The isotopic reference material IRMM-3100a was prepared by gravimetrical dilution of IRMM-3101. The primary solution IRMM-3101 was designed such that the material consists of equivalent parts of four individual isotopes n(233U)/n(235U)/n(236U)/n(238U) with a ratio of one. 
The certified isotope amount ratio  for ratio n(233U)/n(236U) has been established by mass metrology and was verified by isotope mass spectrometry. The certified ratios n(234U)/n(236U), n(235U)/n(236U) and n(238U)/n(236U) have been measured  by TIMS in multi-dynamic mode and using the n(233U)/n(236U) ratio for internal normalization. The preparation of IRMM-3101 is in full described elsewhere. [1]
The Isotopic Reference Material IRMM-3100a is part of a systematic IRMM programme to supply Isotopic Reference Materials of various isotopes at different concentrations. The Isotopic Reference Material is supplied in a quartz ampoule containing 0.5 mL of a 1 M nitric acid solution.JRC.DG.D.2-Reference material

AREGBE Yetunde

EYKENS Roger

JAKOBSSON Ulf

KEHOE Frances

KUEHN Heinz

RICHTER Stephan

VERBRUGGEN Andre

JRC Publications Repository

  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
EUR 24559 EN  -  2010 
Preparation and Verification of QUAD 
Uranium Isotopic Reference Material 
IRMM-3100a 
A. Verbruggen, R. Eykens, F. Kehoe, H. Kühn, U. Jacobsson, 
S. Richter, Y. Aregbe 
 
  
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JRC 61143 
 
EUR 24559 EN 
ISBN 978-92-79-17197-0 
ISSN 1018-5593 
doi:10.2787/31471 
 
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© European Union, 2010 
 
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IRMM information 
REFERENCE MATERIALS 
 
 
 
 
Preparation and Verification of QUAD 
Uranium Isotopic Reference Material  
 
IRMM-3100a 
 
 
A. Verbruggen, R. Eykens, F. Kehoe, H. Kühn, U. Jacobsson, 
S. Richter, Y. Aregbe 
 
 
 
 
European Commission,  
Joint Research Centre 
Institute for Reference Materials and Measurements 
Retieseweg 111 
2440 Geel, Belgium 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
        
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Disclaimer 
 
 
Certain commercial equipment, instruments, and materials are identified in 
this report to specify adequately the experimental procedure. In no case does such identification imply 
recommendation or endorsement by the European Commission, nor does it imply that the material or equipment 
is necessarily the best available for the purpose. 
 
 1 
Table of Contents 
 
1 Introduction 2 
2 Design of IRMM-3100a 2 
3 Verification of IRMM-3100a 2 
4 Certification of IRMM-3100a 4 
5 Ampouling of IRMM-3100a 5 
6 Conclusions 5 
7 References 5 
 
Table 1: Verification measurements for IRMM-3100a 3 
Table 2: Isotopic composition of IRMM-3100a 4 
 
Figure 1: Verification measurements for IRMM-3100a 4 
Figure 2: Certificate IRMM-3100a 7 
 2 
1 Introduction 
Isotopic reference material IRMM-3100a was prepared by gravimetrical dilution of IRMM-
3101. The primary solution IRMM-3101 was designed such that the material consists of 
equivalent parts of four individual isotopes n(233U)/n(235U)/n(236U)/n(238U) with a ratio of one.  
The certified isotope amount ratio1 for ratio n(233U)/n(236U) has been established by mass 
metrology and was verified by isotope mass spectrometry. The certified ratios 
n(234U)/n(236U), n(235U)/n(236U) and n(238U)/n(236U) have been measured  by TIMS in multi-
dynamic mode and using the n(233U)/n(236U) ratio for internal normalization. The preparation 
of IRMM-3101 is described elsewhere [1]. 
The Isotopic Reference Material IRMM-3100a is part of a systematic IRMM programme to 
supply Isotopic Reference Materials of various isotopes at different concentrations. The 
Isotopic Reference Material is supplied in a quartz ampoule containing 1 mL of a 1 M nitric 
acid solution. 
 
2 Design of IRMM-3100a 
The primary solution IRMM-3101 was designed such that the material consists of equivalent 
parts of four individual isotopes n(233U)/n(235U)/n(236U)/n(238U) with a ratio of one. The 
starting materials, highly enriched 99.96% 233U (IRMM-3630), 99.994% 235U (IRMM-3650), 
99.97% 236U (IRMM-3660) and 99.99998% 238U (IRMM-3680), were selected to prepare the 
primary QUAD IRM solution. A further 10-fold dilution of the primary mixture was made to 
prepare IRMM-3100a in 1 M nitric acid matrix. The uranium concentration is at the level of 
0.1 mg U per g of solution, the isotopic composition is should be identical to the certified 
isotopic composition of IRMM-3100. 
The n(233U)/n(236U) isotopic ratio of IRMM-3101 was calculated from the masses of the 
starting solutions mixed together and their respective isotopic compositions, the remaining 
isotope ratios were derived from the results of the TIMS measurements using n(233U)/n(236U) 
as internal standard. The certification of isotopic ratios in the starting materials and IRMM-
3101 has been reported [1]. 
 
