The U. S. Department of Energy’s Mixed-Analyte Performance Evaluation Program - MAPEP FY 2015 Review Anita Bhatt, Shane Steidley DOE Radiological and Environmental Sciences Laboratory ASP Meeting 2015 Sept. 14, 2015

2 ASP Objectives Assure that data acquired from analytical environmental laboratories are valid, reliable and defensible. Provide quality assurance, risk reduction, & cost efficiencies for DOE site managers, workers, and the public. Defensible environmental data support confident decision- making and regulatory (milestones) compliance.

3 MAPEP Objectives Supports ASP objectives in addition to the DOE mission. Performance Evaluation Program.  Evaluates analytical work based on performance. Address specific analytical issues routinely encountered that affect the accuracy of the results. Tests the accuracy of analytical procedures on a variety of real samples being submitted to DOE for analysis.

4 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

5 MAPEP Criticism “In my opinion the MAPEP sessions came off with an arrogant tone” … “I think RESL MAPEP program is one of the best in the world – if not the best” … not notifying or providing any communication that changes were being initiated. … intention by RESL deceive (or trick) the participating laboratories without stating the changes to the uranium sample/standard… “MAPEP personnel need to stop telling labs how incompetent they are. … Feel free to provide my name with this comment”.

6 Job of the Analytical Chemist “The responsibility of an analytical chemist is to accurately determine the analyte of interest in the sample being submitted for analysis. Lately, there has been a trend to excuse poor performance and rationalize inadequate chemical procedures or inaccurate work as acceptable.” David S. Sill

7 Discussion In Last ASP “We don’t have insoluble forms of Plutonium in our samples…we know our source term and it only contains analytes that are leachable.”  How do they know???  It is impossible to determine the species of Plutonium without doing the analytical work.  Insoluble Plutonium can be formed in the analytical method itself. It does not have to be present in the original sample. – Muffling the organic sample, evaporation to dryness, etc.  The most stable form of Plutonium is the insoluble form.

8 Discussion In Last ASP “Deposited Plutonium on urban matrices does not require total dissolution.”  It is the chemical form (oxidation state) of the Plutonium, not its physical location that is important. – The Plutonium on the surface of concrete, glass, or building materials can be just as insoluble as if it were in the middle of the sample. – Leaching will not produce an accurate result on superficially contaminated urban matrices when insoluble Plutonium is present.

9 Discussion In Last ASP “Total dissolution is not economically or physically feasible for commercial labs...”  Bids should reflect what it actually costs to produce accurate results.  There are numerous dissolution techniques that produce accurate and reliable results without being economically burdensome.

10 Discussion In Last ASP “DOECAP Priority 1 finding hurts the reputation of the Laboratory.”  Repeated analytical failure generate Priority 1 finding.  Many laboratories that fail MAPEP claim the test is unfair as they are contractually obligated to use certain methods.  This situation is similar to DU, I-129, Sb, and False Positive testing problems encountered by MAPEP.  Problems are degenerating into personal attacks.

11 Discussion In Last ASP “Our customer (DOE) doesn’t want total numbers; they prefer leachable numbers…labs are contractually obligated to use leaching procedures…”  Is it acceptable to knowingly underestimate the amount of Plutonium in the environment or leave an unknown quantity of radioactive material undetected in the sample?  DOE does not condone the generation of inaccurate results.  Many data users don’t know that there are insoluble forms of radionuclides and may assume leachable results represent the total.

12 Specifics Suggestions Chemical dissolution techniques should address the common problems encountered in real world samples. Results obtained by acid leaching of the sample will not be accurate if insoluble compounds or insoluble matrix components are present, and there is no way to tell without proper analysis.

13 Specifics Suggestions Leaching techniques should only be used when proven to be effective and demonstrated to produce accurate results equal to total dissolution methods. MAPEP is performance based and does not mandate the use of specific analytical techniques. MAPEP evaluates analytical performance based on NIST Traceable reference values, and not experimentally determined consensus values.

14 Technical Assistance MAPEP provided technical assistance with sample dissolution techniques. U-234 Bias

15 Initial Participation in New Matrices When new matrices are offered, the participation is only ~20%.

16 MAPEP Series Overview MAPEP System Usage Agreement Technical Highlights  Uranium in Soil  False Positive/Sensitivity Tests  Sr-89/90 Air Filter  Tc-99 Soil Note  Pu-239 & Am-241 Reported by Mass Spectrometry

17 MAPEP System Usage Agreement Agree to abide by MAPEP’s System Usage Agreement or Export Control Agreement. Labs are required to update SUA after 6 months.

18 Uranium Results Reported By Alpha Spectrometry

19 MAS U-234 Letters of Concern

20 MAPEP Series 32 False Positives

21 False Positives Testing

22 MAPEP Series 32 Sensitivity Tests

23 Sr-89/90 Air Filter Sr-89/90 Activity Ratio SrF3112 SrF3245

24 Tc-99 Soil Letter of Concerns by Series

25 Performance Evaluation of Tc-99 in Soil TcO 4 - anion should be a completely water soluble species, unlike plutonium. However… It has been found that TcO 4 - is extremely insoluble in some soils. Treatment of the soils using alkaline fusion techniques and/or treatment with HF was necessary for accurate results.

26 Base Soil Analytical Values

27 Pu-239/240 Alpha Spec

28 MASS Determinations Mass determinations of Pu-239 and Am-241 were evaluated for the 1st time in MaW32 session.

29 Special Radiological Matrix XrM for Series 33 Special Radiological Matrix (XrM)  Undisclosed sample matrix and radionuclides.  Activity to be reported per sample.  Results will be evaluated based on bias from the known.  Acceptance flags will not be assigned to results. – Non punative, promote increased scientific capability, … Designed to encourage participants to test full analytical capabilities.  Thirty seven laboratories requested the XrM sample.

30 Performance Testing Material Ra-226 Based on customer requests, RESL is considering a Ra-226 Performance Testing Material.  Water ?  Soil, Vegetation, Filters ? Is there an interest in a Ra-226 standard? 

31 RESL Contacts Anita Bhatt, RESL Director – Shane Steidley, MAPEP Database – Guy Marlette, MAPEP Coordinator – Technical assistance can be requested from MAPEP chemists.

32 Public access Statistical summary Requires account /password Used for reporting/reviewing data Various search utilities, historical performance reviews, graphs, individual laboratory reports, sample descriptions, program information. MAPEP Websites

33 Send completed forms to Any questions contact MAPEP coordinator Guy Marlette ( ), MAPEP Application