Lorenzo
Perna
ab,
Maria
Betti
*b,
Josepha Maria Barrero
Moreno†
b and
Roger
Fuoco
a
aUniversità degli Studi di Pisa, Department of Chemistry Industrial Chemistry, Via Risorgimento 35, 56126, Pisa, Italy
bEuropean Commission JRC, Institute for Transuranium Elements, Postfach 2340, 76125, Karlsruhe, Germany
First published on 15th December 2000
A method based on the use of the UTEVA-Spec. Eichrom resin as the stationary chromatographic phase is described. The column was coupled on-line to an ICP-MS detector for the determination of actinides. The method is compared with one based on the use of commercially available cation-exchange stationary phases. The analytical procedure was validated by the use of certified reference materials as well as by other independent analytical techniques. It was demonstrated that the UTEVA-Spec. column can be used at the same time as a pre-concentration column, as well as a chromatographic column, lowering the detection limit of analysis down to a few pg g−1.
Quadrupole and sector ICP-MS are very intensively exploited for the determination of longer lived radioisotopes.2–4
In the case of the spectroscopic interferences due to isobars of different elements, for example, those for transuranium elements or fission products (Table 1), even the resolution of sector field ICP-MS is insufficient. In these cases a chemical separation of the elements is necessary. In our laboratory, the use of a chromatographic separations system coupled on-line to an ICP-MS quadrupole instrument has been exploited for the determination of the complete inventory of fission products and actinides in solutions of spent nuclear fuel as well as in environmental samples.5–7 The chromatographic phases used consisted of commercially available columns from Dionex and the separation mechanisms were based on cation exchange. Automated radiochemical separation based on the use of Eichrom resins has been recently revised.8 The use of UTEVA-Spec. has also been investigated for the separation on-batch of U and Pu from fission product and minor actinides before their measurements by thermal ionization mass spectrometry (TIMS).9 In this paper we investigated the use of UTEVA-Spec. as a stationary chromatographic phase coupled on-line with ICP-MS. A method based on extraction chromatography for the simultaneous determinations for Th, Np, U and Pu isotopes was developed. Interferences from Am and Cm could be avoided by exploiting their elution in the dead volume of the column.
Mass | Elements |
---|---|
134 | Cs–Ba |
135 | Cs–Ba |
137 | Cs–Ba |
144 | Ce–Nd |
147 | Pm–Sm |
151 | Sm–Eu |
155 | Eu–Gd |
232 | Th–U |
238 | U–Pu |
241 | Am–Pu |
242 | Pu–Cm |
243 | Am–Cm |
The method has been compared with that based on the use of the CS10 (Dionex) column for the separation of Np, U and Pu.6
Nitric acid and hydrochloric acid were Suprapur grade from Merck (Darmstadt, Germany). Oxalic acid, ascorbic acid, hydrogen peroxide, sodium nitrite, sodium sulfite, hydroxyl-amine and Mohr's salt [(NH4)2Fe(SO4)2·6H2O] were obtained from Merck (Darmstadt, Germany). Water purified in a Milli-Q system (Millipore, Eschborn, Germany) was used throughout.
All standard solutions, spikes and sample were prepared by dilution by mass in polyethylene bottles. Radioactive samples and standards were treated in a glove-box.
A sediment reference sample, IAEA 135, certified for 232Th was used. The sample was prepared in a clean laboratory (class 10-100) using a microwave digestor (Gesa 301, Prolabo, France).
In particular the UTEVA-Spec. resin, exploited in this investigation, consisted of particles with an external diameter of 100–150 µm.
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Fig. 1 Four-way valve configuration for chromatographic separation on UTEVA-Spec: A, normal chromatographic elution and B, on-line preconcentration and successive chromatographic separation. |
To carry out the on-line preconcentration of the actinides, the system was modified as follows (Fig. 1B): when the valve is closed (off), the sample solution is loaded onto the column (4–8) by a two-way peristaltic pump. In this way the actinides are retained on the column, while the matrix flows to waste (7). The eluent enters in (5), flows through the connection tube and exits at (1), and then goes directly to the ICP-MS instrument. When the preconcentration operation is finished, the valve is opened and the eluent flows through the chromatographic column (8–4), exits at (1) and goes to the ICP-MS instrument.
