A Bulk Resin Bead Procedure To Obtain Uranium And Plutonium From Radioactive Solutions For Mass Spectrometric Analysis

Abstract

A method is described for extracting representative uranium and plutonium samples from highly radioactive solutions for isotopic mass spectrometric analysis. Anion resin beads in the nitrate form are used to effect separation from fission products and other actinides. Conditions required to achieve separation are proper adjustment of the uranium and nitric acid concentrations. Once uranium and plutonium are adsorbed, each bead serves as a sample for mass spectrometric analysis, with plutonium and uranium being run sequentially from the same bead. Quantitative determination of the two elements is effected through the technique of isotopic dilution.     

Influence of manganese dioxide on the oxidation states of plutonium

When manganese dioxide impregnated filters have been used to concentrate plutonium from water solutions some anomalies were detected, which were ascribed to the probable existence of plutonium in two different oxidation states. The results of this paper seem to confirm this assumption that the Pu in the solution is a mixture of Pu(III) and Pu(IV). After contact with MnO₂, plutonium in the solution consists of only Pu(IV).     

Plutonium(III) oxidation under α-irradiation in nitric acid solutions

Plutonium(III) oxidation under high energy α-irradiation in nitric acid solutions has been studied relative to concentrations of both nitric acid (0.12–2.9 mol/l) and plutonium (1.4–10 mmol/l) using spectrophotometric techniques. Curium-244 has been used as the basic alpha-irradiation source. It has been stated that in solutions with nitric acid concentrations lower than 0.5 mol/l plutonium(III) does not oxidize completely. In the course of the process the formation of a plutonium(IV) peroxide complex is observed. Increase in the nitric acid concentration results in that in both the rate and degree of plutonium(III) oxidation. When c_{HNO 3} is higher than 0.5 mol/l the peroxide complex does not form and the process assumes an autocatalytic character. It has also been shown that plutonium(III) oxidation kinetics is significantly affected by nitrous acid, one of the nitrate ion radiolysis products. To describe plutonium chemical transformations under irradiation in nitric acid solutions, a kinetic scheme is proposed. The calculations have been carried out on a BESM-6 computer; a satisfactory agreement between the calculated and experimental data has been obtained.     

Simultaneous Determination of Timolol Maleate and Pilocarpine Hydrochloride in Ophthalmic Solutions by First Derivative UV Spectrophotometry and PLS-1 Multivariate Calibration

ABSTRACT

The use of UV spectrophotometry (first-derivative/zero-crossing and zero-order spectra/multivariate calibration) is reported for the analysis of two miotic agents in ophthalmic solutions. The resolution of these mixtures has been accomplished without prior separation or derivatisation by using: 1) first-derivative measurements at two appropriate zero-crossing points: λ₁ = 222 nm, where the absorption corresponding to excipients is negligible, and λ₂ = 307 nm, where the contribution of pilocarpine and excipients to the overall absorption is negligible, and 2) partial least squares (PLS-1) regression analysis of zero-order spectral data. Although the components show an important degree of spectral overlap, they have been simultaneously determined with high accuracy, and with no interference from ophthalmic solution excipients.     

Studies on the recovery of Pu(IV) from hydrochloric acid-oxalic acid solutions using an anion exchange method

Sorption of Pu(IV) from hydrochloric acid-oxalic acid solutions has been investigated using different anion exchangers, viz., Dowex-1X4, Amberlite XE-270 (MP) and Amberlyst A-26 (MP) for the recovery of plutonium from plutonium oxalate solutions. Distribution ratios of Pu(IV) for its sorption on these anion exchangers have been determined. The sorption of Pu(IV) from hydrochloric acid solutions decreases drastically in the presence of oxalic acid. However, addition of aluminium chloride enhances the sorption of plutonium in the presence of oxalic acid, indicating the feasibility of recovery of plutonium. Pu(IV) breakthrough capacities have been determined with a 10 ml resin bed of each of these anion exchangers at a flow rate of 60 ml per hour using a solution of Pu(IV) with the composition: 6M HCl+0.05M HNO₃+0.1M H₂C₂O₄+0.5M AlCl₃+100 mg.l^–1 Pu(IV). The 10% Pu(IV) breakthrough capacities for Dowex-1X4, Amberlite XE-270 (MP) and Amberlyst A-26 (MP) are 15.0, 8.9 and 6.2 g of Pu(IV) l^–1 of resin respectively.     

SPECTROPHOTOMETRIC DETERMINATION OF TRACE AMOUNTS OF FLUORIDE IN PLUTONIUM

Abstract

A simple and rapid spectrophotometric method for the determination of 10 to 70 μg of fluoride with Eriochrome Cyanine R in up to 10 mg of plutonium has been developed. In this method interference from the plutonium is eliminated by reduction of this element to the tripositive oxidation state with mercaptoacetic acid.     