3 Verification of IRMM-3100a 
Verification measurements were carried out using the TRITON TIMS and using the total 
evaporation procedure [3, 4]. 
For the mass fractionation correction two certified reference materials were used. The 
certified reference material IRMM-3636a has a n(233U)/n(236U) ratio of 1.01906 ± 0.016%, 
close to unity. IRMM-3636a (0.1 mg U/g) is a dilution of IRMM-3636 (1 mg U/g), a mixture of 
highly enriched 233U and 236U materials; the very same solutions were used within few days 
time also to prepare the original quad mixture IRMM-3101. Therefore IRMM-3636a is 
suitable standard for the verification measurement of IRMM-3100a. 
As an additional standard, IRMM-074/10 with a n(235U)/n(238U) ratio of 1.00026 ± 0.015% 
was used. The new reference material IRMM-3100a is a 1/10 dilution of IRMM-3101 and 
should therefore have the same isotopic composition. This was confirmed, as shown in 
Table 1 and Figure 1, by means of verification for the n(233U)/n(236U), n(235U)/n(236U) and 
n(238U)/n(236U) ratios of IRMM-3100a, using IRMM-3636a and IRMM-074/10 as standards. 
As a conclusion, the isotopic compositions of IRMM-3100a and the original quad mixture 
IRMM-3101 are in agreement. 
 
                                                     
 
 
 
1
 Note: All uncertainties indicated are expanded uncertainties U = k·uc where uc is the combined 
standard uncertainty calculated according to the ISO guide. They are given in parentheses and 
include a coverage factor k = 2. They apply to the last two digits of the value. The values certified are 
traceable to the SI. 
 3 
Table 1: Verification measurements for IRMM-3100a 
 
Deviation of measured 
n(233U)/n(236U) ratio 
from gravimetrical value 
Uncertainty 
k=2 
Augmented* 
Uncertainty, 
k=2 
TE TRITON 1-Turret T091109 -0.033% 0.026% 0.042% 
TE TRITON 1-Turret T091207 -0.024% 0.024% 0.041% 
TE TRITON 2-Turret P100126 -0.033% 0.039% 0.051% 
TE TRITON 2-Turret P100503 -0.011% 0.035% 0.048% 
TE TRITON 2-Turret P100514 -0.010% 0.031% 0.045% 
 
 
Deviation of measured 
n(235U)/n(236U) ratio 
from gravimetrical value 
Uncertainty 
k=2 
Augmented* 
Uncertainty, 
k=2 
TE TRITON 1-Turret T091109 -0.010% 0.008% 0.014% 
TE TRITON 1-Turret T091207 -0.007% 0.008% 0.014% 
TE TRITON 2-Turret P100126 -0.008% 0.013% 0.017% 
TE TRITON 2-Turret P100503 0.000% 0.012% 0.016% 
TE TRITON 2-Turret P100514 0.000% 0.010% 0.015% 
 
 
Deviation of measured 
n(238U)/n(236U) ratio 
from gravimetrical value 
Uncertainty 
k=2 
Augmented* 
Uncertainty, 
k=2 
TE TRITON 1-Turret T091109 0.015% 0.017% 0.028% 
TE TRITON 1-Turret T091207 0.009% 0.016% 0.027% 
TE TRITON 2-Turret P100126 0.037% 0.036% 0.043% 
TE TRITON 2-Turret P100503 0.029% 0.023% 0.032% 
TE TRITON 2-Turret P100514 0.027% 0.020% 0.030% 
 
TE = total evaporation method. 
TRITON 1 and TRITON 2 are two TIMS instruments at IRMM. 
*The uncertainties have been augmented by an additional relative uncertainty 
component associated to the external calibration of the TE method using a standard. 
This uncertainty contribution was quantified to be 0.032%, based on measurements 
of the gravimetrically prepared reference materials such as IRMM-074/10 and 
IRMM-3636a against each other [7].  
 
 4 
Verification Measurements for IRMM-3100a
-0,15%
-0,10%
-0,05%
0,00%
0,05%
0,10%
0,15%
Gravimetrical
Value
TE TRITON 1,
T091109
TE TRITON 1,
T091207
TE TRITON 2,
P100126
TE TRITON 2,
P100503
TE TRITON 2,
P100514
D
ev
ia
tio
n
 
o
f  
 
n
(23
3 U
)/n
(23
6 U
) fr
om
 
gr
a
v.
 
va
lu
e
Gravimetrical Value
Uc of grav value (0.016%)
 
Figure 1: Verification measurements for the n(233U)/n(236U) ratio of IRMM-3100a. Error bars represent 
uncertainties with a coverage factor k = 2. 
 
