The EQRAIN Plutonium N° 10 is an evaluation program set up by CEA/CETAMA in order to evaluate the quality of results from nuclear measurement laboratories. The objective of this programme is to determine the plutonium concentration of a plutonium nitrate solution. Three ampoules were sent to each participant.
At the IM/nuclear group, it was decided to analyse both of the EQRAIN N° 10 samples, H53 and H91. The results of this exercise would possibly enable us to identify problems occuring during the handling and measurements by mass spectrometric isotope dilution analysis (IDMS) of Pu.
The evaluation of the mass-spectrometry analysis as part of this program could indicate unexplained processes such as the behaviour of the fractionation factor and outlier results not identified during measurements.JRC.D.4-Isotope measurement

AREGBE YETUNDE

EYKENS ROGER

KEHOE FRANCES

KUEHN HEINZ

RICHTER STEPHAN

VERBRUGGEN ANDRE

JRC Publications Repository

 
 
 
Certification Report of EQRAIN 
Plutonium Program N° 10 
 
 
 
 
A. Verbruggen, R. Eykens, F. Kehoe, H. Kühn, S. Richter, Y. Aregbe 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
PUBSY ID - EUR 22787 EN         2007 
          
 
 
 
  
The mission of IRMM is to promote a common and reliable European 
measurement system in support of EU policies. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
European Commission 
Directorate-General Joint Research Centre 
Institute for Reference Materials and Measurements 
 
Contact information 
André Verbruggen  
European Commission 
Directorate-General Joint Research Centre 
Institute for Reference Materials and Measurements  
Retieseweg 111 
B-2440 Geel • Belgium 
 
Email: andre.verbruggen@ec.europa.eu 
 
Tel.: +32 (0)14 571 617 
Fax: +32 (0)14 571 863 
 
http://www.irmm.jrc.be 
http://www.jrc.ec.europa.eu 
 
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Neither the European Commission nor any person acting on behalf of the Commission is 
responsible for the use which might be made of the following information. 
 
A great deal of additional information on the European Union is available on the Internet. 
It can be accessed through the Europa server 
http://europa.eu.int 
 
EUR Report 22787 EN 
ISBN 978-92-79-06026-7 
ISSN 1018-5593 
Luxembourg: Office for Official Publications of the European Communities 
 
© European Communities, 2007 
 
Reproduction is authorised provided the source is acknowledged 
 
Printed in Belgium 
  
 
 
Certification Report of EQRAIN Plutonium 
Program N° 10 
 
  
A. Verbruggen,  R. Eykens, F. Kehoe, H. Kühn, 
S. Richter, Y. Aregbe 
 4 
Contents 
 
 
Contents.............................................................................................................................. 4 
Introduction ......................................................................................................................... 5 
Isotopic amount ratios ......................................................................................................... 5 
Measurement of isotopic amount concentrations................................................................ 5 
Conclusions......................................................................................................................... 8 
References 8 
 5 
Introduction 
The EQRAIN Plutonium N°10 (Evaluation de la Qualité des Résultats d'Analyse dans 
l'Industrie Nucléaire) is an evaluation program set up by CETAMA (la Commission 
d’Etablissement de Methodes d’Analyses) in order to evaluate the quality of results from 
nuclear measurement laboratories. 
The objective of this programme is to determine the plutonium concentration of a plutonium 
nitrate solution. Three ampoules were sent to each participant. 
At the IM/nuclear group, it was decided to analyse both of the EQRAIN N°10 samples, more 
specifically sample Pu H53 and Pu H91. The results of this exercise would possibly enable us 
to identify problems occurring during the handling and measurements by mass-spectrometric 
Isotope dilution analysis (IDMS) of Pu. 
The evaluation of the mass-spectrometry analysis as part of this program could indicate 
unexplained processes such as the behaviour of the fractionation factor and outlier results not 
identified during measurements. 
 
Isotopic amount ratios 
As the material is originally a MP2 metal, the isotope abundance ratios from the IRMM 
measurement certificate were used. Recertification of the isotope amount ratios of MP2 was 
accomplished recently and a certificate was issued valid for 1 January 2007. The values were 
recalculated for decay to the date of measurement 13 March 2007. 
 
