Check Program (HCC) Nuclear Power Plant Effluents (higher activity) Environmental Radiochemical Cross-Check Program (ECC) Broad Range of Environmental Samples Projects Global Fallout Monitoring (mixed fission products) Emergency Response Method Proficiency

25 Cross-Check Program Overview Blind samples are distributed four times per year (Quarterly). Samples are prepared in customer supplied containers or containers purchased by us. Samples are prepared using NIST traceable radionuclide solutions. Participants provide measured results to Eckert & Ziegler. Customer Summary Report issued.

26 Effluent Monitoring PT Program Our Radiochemical Cross-Check Program is designed to provide performance evaluation samples for monitoring all effluent pathways at nuclear power plants as considered acceptable in NRC Reg. Guide 4.15: 1. liquid radioactive waste samples 2. gaseous radioactive waste samples 3. charcoal/silver zeolite cartridges 4. air particulate samples 5. reactor coolant water

27 Effluent Monitoring PT Program Sample Analysis Form Activity Fe mL liquid 185 Bq/g Gross alpha (Am-241) 20-mL liquid 3.7 Bq/g Gross beta (Cs-137) 20-mL liquid 185 Bq/g Gamma Isotopic (Ce-141, Co-58, Cr-51, Mn-54, Cs-134, Cs-137, Zn-65, Co-60) 20-mL liquid 3700 Bq/g Sr-89/Sr mL liquid Bq/g Tritium 20-mL liquid 185 Bq/g

28 Effluent Monitoring PT Program Sample Analysis Form Activity Gross alpha (Am-241) Gross beta (Cs-137) Gamma Isotopic (Ce-141, Co-58, Cr-51, Mn-54, Cs-134, Cs-137, Zn-65, Co-60) Evaporated Salt (Filter Paper) Evaporated Salt (Filter Paper) Evp. Salt (Filter Paper), Solid (Resin), Simulated Gas 185 Bq 185 Bq 1850 Bq Sr-89/Sr-90 Evp. Salt (Filter Paper) Bq/g I-131 Solid (Char. Cartridge) 185 Bq Gamma Whole Body Solid (Resin) 1.85E5 Bq Noble Gases 14 cc ampoule 1.85E5 & 3.7E4 Bq Noble Gases 33 cc sphere 3.7E4 & 2.96E6 Bq

29 Environmental Monitoring PT Program Our Environmental Radiochemical Cross-Check Program provides more media / radionuclides at lower activity levels than the Radiochemical Cross-Check Program: 1. Charcoal cartridges 2. Soil 3. Water 4. Vegetation 5. Air Filters 6. Milk 7. Biota (Fish)

30 Environmental Monitoring PT Program Analysis Radionuclides Form Activity, Bq/L Alpha/Beta Am-241, Cs-137 Water, Soil, Filter Tritium H-3 Water Gamma-ray emitters Ce-141, Co-58, Cr-51, Mn-54, Cs-134 Cs-137, Zn-65, Co-60 Water, Soil, Filter, Vegetation, Milk Radiochemical I-131, Sr-90 Milk Transuranics Natural Radioactivity Am-241, Pu-238, Pu- 239, Np-237, Cm-244 U-nat, Th-232, Ra-228, Ra-226 Water, Soil, Filter Water, Soil, Filter Beta Emitters Sr-89, Sr-90, Tc-99 Water, Soil, Filter *Volumes: Liquids / Vegetation / Soils = up to 1 liter

31 Establishing Traceability ISO QA Program 5.6.2: Unbroken Chain of Calibrations Linking to Primary Standards NRC Guide 4.15 QA For Radiological Monitoring-Effluents, Environment ANSI N Traceability to NIST

32 ANSI N42.22-Traceability of Radioactive Sources To NIST Section 6: Unbroken Chain to Primary Standards (NIST) Participation in NIST MAP (NRMAP) 6.1.2: Test Requirements (Verification) Gammas <250 kev Gammas >250 KeV Betas <100 kev Betas >100 kev Total Alphas Alphas by alpha spectrometry 6.2: Acceptance criteria Difference between NIST value and test value μ NIST + μ Test

33 2013 NRMAP Program Analytes Gammas <250 kev: Xe-133 (81 kev) Gammas >250 KeV: Kr-85(514 kev) Betas <100 kev: Pu-241, I-129 Betas >100 kev: Sr-89 Total Alphas: Np-237 by LSC Alphas by alpha spectrometry: Np-237 (for impurities)