4 Certification of IRMM-3100a 
As confirmed by the verification measurements, IRMM-3100a and IRMM-3101 have 
the same isotopic composition. The certified values for the isotope amount ratios 
and uncertainties are published earlier [1] and were calculated according to 
ISO/GUM recommendations [8] using the GUM Workbench [9] as listed in Table 2.  
The uncertainty budget shows for all ratios an almost 100% contribution from the 
n(233U)/n(236U) ratio used for internal mass fractionation. The uncertainty for the 
n(234U)/n(236U) ratio is dominated by Faraday collector noise. 
 
Table 2: Isotopic composition of IRMM-3100a 
Certified amount ratios 
n(233U)/n(236U) 1.019 90(16) 
n(234U)/n(236U) 0.000 383 7(20) 
n(235U)/n(236U) 1.004 354(54) 
n(238U)/n(236U) 0.987 98(11) 
amount fraction (·100) mass fraction (·100) 
n(233U)/n(U) 25.417 3(34) m(233U)/m(U) 25.149 2(33) 
n(234U)/n(U) 0.009 562(50) m(234U)/m(U) 0.009 502(50) 
n(235U)/n(U) 25.029 89(64) m(235U)/m(U) 24.978 84(66) 
n(236U)/n(U) 24.921 37(69) m(236U)/m(U) 24.976 52(68) 
n(238U)/n(U) 24.621 9(33) m(238U)/m(U) 24.886 0(33) 
The molar mass of the uranium is 235.524 36(17) g·mol-1 
 5 
5 Ampouling of IRMM-3100a  
Sampling of batch IRMM-3100a was carried out in a double section fume hood in 
the controlled area. The precleaned 2 mL quartz ampoules were filled with about 
1 mL of solution by means of a 5 mL size dispenser. Each ampoule contained about 
100 µg total uranium. The fume hood was fitted with a new plastic interior. A part 
was used to set up flask and liquid dispenser. A sufficient number of clean quartz 
ampoules, dispensers and tubing were brought into the controlled area from the 
clean lab. The area around and under the filling station was covered with a fresh 
layer of clean room wipes prior to ampuling. 
The flask containing the IRMM-3100a solution to be processed was then opened. 
The dispenser was carefully fitted onto the flask, taking care to keep the ends of the 
tubing clean. One tube was then carefully inserted into the flask so that it reached 
the bottom of the flask. The other tubing was inserted into the vial. The required 
volume was then transferred from flask into the ampoule with the dispenser. The 
ampoule was inspected that there was no solution on the top or outside and placed 
into a rack.  
From there it was put into a small PTFE holder and sealed using an oxygen-
acetylene flame. After visual inspection the ampoule was placed into a rack to cool. 
This was done in a continuous process, with one ampoule being processed in less 
than a minute, on the average.  
From earlier experiments and testing carried out during similar operations [8], the 
maximum possible contamination from environmental uranium during the 
preparation of the mother solutions, dilutions, ampoule filling and the sealing 
process is estimated to be about 26 pg uranium (1.1·10- 6 mol). Possible 
contamination at this level of uranium with natural isotopic composition has no 
significant effect on the isotopic ratios of IRMM-3100a. 
 
6 Conclusions 
The preparation of IRMM-3100a has been successfully accomplished by dilution of IRMM-
3101 a material prepared at IRMM to be used for production of the uranium QUAD series.  
IRMM-3100a has been prepared and verification measurements were accomplished 
successfully. The certified values of the isotope amount ratio of n(233U)/n(236U) have 
been calculated based on the masses of oxides and solutions and verified by the 
uncertainties of the mixing calculations and by independent TIMS measurements. 
The remaining isotope ratios n(234U)/n(236U), n(235U)/n(236U) and n(238U)/n(236U) were 
determined by thermal ionization mass spectrometry used in a multi dynamic mode, 
using the n(233U)/n(236U) ratio for internal mass fractionation correction.  
Verification measurements for the certified isotopic composition of IRMM-3100a 
were performed successfully by the Safeguards Analytical Services (SGAS) of the 
International Atomic Energy Agency (IAEA) using thermal ionization mass 
spectrometry [10]. 
The isotopic reference material IRMM-3100a is commercially available from IRMM. 
 