Table 1: Isotopic ratios and abundances 
 
Isotope amount  ratio(s) 
n(238Pu)/n(239Pu) 0.000 030 78(29) 
n(240Pu)/n(239Pu) 0.022 432 1(51) 
n(241Pu)/n(239Pu) 0.000 235 4(31) 
n(242Pu)/n(239Pu) 0.000 075 70(78) 
 
amount fraction (·100) mass fraction (·100) 
n(238Pu)/n(Pu) 0.003 010(28) m(
238Pu)/m(Pu) 0.002 997(28) 
n(239Pu)/n(Pu) 97.773 31(58) m(
239Pu)/m(Pu) 97.764 06(58) 
n(240Pu)/n(Pu) 2.193 26(49) m(
240Pu)/m(Pu) 2.202 24(49) 
n(241Pu)/n(Pu) 0.023 02(30) m(
241Pu)/m(Pu) 0.023 21(30) 
n(242Pu)/n(Pu) 0.007 402(76) m(
242Pu)/m(Pu) 0.007 49(77) 
 
Measurement of isotopic amount concentrations 
The isotope concentrations of the Eqrain N°10 sample were measured by IDMS. From both 
samples, 3 blends were prepared consisting of 0.15 - 0.20 - 0.25 g sample spiked with 5 g 
IRMM-049c. Prior to mass-spectrometric measurement the samples were chemically 
conditioned and purified by anion exchange with nitric acid as medium. 
The n(239Pu)/n(242Pu) ratios of the blends were measured on the Finnigan MAT262 thermal 
ionisation mass spectrometer. A turret  was loaded with the 6 blends and 5 standards (IRMM-
290 A3, E and G3) and stored with following filename: 27116. 
 
The isotopic measurements were carried out in static Faraday multi-collector mode using the 
total evaporation technique as described in [1, 2] and in working instruction WI-0115 of the 
IRMM IM-Unit quality system. 
 
The fractionation factor derived from the measurements of the series of IRMM-290 samples 
was applied in the IDMS GUM workbenches [3, 4] as follows: 
Kapplied = Kmeas *  Kbase 
 6 
where Kbase  = 1 with a relative standard uncertainty = 0.015% 
  
Kbase is included to eliminate inadvertently arriving at a K factor with negligible uncertainty: 
always a risk with a small series of measurements. 
The overview of measurement results for the samples is shown in Table 2. The K factor, 
calculated by the ratio of the observed values and certified values for n(242Pu)/n(239Pu) for this 
part of the campaign is shown in Table 3. Mean values per magazine were calculated as well 
as the overall value of Kmeas = 0.999 71 ± 0.000 23 (SE for n=6). 
 
For the calculation of the isotopic concentrations of the samples of Eqrain N°10, the values of 
Table 1, 2 and 3 are the input values of the GUM workbench. In the calculation using GUM 
workbench, a term δi is added to each individual isotope dilution calculation. This term 
expresses a possible effect in the measurement which contributes to the uncertainty – if 
present. Each δ has a value of zero and a standard uncertainty that can be adjusted if 
necessary. Each δ has the same uncertainty, u(δ). 
The value of u(δ) is assigned after inspection of the absolute difference between individual 
isotope dilution results and their mean value as given in each case by: 
εi = | cPui - cPumean| 
 
In this measurement campaign the uncertainty contribution from each εi to the final 
uncertainty of CPu was 1.7%. This is negligible contribution to the overall uncertainty and 
shows that the assumption that an extra effect is present in the IDMS measurements is not 
warranted. 
 
Table 4 shows the result of the IRMM measurements. 
Table 5 shows the components of uncertainty for samples H53 and H91 of Eqrain N°10. 
All data used can be found in S:\Im UNIT\Secure Data\Project Data\EQRAIN10 
All values for plutonium isotope ratios and concentrations are corrected for decay to 13 March 
2007. 
 