34 2014 NRMAP Program Analytes Gammas <250 kev: Cd-109 (88keV) Gammas >250 KeV: Cs-137 (661.7 kev) Betas <100 kev: H-3 Betas >100 kev: P-32 Total Alphas: Pu-239 by LSC Alphas by alpha spectrometry: Pu-239 (for impurities)

35 Conclusions EZIP has regularly operating PT Programs EZIP participates in a Measurement Assurance Program(MAP) with NIST and other National Metrology Institutes(NMI) to establish traceability as specifically required by ANSI N42.22, establishing an unbroken chain to primary standards globally (ISO 17025) Decommissioning and security activities may benefit from additions to our established PT programs for training, R&D, method validation and routine work We welcome the opportunity to collaborate with you to build next generation PT programs to meet current and future demands

36 Proficiency Test Providers Workshop EU member state PTEs Simon Jerome National Physical Laboratory, UK RRMC Workshop for PT Providers Sheraton Hotel, Iowa City, 27 th October 2015

37 Brief look at comparisons Last year - Germany and the UK This year - Spain - Italy

38 Spain PTEs jointly organised by - University of Barcelona - CIEMAT (Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas Energy, Environment and Technology Research Center) Madrid centre includes Radionuclide Metrology Scope - Varies from year to year 2011: Water (containing NORM) Spiked with artificial radionuclides 137 Cs, 60 Co, 55 Fe, 63 Ni, 90 Sr, 241 Am, Pu and 238 Pu 2012: Soil (containing NORM) Spiked with artificial radionuclides 137 Cs, 60 Co, 55 Fe, 63 Ni, 90 Sr, 241 Am, Pu and 238 Pu 2013: Filters (containing NORM) Spiked with artificial radionuclides 137 Cs, 60 Co, 57 Co

39 Data analysis Z-score - Usual z = LLL RRR σ PPP Pass: z<2 Acceptable: 2<z<3 Fail: >3 Robust z - Takes account of overall exercise performance LLL MMMMMM z(mm) = Pass: z<2 Acceptable: 2<z<3 Fail: >3 SS rrrrrr

40 Italy PTEs jointly organised by - ENEA Institute of Ionizing Radiation Metrology (ENEA-INMRI) - The Institute for Environmental Protection and Research (ISPRA) Basis - Participants are laboratories belonging to the National Radioactivity Surveillance Network (about 50 laboratories in the Country) - Proficiency Testing actions are part of a wider National Quality Assurance programme - Also includes Calibration campaigns, Workshop for discussion of PT results and Development of Guidelines. - Data Analysis are most often but not always those recommended by ISO (Deviation plot, z scores)

41 Italy Scope (2015) - General objective: identification and quantification of γ emitters, α and β in aqueous with a density close to that of water - Specific objectives: Identification and determination of concentrations of γ-emitting radionuclides (40 kev < Eγ < 2 MeV) Total α Total β 90 Sr Determination of the MDA for nuclides not present Experimental determination of repeatability and reproducibility of the measurement methods used in measuring conditions. - Nuclides: 60 Co, 90 Sr, 137 Cs, 241 Am

42 Matrices Varies, depending on requirements - Has included - Soil - Water - Air filters - &c

43 Thank you. Any questions?

44 The Nuances of Making Quality Proficiency Testing Materials. PART II: Infrastructure Guy Backstrom US DOE Radiological and Environmental Sciences Laboratory Radiological Proficiency Testing Providers Workshop RRMC 2015

45 EXPECTATIONS Our Participants Have the right to expect that the Reference Value in the Proficiency Testing Material represents what is Actually in the sample. The Proficiency Testing Provider should have the INFRASTRUCURE to VERIFY reference values, homogeneity, interferences, contaminants, mistakes and everything else that goes wrong to avoid accusing participants of poor performance. Unimpeachable Integrity If the Reference Value cannot be assured then the Proficiency Testing Material isn t worth making. 2

46 Inaccurate Standards From Certified Commercial Vendors Th-230 ~ 18% High H-3 ~ 20% Low U g actual vs 5.45g contained Pu-239 Calculated Incorrectly (missed Pu-240) Th-230 source was actually Am-241 Fe-55 Contaminant in Mn-54 Standard Zn-65 Contaminant in Co-60 Standard Sr-90 Contaminant in Sr-85 Standard Sr-90 Contaminant in Sr-89 Standard 3