7 References 
 
[1] A. Verbruggen, A. Alonso, R. Eykens, F. Kehoe, H. Kühn, S. Richter, G. Van Baelen, 
R. Wellum, Preparation and Certification of uranium QUAD isotopic reference materials 
IRMM-3100 and IRMM-3102, Report EUR 23543 EN, JRC 48379, ISBN 978-92-79-
10326-1, ISSN 1018-5593. 
[2] A. Verbruggen, A. Alonso, R. Eykens, F. Kehoe, H. Kühn, S. Richter, R. Wellum, Y. 
Aregbe, Preparation and certification of IRMM-075, Report EUR 40265 EN 
[3] Richter S., S. A. Goldberg (2003), Improved Techniques for High Accuracy Isotope 
Ratio Measurements of Nuclear Materials using Thermal Ionization Mass 
 6 
Spectrometry, International Journal of Mass Spectrometry, 229 (2003) 181-197. 
[4] Richter S., A. Alonso, H. Kühn, R. Wellum, P.D.P. Taylor (2004), New Procedures for 
Uranium Isotope Ratio Measurements using the new TRITON Thermal Ionisation Mass 
Spectrometer, Internal Report IRMM, GE/R/IM/19/04 
[5] A. Verbruggen, A. Alonso, R. Eykens, F. Kehoe, H. Kühn, S. Richter, Y. Aregbe, 
Preparation and certification of IRMM-3636 and 3636a, Report EUR 23408 EN 
[6] Richter, S., A. Alonso, R. Eykens, U Jacobsson, H. Kühn, A. Verbruggen, Y. Aregbe, R. 
Wellum, E. Keegan, The Isotopic Composition of Natural Uranium Samples - 
Measurements using the new n(233U)/n(236U) Double Spike IRMM-3636, International 
Journal of Mass Spectrometry 269 (2008) 145–148 
[7] S Richter, H Kühn, Y Aregbe, M Hedberg, J Horta-Domenech, K Mayer, E Zuleger, S 
Bürger, S Boulyga, A Köpf, J Poths, K Matthew, Improvements for Routine Uranium 
Isotope Ratio Measurements using the Modified Total Evaporation Method, drafted, to 
be published in 2010. 
[8] International Organisation for Standardisation, Guide to the Expression of Uncertainty 
in Measurements, ISO/IEC Guide 98-3:2008, Geneva, Switzerland 2008. 
[9] GUM Workbench, Metrodata GmbH, www.metrodata.de 
[10] S Richter, A Alonso-Munoz, Y Aregbe, R Eykens, U Jacobsson, H. Kuehn, A 
Verbruggen, R Wellum, S Bürger, S Boulyga, J. Poths, IRMM-3100a: A New Certified 
Isotopic Reference Material with Equal Abundances of 233U, 235U, 236U and 238U, 
submitted to IJMS. 
 
 
 7 
Figure 2: Draft Certificate IRMM-3100a 
 
 
 8 
 
 
 
 
 
 9 
 
 
 
 
  
  
European Commission 
 
EUR 24559 EN – Joint Research Centre – Institute for Reference Materials and Measurements 
Title: Preparation and Verification of QUAD Uranium Isotopic Reference Material IRMM-3100a 
Author(s): A. Verbruggen, R. Eykens, F. Kehoe, H. Kühn, U. Jacobsson, S. Richter, Y. Aregbe 
Luxembourg: Publication Office of the European Union 
2010 – 9 pp. – 21.0 x 29.7 cm 
EUR – Scientific and Technical Research series – ISSN 1018-5593 
ISBN 978-92-79-17197-0 
doi:10.2787/31471 
 
Abstract 
 
The isotopic reference material IRMM-3100a was prepared by gravimetrical dilution of IRMM-3101. 
The primary solution IRMM-3101 was designed such that the material consists of equivalent parts of 
four individual isotopes n(233U)/n(235U)/n(236U)/n(238U) with a ratio of one.  
The certified isotope amount ratio2 for ratio n(233U)/n(236U) has been established by mass metrology 
and was verified by isotope mass spectrometry. The certified ratios n(234U)/n(236U), n(235U)/n(236U) 
and n(238U)/n(236U) have been measured  by TIMS in multi-dynamic mode and using the 
n(233U)/n(236U) ratio for internal normalization. The preparation of IRMM-3101 is in full described 
elsewhere. [1] 
The Isotopic Reference Material IRMM-3100a is part of a systematic IRMM programme to supply 
Isotopic Reference Materials of various isotopes at different concentrations. The Isotopic Reference 
Material is supplied in a quartz ampoule containing 0.5 mL of a 1 M nitric acid solution. 
 
 
 
 
 
 
 
                                                     
 
 
 
2
 Note: All uncertainties indicated are expanded uncertainties U = k·uc where uc is the combined standard 
uncertainty calculated according to the ISO/BIPM guide. They are given in parentheses and include a coverage 
factor k = 2. They apply to the last two digits of the value. The values certified are traceable to the SI. 
  
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Preparation and Verification of QUAD Uranium Isotopic Reference Material IRMM-3100a

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Preparation and Verification of QUAD Uranium Isotopic Reference Material IRMM-3100a

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