Table 2: Measurements of blends  
 ID filename n(242Pu)/n(239Pu) 
1 FIL 03 H53 015 27308.CSV 0.696 644 
2 FIL 05 H53 020 2730806.CSV 0.533 245 
3 FIL 07 H53 030 2730808.CSV 0.425 158 
4 FIL 09 H91 015 2730810.CSV 0.684 964 
5 FIL 11 H91 020 2730812.CSV 0.484 927 
6 FIL 13 H91 025 2730814.CSV 0.427 092 
 
Table 3: Calculated fraction factor for n(239Pu)/n(242Pu) ratio  
Date ID Reference Mat K[n(
242Pu)/n(239Pu)] 
13/05/04 FIL 04 E3 TE IRMM-290 E3 0.999 94 
13/05/04 FIL 06 G3 TE IRMM-290 G3 0.999 65 
13/05/04 FIL 08 A3 TE IRMM-290 A3 1.000 04 
13/05/04 FIL 10 E3 TE IRMM-290 E3 0.998 86 
13/05/04 FIL 12 G3 TE IRMM-290 G3 1.000 09 
  average 0.999 71 
  SE 0.000 23 
 
 
Table 4: Measured Isotope concentration of Eqrain N°10 samples (Uc k=2) 
 
Solution Reference Pu mass content (g·kg-1) 
measured 
Pu mass content (g·kg-1) 
certified 
H53 4.161 2(70) 4.162(4) 
H91 4.256 9(64) 4.261(4) 
 7 
 
 
 
 
 
Table 5: Components of uncertainty for IDMS of sample H53 
 
Quantity Value Standard Uncertainty Index 
ΔtMP2 0.20260 a 1.56·10-3 a 0.0 % 
R238/239 30.833·10-6 mol/mol 146·10-9 mol/mol 0.0 % 
R240/239 0.02243240 mol/mol 2.54·10-6 mol/mol 0.0 % 
R241/239 237.77·10-6 mol/mol 1.55·10-6 mol/mol 0.0 % 
R242/239 75.704·10-6 mol/mol 389·10-9 mol/mol 0.0 % 
τ 238 87.700 a 0.300 a 0.0 % 
τ 239 24110.0 a 30.0 a 0.0 % 
τ 240 6563.00 a 7.00 a 0.0 % 
τ 241 14.2900 a 0.0600 a 0.0 % 
τ 242 373.50·103 a 1100 a 0.0 % 
cy.IRMM049c 366.650·10-9 g/mol 245·10-12 g/mol 62.6 % 
R239/242Pu.IRMM049c 2.2120·10-3 mol/mol 17.0·10-6 mol/mol 0.0 % 
Δtspike 10.8695 a 0.0111 a 0.0 % 
Rb1 1.435450 144·10-6 0.2 % 
Rb2 1.875310 188·10-6 0.2 % 
Rb3 2.352070 235·10-6 0.2 % 
mx1 0.154320 g 28.9·10-6 g 0.5 % 
mx2 0.201620 g 28.9·10-6 g 0.3 % 
mx3 0.254390 g 28.9·10-6 g 0.2 % 
my1 4.996700 g 289·10-6 g 0.0 % 
my2 4.999000 g 289·10-6 g 0.0 % 
my3 5.016400 g 289·10-6 g 0.0 % 
Kmeas 1.000285 228·10-6 7.3 % 
Kbase 1.000000 150·10-6 3.2 % 
δ 1 0.0 10.0·10-9 8.4 % 
δ 2 0.0 10.0·10-9 8.4 % 
δ 3 0.0 10.0·10-9 8.4 % 
γPu 4.16119·10-3 g/g 3.51·10-6 g/g 
 
Table 6: Components of uncertainty for IDMS of sample H91 
 
Quantity Value Standard Uncertainty Index 
ΔtMP2 0.20260 a 1.56·10-3 a 0.0 % 
R238/239 30.833·10-6 mol/mol 146·10-9 mol/mol 0.0 % 
R240/239 0.02243240 mol/mol 2.54·10-6 mol/mol 0.0 % 
R241/239 237.77·10-6 mol/mol 1.55·10-6 mol/mol 0.0 % 
R242/239 75.704·10-6 mol/mol 389·10-9 mol/mol 0.0 % 
τ 238 87.700 a 0.300 a 0.0 % 
τ 239 24110.0 a 30.0 a 0.0 % 
 8 
Quantity Value Standard Uncertainty Index 
τ 240 6563.00 a 7.00 a 0.0 % 
τ 241 14.2900 a 0.0600 a 0.0 % 
τ 242 373.50·103 a 1100 a 0.0 % 
cy.IRMM049c 366.650·10-9 g/mol 245·10-12 g/mol 78.0 % 
R239/242Pu.IRMM049c 2.2120·10-3 mol/mol 17.0·10-6 mol/mol 0.0 % 
Δtspike 10.8695 a 0.0111 a 0.0 % 
Rb1 1.459930 146·10-6 0.2 % 
Rb2 2.062160 206·10-6 0.2 % 
Rb3 2.341420 234·10-6 0.2 % 
mx1 0.153500 g 28.9·10-6 g 0.7 % 
mx2 0.217300 g 28.9·10-6 g 0.3 % 
mx3 0.245800 g 28.9·10-6 g 0.3 % 
my1 4.995200 g 289·10-6 g 0.0 % 
my2 5.008400 g 289·10-6 g 0.0 % 
my3 4.988100 g 289·10-6 g 0.0 % 
Kmeas 1.000285 228·10-6 9.1 % 
Kbase 1.000000 150·10-6 3.9 % 
δ 1 0.0 6.00·10-9 2.3 % 
δ 2 0.0 6.00·10-9 2.3 % 
δ 3 0.0 6.00·10-9 2.3 % 
γPu 4.25693·10-3 g/g 3.22·10-6 g/g 
 
