Proficiency Test on Radiological Characterization of irradiated graphite

Transcription

1 Proficiency Test on Radiological Characterization of irradiated graphite Dr. Gabriel Piña Lucas Mrs. José Luis Leganes ASOCIACIÓN CIEMAT-ENRESA 23/11/2012

2 Who?

3 CWRRT. Design of Inter-laboratory Test Objectives Determine the performance of individual lab for radioactive measurement of graphite Establish the effectiveness and comparability of new or/and established methods Identify iter-laboratory differences Identify problems in labs and initiate remedial actions Provide additional confidence to laboratory clients Selected scheme: Split-level Framework Coordinator and Evaluator: CIEMAT Partners: free to use a method of their choice Coordinator request details of the methods!

4 Roadmap SAMPLING TESTING HOMOGENEITY PACKAGING TRANSPORT SCHEME SENDING DELIVERY FINAL CONCLUSIONS EVALUATION INTERACTIVE` CONSULTANCY LAB`S DATA COOKING BOOK STATISTICAL APPROACH

5 Sample A Aliquot-0 Aliquot-1 Aliquot-2 Subaliq-1-1 TREATMENT Subaliq-1-2 Subaliq-1-3 Replic Replic Replic SEPARATION Subaliq-2-1 Subaliq-2-2 Subaliq-2-3 RRT.Sampling Samples: Irradiated graphite (real waste): Powder from sleeves treatment of an UNGG reactor ~ 5 g / participant Lab 2 blind sub-samples per partner (2 g) and 1 g as reserve Nuclides to be determined Co-60; H-3, C-14, Cl-36 and Ni-63 as mandatory additionally Sr-90 analyses can be done over the samples and others will be checked in function of lab members interested

6 Homogeneity Homogeneity was checked by gamma spectrometry F test will be applied (ANOVA test of 4 gamma lines of each sample) ANOVA 1 Label m(g) L1 5,9246 L2 5,8083 L3 5,7638 L4 5,5171 L5 5,4929 L6 5,4027 L7 4,3498 L8 5,8259 L9 5,7722 L10 5,3328 L11 5,3560 L12 1,0621 Origin Sum X^2 Degre Fre SQ Aver. F Prob Crit.Value Am. Group 3372, , ,201 1,678E-79 3, In Group 12, , Total 3385, ANOVA 2 Origin Sum X^2 Degre Fre SQ Aver. F Prob Crit.Value Am. Group 2660, , ,679 7,367E-77 3, In Group 11, , Total 2672, ANOVA 3 Origin Sum X^2 Degre Fre SQ Aver. F Prob Crit.Value Am. Group 35, , , ,89E-23 3, In Group 9, , Total 45, ANOVA 4 Origin Sum X^2 Degre Fre SQ Aver. F Prob Crit.Value Am. Group 46, , ,9123 2,7E-26 3, In Group 9, , Co (1174 kev) 60 Co (1332 kev) 152 Eu (344 kev) Total 55, Cs (661 kev)

7 1Sample: 2 sub samples to mineralization process 3 aliquots per nuclide 3 replicates per measurement CWRRT. Data from the Labs Final results 6 specific activity data per Lab /nuclide and their uncertainty Each lab will receive the excel file to complete with the analytical data Lab label (Lab#) Private communication: all the result sending by to evaluator/coordinator only Lab and Evaluator will known this ID code Uncertainty estimation will be performed according to ISO/TS Guidance for the use of repeatability and trueness estimates in measurement uncertainty estimation 8-10/02/2012, PITESTI (RO) Radioactive CW-WP3&4 Waste MEETING Characterization - Practices and Trends

8 Lab data Calculations Intra-lab data calculation per sample (G1 and G2) Calculation of individual activity and uncertainty data to reference date 1/04/2008. Calculation of weighted average per sample and their uncertainty (6 data) Calculation of mean values and variance (selection of outliers) ( ) ( ) = = = = = n 1 j 2 j i n 1 j 2 j n 1 j j j i u 1 1 U u 1 u x X 2 i n 1 j 2 j i n 1 j j i Mean n x Var n x Mean = = = =