In order to obtain Pu and Np in the oxidation state IV, different redox agents were tested; reported in Table 2 along with the oxidation states obtained by their use for both Pu and Np. Among the different agents studied, as can be seen from the Table 2, only hydrogen peroxide is capable of giving both elements in the oxidation state (IV). Nevertheless, the procedure employing hydrogen peroxide is quite complicated and it is necessary to bring the solution to the boiling point; a potential hazard when performed in a glove-box on radioactive samples. In view of this, it was decided to employ another procedure consisting of the combined use of two redox agents. According to this procedure, the Mohr's salt was used in order to convert all Np to the Np(IV). The Pu was converted to Pu(III). After 4 min, which is the necessary time to complete the reaction to obtain all Np in the oxidation state (IV), sodium nitrite is added in order to oxidise the Pu(III) to Pu(IV). This procedure is less complicated, but sensitive to the reaction time. In Fig. 2(a) and (b) the kinetic of the reaction after addition of sodium nitrite to the sample treated with Mohr's salt is reported. A solution containing 50 ng g−1 of Np and Pu was analyzed at different times using the UTEVA Spec. resin in the chromatographic column coupled on-line to the ICP-MS detector. As can be seen, after 10 min of reaction with sodium nitrite, the oxidation to state IV is complete for both the analytes.
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Fig. 2 (a) Kinetc of reaction of 237Np with sodium nitrite (redox agent) and (b) kinetic of reaction of 239Pu with sodium nitrite (redox agent). |
Redox agent | Plutonium | Neptunium |
---|---|---|
Ammonium and iron (II) sulfate. | III | IV |
Sodium sulfite | III and IV | IV and V |
Hydrogen peroxide | IV | IV |
Sodium nitrite | IV | IV and V |
Ascorbic acid | III | IV |
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Fig. 3 Chromatogram of a solution containing Th, Np, Pu and U (50 ng g−1 of each) and Am (10 ng g−1), obtained according to the elution conditions of Table 3. |
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Fig. 4 Chromatogram of a solution containing Th, Np, Pu and U (50 ng g−1 of each) and Am (10 ng g−1) adding 0.1 M oxalic acid to the eluent at step 3 of Table 3. |
The certified sediment was treated in a clean laboratory class 10-100. The dissolution was performed by means of a digester operating with microwaves, and ultra pure acid. After that, the sample solution was introduced into a glove-box and 237Np was added in known amounts in order to validate the procedure for this element. The amount of Np added was of the same order of magnitude as the other actinides in the sample solution (several ng g−1). Four different aliquots were prepared from this sample solution. For each of the four aliquots, 233U and 230Th were added in a concentration equal to 10 ng g−1 for isotope dilution analysis. In the other three aliquots, increasing amounts of 238U, 232Th and 237Np were added in order to calculate the concentration of the three elements by means of the standard additions method. All solutions were analyzed with chromatographic separation using UTEVA-Spec. and ICP-MS. For all aliquots, the reaction with Mohr's salt and sodium nitrite was performed. A 250 µl sample was injected onto the column. In Fig. 5 a typical chromatogram is reported. The appearance of a peak at 300 s is imputed to the change in the eluent at this time (c.f., Table 3 step 4). This peak shape does not influence the quantitative determination of U because it is reproducible in the chromatograms of the spiked samples.
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Fig. 5 Chromatogram obtained for the sample IAEA 135. |
In Table 4 the parameters of the calibration curves obtained for the different samples are reported together with the experimental values, expected values and certified values in terms of concentration. As can be seen, the experimental values are in good agreement with the expected values.
The second sample analyzed for the validation of the analytical procedure consisted of a leaching solution containing 238U and 238Pu. This sample was previously analyzed in the laboratory by several analytical procedures based on independent techniques.14 Also, for the calculation of the concentration, the method of internal standard additions was performed. The same experimental conditions used for the analysis of the sample IAEA 135 were also used for the analysis of this leaching solution. In Fig. 6 the chromatogram obtained for this solution is reported. In Table 5 are reported the parameters relative to the calibration curve obtained for 238U and 238Pu, together with the concentrations obtained versus the expected concentrations, according to the other measurements performed in the laboratory. Moreover, the same leaching solution was also analyzed using a method developed in the laboratory based on oxidation with silver oxide and chromatographic elution with DAP (40 mM) in HNO3 (0.6 M) on IonPac CS10.6 The results are also compared in Table 5. As can be seen they are all in good agreement. However the accuracy, at least for 238U, is better when using UTEVA-Spec. than the CS10 column. In the case of UTEVA-Spec., the chromatography based on the extraction mechanism improves the efficiency of elution with respect to that based on a cation-exchange mechanism.