Conclusions 
The measurement of the samples provided through the Eqrain N°10 program has proven to 
be very useful. A number of conclusions could be drawn: 
Analysis of the components of uncertainty on the ratio of measured values of IDMS on the 
MAT262 gave very satisfactory result. The major contributor to the total uncertainty is the 
uncertainty of the spike isotopic reference material used (62.6% and 78.0%); the influence of 
the fractionation is ca 10-15%. The variation within the IDMS sub-samples can contribute up 
to 25 % of the total uncertainty. 
The results of the independent measurements of the samples show that we can have high 
confidence in our capacity to provide reliable results. We have found acceptable agreement 
with the certified value demonstrating the reliability of our procedures, methodology and 
competence of the people. 
 
References 
[1] R. Fiedler, Int. J. of Mass Spectr., 146,147 (1995) 91-97. 
[2] E. L. Callis and R. M. Abernathy, Int. J. of Mass Spectr., 103, (1991) 93-105. 
[3] International Organisaton for Standardisation, Guide to the Expression of Uncertainty in 
Measurements, ©ISO, ISBN 92-67-10188-9, Geneva, Switserland 1993 
[4] GUM Workbench, Metrodata GmbH, www.metrodata.de 
 9 
 
European Commission 
 
EUR 22787 EN – DG Joint Research Centre, Institute for Reference Materials and Measurements – 
Certification Report of EQRAIN Plutnium Program N° 10 
Authors: A. Verbruggen, R. Eykens, F. Kehoe, H. Kühn , S. Richter, Y. Aregbe 
Luxembourg: Office for Official Publications of the European Communities 
2007 – 9 pp. – 21.0 x 29.7 cm  
EUR - Scientific and Technical Research series; ISSN 1018-5593 
ISBN 978-92-79-06026-7 
 
 
 
Abstract 
The EQRAIN Plutonium N°10 (Evaluation de la Qualité des Résultats d'Analyse dans l'Industrie Nucléaire) 
is an evaluation program set up by CETAMA (la Commission d’Etablissement de Methodes d’Analyses) in 
order to evaluate the quality of results from nuclear measurement laboratories. 
The objective of this programme is to determine the plutonium concentration of a plutonium nitrate 
solution. Three ampoules were sent to each participant. At the IM/nuclear group, it was decided to analyse 
both of the EQRAIN N°10 samples, more specifically sample Pu H53 and Pu H91. The results of this 
exercise would possibly enable us to identify problems occurring during the handling and measurements 
by mass-spectrometric Isotope dilution analysis (IDMS) of Pu. 
The evaluation of the mass-spectrometry analysis as part of this program could indicate unexplained 
processes such as the behaviour of the fractionation factor and outlier results not identified during 
measurements.  
  
 
 
The mission of the Joint Research Centre is to provide customer-driven scientific and technical 
support for the conception, development, implementation and monitoring of European Union policies. 
As a service of the European Commission, the JRC functions as a reference centre of science and 
technology for the Community. Close to the policy-making process, it serves the common interest of 
the Member States, while being independent of special interests, whether private or national. 
 
                                                                                                           
 
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Certification Report of EQRAIN Plutonium - Program N° 10

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Certification Report of EQRAIN Plutonium - Program N° 10

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