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Talanta
journal homepage: www.elsevier.com/locate/talanta
a r t i c l e i n f o a b s t r a c t
Article history: The determination of uranium isotope ratios in individual particles is of great importance for nuclear
Received 15 October 2008 safeguards. In the present study, an analytical technique by inductively coupled plasma mass spectrom-
Received in revised form etry (ICP-MS) with a desolvation sample introduction system was applied to isotope ratio analysis of
10 November 2008
individual uranium particles. In ICP-MS analysis of individual uranium particles with diameters ranging
Accepted 10 November 2008
from 0.6 to 4.2 m in a standard reference material (NBL CRM U050), the use of the desolvation system for
Available online 21 November 2008
sample introduction improved the precision of 234 U/238 U and 236 U/238 U isotope ratios. The performance
of ICP-MS with desolvation was compared with that of a conventionally used method, i.e., secondary ion
Keywords:
Uranium
mass spectrometry (SIMS). The analysis of test swipe samples taken at nuclear facilities implied that the
Isotope ratio performance of ICP-MS with desolvation was superior to that of SIMS in a viewpoint of accuracy, because
Particles the problems of agglomeration of uranium particles and molecular ion interferences by other elements
ICP-MS could be avoided. These results indicated that ICP-MS with desolvation has an enough ability to become
SIMS an effective tool for nuclear safeguards.
© 2008 Elsevier B.V. All rights reserved.
ity.
In the present study, a desolvation sample introduction system
was used to improve sensitivity in ICP-MS analysis for individual
∗ Corresponding author. Tel.: +81 29 282 6165; fax: +81 29 282 6950. particles. Moreover, the performance for isotope ratio analysis of
E-mail address: esaka.fumitaka@jaea.go.jp (F. Esaka). individual particles was evaluated by using test swipe samples
0039-9140/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2008.11.011
F. Esaka et al. / Talanta 78 (2009) 290–294 291
Fig. 1. (a) The 238 U ion signal intensities measured for individual NBL CRM U050 particles by ICP-MS with () and without () desolvation. (b) Example of the SEM images
of measured uranium particles.
containing uranium particles and compared with that of SIMS and nium particle to be analyzed was manipulated with the glass
manipulation-SIMS methods. needle attached to the manipulator and transferred onto the blank
planchet. For test swipe samples, uranium particles without manip-
2. Experimental procedure ulation were also prepared for SIMS analysis.
Uranium particles in a certified reference material (grains of An Apex-Q desolvation system (Elemental Scientific Inc., USA)
U3 O8 powder, CRM U050, New Brunswick Laboratory (NBL), USA) was used for sample introduction to ICP-MS. This system consists
were used in this study. The uranium particles were smeared onto a of a heated cyclonic spray chamber, a Peltier cooled condenser
cotton cloth (TexWipe® TX304, used for safeguards environmental and an ACM Naflon fluoropolymer membrane desolvation mod-
sampling by IAEA inspectors). In addition, two kinds of test swipe ule, allowing high efficient sample introduction. Uranium isotope
samples taken at nuclear facilities were used to compare the per- ratios were measured using a high resolution ICP-MS model ELE-
formance of ICP-MS with SIMS. MENT 1 (Thermo Fisher Scientific, USA), which has an ICP ion source
with Guard electrode and a double-focusing mass spectrometer.
2.2. Sample preparation for ICP-MS The instrument was operated in electric scanning (E-scan) modes
with a mass resolution (M/M) of 300. A PFA micro-flow nebulizer
Particles on the cotton cloth were recovered onto a Si disk (Nihon (self-aspirating mode) was used in combination with a Scott-type
Exceed Co. Ltd., Japan) with a diameter of 25 mm and a thickness of double pass spray chamber cooled at 4 ◦ C. The instrument with-
3 mm by an impaction method [12]. Si chips (5 mm × 5 mm, Semitec out desolvation was tuned daily for optimal 238 U sensitivity (2300
Co. Ltd., Japan) were cleaned, in sequence, with 40%, 2% HNO3 cps/ppt). Four mono-atomic ions (234 U+ , 235 U+ , 236 U+ and 238 U+ )
(high purity, Tama Chemicals Co. Ltd.) and deionized Milli-Q water were measured in a peak-jumping mode. The signal intensity of
238 U16 O+ was also measured for monitoring the stability of the
(18 M). The Si disk and the Si chips were introduced into a cham-
ber of a scanning electron microscope (SEM, JSM-6700F, Jeol Co. instrument. The formation rate of 238 U16 O+ to 238 U+ was between 2
Ltd., Japan) simultaneously. Individual uranium particles on the Si and 3%. The operating condition for the ICP-MS is listed in Table 1.
disk were observed with SEM and identified with energy disper- The interference of 235 U1 H+ on 236 U+ was corrected with prelimi-
sive X-ray (EDX) analysis. Single uranium particle was manipulated
with a glass needle attached to a manipulator and transferred onto Table 1
the center of each Si chip. Teflon bottles with a volume of 8 mL were Analytical condition in ICP-MS.
cleaned with 4% HNO3 and deionized Milli-Q water. The 8 mL of 4%
Parameter Setting
HNO3 was, then, added to the bottle and the count rate at a mass
238 was measured with ICP-MS to check the cleanliness of the bot- ICP-MS
RF power 1148 W
tle. Each Si chip containing a single uranium particle was dropped Cooling gas flow rate 16.0 L/min
into the bottle and 250 L of 40% HNO3 was added. The particle Auxiliary gas flow rate 0.85 L/min
was soaked overnight and dissolved at 55 ◦ C for 4 h under ultrason- Sample gas flow rate 0.79–0.86 L/min
eration. The solution was finally adjusted to 4% HNO3 by adding Solution uptake rate 0.18 mL/min
Sampling time per isotope 50 ms
2.75 mL of deionized Milli-Q water.
