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
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.
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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.
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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
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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”.
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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
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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Technical Assistance
 MAPEP provided technical assistance with sample dissolution
techniques.
U-234 Bias
Lab 1 Lab 2 Lab 3 Lab 4 Lab 5 Lab 6 Lab 7
MaS 30
-63%
-62%
-64%
-68%
-62%
-65%
-61%
MaS 31
-3.8%
4.9%
-25.9%
-7.6%
1.7%
-13.1%
-0.8%
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Initial Participation in
New Matrices
 When new matrices are offered, the participation is only ~20%.
Initial
Participation
Tc-99
MaS
I-129
XaW
Sr-89/90
Filter
20%
21%
17%
XrM
Ra-226
Unknown
27%
?
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MAPEP Series 31-32 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
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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.
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Uranium Results Reported By
Alpha Spectrometry
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MAS U-234 Letters of Concern
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MAPEP Series 32
False Positives
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False Positives Testing
False Positive Test
Antimony in water
25
20
15
10
5
Not Acceptable
Warning
0
MaW31
MaW32
Acceptable
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MAPEP Series 32 Sensitivity Tests
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Sr-89/90 Air Filter
Sr-89/90
Activity Ratio
SrF31
12
SrF32
45
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Tc-99 Soil Letter of Concerns
by Series
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Performance Evaluation of Tc-99
in Soil
 TcO4- anion should be a completely water soluble species, unlike
plutonium.
 However…
 It has been found that TcO4- is extremely insoluble in some soils.
 Treatment of the soils using alkaline fusion techniques and/or
treatment with HF was necessary for accurate results.
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Base Soil Analytical Values
Soil 1
Element
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lead
Nickel
Thallium
Vanadium
Zinc
Soil 2
Total
% Leachable mg/Kg
73
10
31
831
100
1.0
100
0.7
36
76
78
83
19
29
39
82
96
91
Total
% Leachable mg/Kg
60
8
31
393
46
2
66
0.3
13
93
75
17
49
36
82
28
39
42
19
0.8
21
121
Soil 3
Total
% Leachable mg/Kg
41
7
31
177
33
1.1
69
0.2
35
35
71
7
91
10
53
9
52
25
63
0.3
39
36
53
63
Soil 4
Soil 5
Total
% Leachable mg/Kg
73
7
21
565
99
0.7
69
0.5
28
51
100
5
100
15
75
13
78
20
36
60
66
85
Total
% Leachable mg/Kg
84
10
28
405
51
1.8
83
0.5
37
57
76
10
50
33
67
18
73
26
60
0.6
41
59
78
105
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Pu-239/240 Alpha Spec
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MASS Determinations
 Mass determinations of Pu-239 and Am-241 were evaluated
for the 1st time in MaW32 session.
Study Analyte Bias %
MaW32
Am-241
-4.1
Pu-239
5.0
U-238
-0.8
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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.
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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?
 Email MAPEP@ID.DOE.GOV
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RESL Contacts
 Anita Bhatt, RESL Director – bhattar@id.doe.gov
 Shane Steidley, MAPEP Database – steidlsd@id.doe.gov
 Guy Marlette, MAPEP Coordinator – marletgm@id.doe.gov
 Technical assistance can be requested from MAPEP chemists.
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MAPEP Websites
http://www.inl.gov/resl/mapep
 Public access
 Statistical summary
http://mapep.inl.gov
 Requires account /password
 Used for reporting/reviewing data
 Various search utilities, historical performance reviews, graphs,
individual laboratory reports, sample descriptions, program
information.
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MAPEP Application
 http://www.inl.gov/resl/mapep
 Send completed forms to MAPEP@ID.DOE.GOV
 Any questions contact MAPEP coordinator
Guy Marlette (208-526-2532), marletgm@id.doe.gov
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