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Fig. 6 Chromatogram obtained for the leaching solution. |
Element | Calibration curve | UTEVA value/ng g−1 | Expected value/ng g−1 | CS 10 value/ng g−1 |
---|---|---|---|---|
238Pu | y = 0.94 x + 0.76 r2 = 0.9991 | 90 ± 2 | 92 ± 2 | 91 ± 2 |
238U | y = 0.74 x + 0.79 r2 = 0.993 | 19.9 ± 0.4 | 20 ± 1 | 21 ± 1 |
The quantity of Np, U and Pu was measured according to the standard additions method. Fig. 7A shows a typical chromatogram for Np determination. The peak relevant to U found by scanning mass 237 is due to the interference of 238U on 237Np and is a good example of the need of a chromatographic separation between U and Np for samples of high U concentration.
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Fig. 7 Chromatogram obtained for a spent fuel solution. A, Separation Np/U. The peak relevant to U at mass 237 is due to the interference of 238U on 237Np. The others U isotopes are also present. B, Separation Pu/U. |
The parameters for the Np calibration curve are: y = 1.06 x + 1.39, r2 = 0.9997. Calculation of Np concentration, according to the above mentioned parameters, gives 13.2 ± 0.2 ng g−1.
Fig. 7B shows the chromatogram relative to 239Pu and 235U determination in the diluted solution. Table 6 reports the calculated concentrations, referred to the diluted spent fuel solution analysed, for 235U and 239Pu as well as the total U and Pu concentrations, obtained by the analytical procedure proposed as well as by TIMS.
Element | Analyzed solution concentration | |
---|---|---|
Proposed analytical procedure | TIMS | |
235U | 69 ± 2 ng g−1 | 67.2 ± 0.6 ng g−1 |
239Pu | 90 ± 2 ng g−1 | 94.7 ± 0.5 ng g−1 |
Utotal | 10 ± 1 µg g−1 | 10.5 ± 0.3 µg g−1 |
Putotal | 0.18 ± 0.02 µg g−1 | 0.18 ± 0.01 µg g−1 |
In order to obtain the isotopic composition for the irradiated fuel solution, Pu and U isotopes were measured. The values in weight % are reported in Table 7 and are in agreement with those obtained by isotope dilution thermal ionization mass spectrometry after chemical separation of U and Pu.
Isotope | Weight (%) | Isotope | Weight (%) | ||
---|---|---|---|---|---|
Proposed analytical procedure | TIMS | Proposed analytical procedure | TIMS | ||
238Pu | 3.1 ± 0.5 | 3.4 ± 0.4 | 234U | 0.03 ± 0.01 | 0.014 ± 0.005 |
239Pu | 50 ± 7 | 51.3 ± 3.6 | 235U | 0.7 ± 0.1 | 0.64 ± 0.05 |
240Pu | 24 ± 3 | 23.2 ± 1.9 | 236U | 0.7 ± 0.1 | 0.60 ± 0.05 |
241Pu | 14 ± 2 | 13.5 ± 0.7 | 238U | 98.5 ± 1.4 | 98.7 ± 0.9 |
242Pu | 9 ± 1 | 8.4 ± 0.5 |
In this way a pre-concentration factor that is proportional to the sample volume flowing through the column is obtained. The advantage is evident when very dilute aqueous solutions have to be analysed. Fig. 8A shows a chromatogram of a waste solution from a uranium enrichment plant. The concentration was about 1 ng g−1, and the chromatogram was obtained with the methodology proposed with the standard configuration. As can be seen, the analytical signal is very disturbed with a low signal-to-noise ratio, and, in this condition, it is difficult to determinate the concentration. Fig. 8B shows the chromatogram of 5 ml of the same solution, analyzed with the preconcentration system described above. In both the measurements the same eluents and conditions were used. In the second case a larger signal-to-noise ratio was obtained and consequently the concentration calculated has a lower error.
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Fig. 8 Chromatogram obtained for a waste solution containg 1 ng g−1 of Th and U, respectively: A, without on-line pre-concentration and B, with on-line pre-concentration. |
Footnote |
† Present address: European Commission, JRC, Institute for Health and Consumer Protection, TP 260, 21020 Ispra, Italy |
This journal is © The Royal Society of Chemistry 2001 |