Scan per replicate 400
Number of replicates 5
2.3. Sample preparation for SIMS Resolution (M/M) 300
Fig. 2. The precision of (a) 234 U/238 U, (b) 235 U/238 U and (c) 236 U/238 U isotope ratios obtained for individual NBL CRM U050 particles by () manipulation-SIMS, () ICP-MS
and () ICP-MS with desolvation.
narily measured 238 U1 H/238 U ratio, 5.0 × 10−5 . The mass bias factor ICP-MS with and without desolvation. These results were plotted
assuming the following equation was determined using a 4 pg/mL against the 238 U amount calculated using the diameter as an aver-
NBL CRM U015 standard solution: age value between the lengths of major and minor axes of each
particle observed with SEM in Fig. 1(a). Fig. 1(b) shows examples
Rt = Rm (1 + C)M (1) of the SEM images of the particles. As shown in Fig. 1(a), the 238 U
count rate obtained with desolvation was several times higher than
where Rt is the certified isotope ratio, Rm is the measured isotope
that without desolvation. The increases of count rates were also
ratio, M is a difference in mass and C is a mass discrimination
observed on masses 234, 235 and 236. In the result measured with
factor.
desolvation, approximate chemical recovery rate was about 90%,
A secondary ion mass spectrometer (IMS-6f, Cameca, France)
which was calculated using the uranium amount estimated from
was used for measuring uranium isotope ratios in individual parti-
particle size and the signal intensity obtained with ICP-MS. This
cles. In SIMS analysis, an O2 + focused beam of 15 keV with a current
recovery rate would depend on the chemical composition of par-
of 1.0–20 nA was rastered over a 50 m × 50 m area. Positive sec-
ticles to be measured. Therefore, chemical dissolution procedure
ondary ions emitted from a particle were accelerated through 5 keV.
should be optimized to perform sensitive measurement.
Transfer optics of 150 m and a field aperture of 1800 m were
In isotope ratio analysis, precision is an important factor to
used. An energy slit was adjusted for a band pass of 50 eV. The
evaluate performance of measurements. In order to compare the
mass resolution was set at 300. Secondary ions at masses 234,
performance between ICP-MS and SIMS, relative standard devia-
235, 236, 238 and 239 were counted in an automatic peak-jumping
tion (R.S.D.) values of uranium isotope ratios obtained by analyzing
mode. An electron multiplier was operated in an ion counting mode
individual U050 particles were plotted against the amounts of ura-
with a dead time of 39 ns. Mass calibration was performed each
nium isotopes and are shown in Fig. 2. The R.S.D. values of 234 U/238 U
time before starting measurements of particles. Mass bias correc-
and 236 U/238 U isotope ratios obtained by ICP-MS with desolvation
tions were conducted by comparing the measured isotope ratios
were smaller than those without desolvation. These implied that
for a certified uranium reference material (NBL CRM U350) with
the use of the desolvation system improved the precision of these
the reference values. The ratio of certified 235 U/238 U to measured
235 U/238 U was around 0.991. The hydride formation rate of ura- isotope ratios. In contrast, no obvious improvement was found in
the analysis of 235 U/238 U isotope ratio. This is related to the increase
nium (238 UH/238 U) was determined (approximately 4 × 10−4 ) for
of 235 U intensity of procedural blank by using the desolvation sys-
each particle and used to subtract the contribution of 235 UH from
tem. Thorough cleaning of the system to reduce the blank value is
the signal of a mass 236.
necessary to perform more precise analysis.
For all isotope ratios, manipulation-SIMS gave better R.S.D. val-
3. Results and discussion ues than ICP-MS analysis. However, in the analysis of relatively large
uranium particles, the R.S.D. values obtained by ICP-MS with des-
3.1. Effect of Apex-Q desolvation system in ICP-MS olvation were nearly equal to those by manipulation-SIMS. This
means that ICP-MS analysis with desolvation has enough perfor-
The Apex-Q desolvation system was used to improve sensitivity mance for individual particle analysis. It should be noted that all
for analysis of individual uranium particles. Prior to the analysis of
uranium particles, procedural blank solution was prepared by per-
forming the same sample preparation procedure without particles. Table 2
The procedural blank values on masses 234, 235, 236 and 238 in ICP-MS with and
Count rates on masses 234, 235, 236 and 238 were measured for without desolvation.
procedural blank solution by ICP-MS with and without desolvation
and are given in Table 2. No obvious differences in the count rates Mass Counts/s
on masses 234 and 236 were found between the results obtained Procedural blank Procedural blank with desolvation
with and without desolvation. In contrast, the use of the desolva- 234 0.5 ± 0.3a 0.7 ± 0.3
tion system caused the increases of the count rates on masses 235 235 0.9 ± 0.5 2.3 ± 1.7
and 238, which would be due to the memory effect of the system. 236 0.2 ± 0.2 0.0 ± 0.1
The 238 U ion signal intensities were measured for individual 238 12.6 ± 6.6 115.8 ± 18.6
Fig. 4. The 234 U/238 U or 236 U/238 U isotope ratio against the 235 U/238 U isotope ratio measured for test swipe sample 1 by: (a) SIMS, (b) manipulation-SIMS and (c) ICP-MS with
desolvation. The error bars represent one standard deviation.
294 F. Esaka et al. / Talanta 78 (2009) 290–294
Fig. 5. The 234 U/238 U or 236 U/238 U isotope ratio against the 235 U/238 U isotope ratio measured for test swipe sample 2 by: (a) SIMS, (b) manipulation-SIMS and (c) ICP-MS with
desolvation. The error bars represent one standard deviation.