47 MaS30 - Uranium-238 4

48 Biased Performance Testing Material MAS28 Technetium-99 5

49 Biased Performance Testing Material MAS28 Technetium-99 6

50 Preservation Requirements For Radioiodine Samples Commonly Thought No Preservation Is Required I - + [Ox] I 2 and I - + H + HI Must Be Kept Alkaline and Reduced (S or S ) Preservation Known Experimental (pci/l) No 99 +/ /- 2 Yes 99 +/ /- 5 7

51 Properties PT Material Should Have Known Activities (Metrological Traceability) Avoid introducing PT producer bias Smaller uncertainties Homogeneous - At Some Sample Size, At Some Precision Unimpeachable Integrity Not Questioned In EVERY PT scheme if a participant fails, it is not because the participant has done poor work or is wrong, it is because the PT provider is. Accusations are directly proportional with the importance of passing 8

52 Types Of PT Material (Standards) DI Water (Worthless) Only proves proficiency in DI water not other matrices Natural Matrix Standards (Semi-Worthless) Hard to overcome Hot Particle Syndrome Spiked Natural Matrices (Best - lesser of two evils) Finding blank material Uranium (Soil/Urine/Feces/Vegetation) Spiked Synthetic Matrices (Best - if achievable) Finding blank material/depends on how low do you want to go Uranium (Ultra Low Mass Spec determinations) 9

53 Advantage of Spiked Natural/Synthetic Matrices Known Activities no Analytical Bias Metrological Traceability Uncertainties Are Much Smaller Than Analyzed Standard Ability to Customize (depending on ability to determine blank) Levels Of Activity Check Accuracy Detection Limits and False Positive Have to check contaminants of Standards Have to know Backgrounds Performance Based Interpretation of Results Unlimited Different Matrices 10

54 Base Soil Analytical Values Soil 1 Soil 2 Soil 3 Soil 4 Soil 5 Element Total Total Total Total Total % Leachable mg/kg % Leachable mg/kg % Leachable mg/kg % Leachable mg/kg % Leachable mg/kg Arsenic Barium Beryllium Cadmium Chromium Cobalt Copper Lead Nickel Thallium Vanadium Zinc

55 Uncertainty of Standard with Background 12

56 Questions to Answer What is the purpose/goal of the testing scheme? What are the testing criteria? Types of Samples, How many samples, Accuracy, uncertainty, levels, sensitivity, analytes, pass/fail, ongoing, defined/not defined sample size, reporting requirements, time frame.. Participants aware of testing criteria? Type of testing determines sample construction. Accuracy, Homogeneity, Stability, False Positive/Negative Testing, Sensitivity/Detection Limit Testing, Unique Isotopic Ratios, Interferences (chemical/radiological), Detect/Not Detect. 13

57 What about Homogeneity Homogeneity Within Bottle For Subdivision Between Bottle Batch Produced Batch Produced (Individuals) Single Shot Indicator analytes to verify homogeneity??? No Chemistry of the Analytes are Different Verifying by gamma spec doesn t ensure homogeneity of actinides or beta s 14

58 Homogeneity NOT The Reference Value Verification of Reference Value and Homogeneity are different Verification Confirmation of the known value at some precision Homogeneity Based on sample size required for testing scheme 15

59 What about Transportation/Stability PT material must be stable from the time of production until the end of the testing scheme and includes storage and shipment to customer (expiration). Problems encountered Evaporation losses Bottles are not created equal Stratification of liquid samples during freeze cycle Stratification of particle samples due to vibration and different particle size. Can t Just Say Have to Prove 16

60 RESL s Established Quality Systems Accredited to ISO/IEC-17025: General Requirements for Chemical Testing & External Dosimetry Accredited to ISO/IEC-17043: General Requirements for Proficiency Testing Provider Accredited to ISO/IEC-G34: General Requirements for Certified Reference Material Producer NIST/RESL Radiological Traceability Program Seeking ISO 13528:2015 Statistical Methods for use in Proficiency Testing by Interlaboratory Comparisons 17

61 Proficiency Test Providers Workshop Uncertainty outlier test NPL Simon Jerome National Physical Laboratory, UK RRMC Workshop for PT Providers Sheraton Hotel, Iowa City, 27 th October 2015

62 Arises from RRMC 2015 What is the test? Evaluates uncertainty R L = u L σ PPP (< 3) Uncertainty outlier test 6500 Result R L value

63 Transforms to

64 Thank you. Any questions?