9 Selection of outliers (max 2/9 of initial value of Lab s) Cochran Test (rejected by intra-lab Variance) Outliners max(var) i Cochram_val= L var i= 1 Grub Test 1 Side (rejected by inter-lab means) Calculation of SD of the L means Cochram_ val> Critical_ val Calculation of SD of the L means except the highest (S H ) Calculation of SD of the L means except the lowest (S L ) SL Side_Grubs_ val = Max 1 ; S if 1Side_Grubs_ val> Critical_ vallab Grub Test 2 sides i ;if S 1 S 1 H ( ) outlier Calculation of SD of the L means in the cases S HL, S LL, S HH SLL SLH SHH 2Sides_Grubs_val = Min 1 ; 1 ; 1 S S S if 2Sides_Grubs_val> Critical_val ( Labs;replicants) outlier ( Lab) outlier

10 Reference Values Calculation of reference value Weighted average of all values except outliners: X ref = xi Ui U = 2 ref 2 ( 1 Ui ) ( 1 Ui ) 1 Two statistical approaches: Relative difference (Estimation of Lab Bias) xi X En = 2 2 En (u) numbers U + U i ref Q = x X 100 X i

11 E n (u) Score evaluation u Value P (%) Evaluation of x vs X Qualification u < Values are not significant differences Satisfactory (S) 2.015< u < < u < < u < < u < 90 Possibly Significant Doubts is cast on X, further evidences are needs for rejection Significant X could have significant differences with x, is needed further data Highly Significant. Probably the values have significant differences with X, needs further data to confirm Very highly significant Values differ Significantly Acceptable (A1) Acceptable (A2) Acceptable (A3) Non Satisfactory (NS) 8-10/02/2012, PITESTI (RO) Radioactive CW-WP3&4 Waste MEETING Characterization - Practices and Trends

12 Flow sheet Data Compilation Cochram Test Aberrant? Yes Drop Calculation Reference Values Calculation mean & Uncertainty No 1 Side Grubbs Test Q and u Evaluation Data Dropping Aberrant? No Yes Drop 2 Sides Grubbs Test Aberrant? Yes Drop Yes No Any Drop Labs? No

13 91 determinations treated from 16 lab results 1 Outliers by VARIANCE Tritium Evaluation 1,3E+00 3 H EVALUATION 1,2E+00 1,1E+00 1,0E+00 9,0E-01 8,0E-01 7,0E-01 6,0E-01 L11-1 L6-2 L6-1 L5-1 L2-1

14 8,0 6,0 4,0 2,0 0,0-2,0-4,0-6,0 L11-1 L5-1 S A1 A2 A3 NS 3 H u-score Tritium Evaluation > 1,30 0,30 0,25 3 H Q-score 0,20 0,15 0,10 0,05 0,00 L6-1 L5-1 L6-2 L2-1 L11-1 1,23-1,30 1,16-1,23 H-3 Activity distribution 0,81-0,88 0,88-0,95 0,95-1,02 1,02-1,09 1,09-1,16 <0,81 L2-1 L6-2 L H-3 Activity distribution by Lab L11 L10 L9 L8 L7 L6 L5 L4 L3 L2 <0,81 0,81-0,88 0,88-0,95 0,95-1,02 1,02-1,09 1,09-1,16 1,16-1,23 1,23-1,30 > 1,30

15 94 determinations treated from 17 labs No OUTLIERS Radiocarbon Evaluation 2,5E C EVALUATION 2,0E+00 1,5E+00 1,0E+00 5,0E-01 0,0E+00 L1-1 L6-2 L6-1 L5-1 L2-1 L11-1

16 C-14 Activity distribution Radiocarbon Evaluation C-14 Activity distribution by Lab % 38% L11 L10 L % 1% 1% 0,25-0, ,70 0,70-0,90 0,90-1,10 1,10-1,30 1,30-1,5 1,5-1,75 >1,75 6% ,25-0, ,70 0,70-0,90 0,90-1,10 1,10-1,30 1,30-1,5 1,5-1,75 >1,75 L8 L7 L6 L5 L4 L3 L2 L1 4,0 2,0 0,0-2,0-4,0-6,0-8,0 L11-1 L6-1 L5-1 L6-2 L C u-score S A1 A2 A3 NS L2-1 0,50 0,45 0,40 0,35 0,30 0,25 0,20 0,15 0,10 0,05 0,00 14 C Q-score L2-1 L1-1 L11-1 L6-1 L5-1 L6-2

17 Cobalt-60 Evaluation 111 determinations treated from 19 labs 2 Outliers by VARIANCE 1,3E+00 1,2E Co EVALUATION 1,1E+00 1,0E+00 9,0E-01 8,0E-01 7,0E-01 L6-2 L6-1 L5-1 L3-2 L2-1 L1-2 L1-1 L11-1

18 Co-60 Activity distribution Cobalt-60 Evaluation Co-60 Activity distribution by Lab % 28% 30 L11 L L % 20 L8 L % 8% 7% 3% <0,84 0,84-0,88 0,88-0,92 0,92-1,00 1,00-1,04 1,04-1,08 <1, <0,84 0,84-0,88 0,88-0,92 0,92-1,00 1,00-1,04 1,04-1,08 <1,08 L6 L5 L4 L3 L2 L1 6,0 4,0 60 Co u-score 0,16 0,14 60 Co Q-score 2,0 0,12 0,0 0,10-2,0-4,0-6,0-8,0-10,0 L11-1 L3-2 L1-1 L5-1 L2-1 L1-2 S A1 A2 A3 NS L6-2 L6-1 0,08 0,06 0,04 0,02 0,00 L1-1 L5-1 L2-1 L11-1 L6-2 L6-1 L3-2 L1-2

19 2,0E+00 1,8E+00 1,6E+00 1,4E+00 1,2E+00 1,0E+00 8,0E-01 6,0E-01 4,0E-01 2,0E-01 0,0E+00 Chlorine-36 Evaluation 6,0 36 Cl EVALUATION 4,0 2,0 L1-1 L1-1 14,0 12,0 10,0 8,0 6,0 4,0 2,0 0,0-2,0-4,0-6,0 S A1 A2 A3 NS 36 Cl u-score 0,70 0,60 0,50 0,40 0,30 0,20 0,10 0,00 L1-1

20 1,8E+00 1,6E Ni EVALUATION Nickel-63 Evaluation 1,4E+00 1,2E+00 1,0E+00 8,0E-01 6,0E-01 4,0E-01 2,0E-01 0,0E+00 L1-2 8,0 6,0 4,0 0,20 0,15 63 Ni Q-score 1,0 0 0,9 0 2,0 0,0-2,0-4,0-6,0-8,0 63 Ni u-score S A1 A2 A3 NS L1-2 0,10 0,05 0,00 L1-2 0,8 0 0,70 0,6 0 0,50 0,4 0 0,3 0 0,2 0

21 2,5E+01 Strontium-90 Evaluation 90 Sr EVALUATION 2,0E+01 1,5E+01 1,0E+01 5,0E+00 0,0E+00 8,0 16,00 90 Sr Q-score 6,0 14,00 4,0 12,00 2,0 10,00 0,0-2,0-4,0-6,0-8,0 90 Sr u-score S A1 A2 A3 NS 8,00 6,00 4,00 2,00 0,00

22 Evaluation by Lab 1,6E+00 1,4E+00 Xnuclide Xi 1,2E+00 1,0E+00 8,0E-01 6,0E-01 4,0E-01 H-3-1 H-3-2 Cl-36-2 Cl-36-1 C-14-2 C-14-1 Ni-63-2 Ni-63-1 Co-60-2 Co-60-1

23 Evaluation by Lab 4,0 3,0 2,0 1,0 0,0-1,0-2,0-3,0 H-3-1 S A1 A2 A3 NS H-3-2 C-14-1 C-14-2 Co-60-1 Cl-36-2 Cl-36-1 Ni-63-2 Ni-63-1 Co ,30 0,25 0,20 0,15 0,10 0,05 0,00 H-3-1 H-3-2 C-14-1 C-14-2 Co-60-1 Cl-36-2 Cl-36-1 Ni-63-2 Ni-63-1 Co-60-2 H-3-1 H-3-2 C-14-1 C-14-2 Cl-36-1 Cl-36-2 Co-60-1 Co-60-2 Ni-63-1 Ni-63-2 CAO CAO CAO CAO TD TD DM DM LLE LLE LSC LSC LSC LSC LSC LSC HGS HGS LSC LSC

24 CWRRT. Evaluation Summary 35 blind samples 12 (11) Lab s 464 x 3 primary data received 81 processed data evaluated Reference Values Calculation of 6 nuclides Extra inter-comparison γ emitters primary data elaborated outliers-c outliers-g H C Cl Co Ni Sr TOTAL u- Score Q-Score 25% 46% 4% 12% 4% 28% 9% 11% 9% 27% 25% S A1 A2 A3 NS < 5% 5-10% 10-25% 25-50% % > 100%

25 THANK YOU