Application of fission track registration technique in the estimation of fissile materials

Analysis of fissile materials in solution by fission track registration technique has been extended to plutonium in solution of its alloys. In these estimations, the results agreed within 1–4% with the average of those obtained by other chemical and instrumental methods like potentiometry, mass-spectrometry and X-ray fluorescence. Some special practical problems encountered in the analysis of plutonium solutions are noted. Various factors affecting the results have been investigated and the necessary precautions for reducing these errors have been indicated. The advantages of the method over some other conventional methods have also been discussed. It is suggested that a source of about 10 μg of²⁵²Cf corresponding to a neutron flux of about 10⁷ n·cm⁻²·sec⁻¹ is ideal for these experiments.     

Simultaneous Plutonium and Uranium Isotopic Analysis from a Single Resin Bead - A Simplified Chemical Technique for Assaying Spent Reactor Fuels

Abstract

The method uses basic anion resin to adsorb plutonium and uranium from 7–8 M HNO₃ solutions containing dissolved spent reactor fuels. After equilibrating the resin with the solution, a single bead is used to determine the isotopic composition of plutonium and uranium on sample sizes as small as 10^?9 to 10^?10 g of each element per bead. Isotopic measurements are essentially free of isobaric interferences and fission product contamination in the mass spectrometer is eliminated. A very small aliquot of dissolver solution containing 10^?6 g of U and 10^?8 g of Pu is sufficient sample for chemically preparing several resin beads. A single prepared bead is loaded onto a rhenium filament and analyzed in a two-stage mass spectrometer using pulse counting for ion detection to obtain the high sensitivity required. Total quantity of the elements, in addition to isotopic abundances, can be determined by isotope dilution. Other areas where the method may be useful are: in plutonium production, isotope separations, and for trace detection of contamination on reactor parts.     

Simultaneous determination of uranium and plutonium at trace levels in process streams using Arsenazo III by derivative spectrophotometry

A derivative spectrophotometric method has been developed for the simultaneous determination of uranium and plutonium at trace levels in various process streams in 3M HNO₃ medium using Arsenazo III. The method was developed with the objective of measuring both uranium and plutonium in the same aliquot in fairly high burn-up fuels. The first derivative absorbances of the uranium and plutonium Arsenazo III complexes at 632 nm and 606.5 nm, respectively, were used for their quantification. Mixed aliquots of uranium (20–28 μg/ml) and plutonium (0.5–1.5 μg/ml) with U/Pu ratio varying from 25 to 40 were analysed using this technique. A relative error of about 5% was obtained for uranium and plutonium. The method is simple, fast and does not require separation of uranium and plutonium. The effect of presence of many fission products, corrosion products and complexing anions on determination of uranium and plutonium was also studied.     

Preparation, characterization and application of thorium oxalate for sorption of plutonium and americium from aqueous solution

Synthetic inorganic exchangers exhibit good thermal and radiation stability. Thorium oxalate precipitate shows potential for co-precipitation of plutonium and americium from oxalate supernatant generated during plutonium oxalate precipitation. In the present study, efforts were made to prepare thorium oxalate precipitate to be used for column operation. Distribution ratios were determined to optimize conditions for sorption of plutonium and americium on thorium oxalate from nitric acid + oxalic acid solutions with composition similar to that of oxalate supernatant. Column experiments were also performed to evaluate the sorption capacity of thorium oxalate for plutonium and americium from the same medium. The result showed that, thorium oxalate prepared in 1.75M HNO₃ at 70 °C is suitable for column operations. These studies showed that plutonium and americium could be simultaneously removed from aqueous solutions with composition similar to plutonium oxalate waste using glass column packed with thorium oxalate and these nuclides could be recovered by eluting with 3M HNO₃.     

Studies on the adsorption of plutonium (IV) on alumina from phosphoric acid-nitric acid solution

Results of experiments on the adsorption of plutonium (IV) on alumina and their application to the recovery of plutonium from analytical waste solutions containing phosphoric-nitric acid are reported. Distribution ratios of plutonium (IV) between alumina and solutions containing varying concentrations of phosphoric acid and nitric acid are determined. The influence of various ions like UO₂ ²⁺, Fe³⁺, MoO₄ ^2–, VO²⁺ and SO₄ ^2– on the distribution ratio is evaluated. Saturation values of adsorption of plutonium (IV) on alumina and optimum conditions for loading and elution of plutonium on a column packed with alumina are described.     

Determination of uranium and plutonium in plutonium based fuels by sequential amperometric titration

A method is described for the sequential determination of uranium and plutonium in plutonium bearing fuel materials. Uranium and plutonium are reduced to U(IV) and Pu(III) with titanous chloride and then titrated with dichromate to two end points which are detected amperometrically using two polarized platinum electrodes. Uranium-plutonium solutions of known concentrations containing plutonium in the proportions of 4, 30, 50, and 70% were analyzed with precisions better than 0.3%, maintaining the amounts of plutonium per aliquot in the range of 2–10 mg. No significant bias could be detected. Several samples of (U, Pu)O₂ and (U, Pu)C were analyzed by this procedure. The effects of iron, fluoride, oxalic acid and mellitic acid on the method were also studied.     

CONCENTRATION AND SOLVENT SENSITIVE VISIBLE SPECTRA OF POLY(TRICYANOVINYLDIMETHYLANILINE): AGGREGATION AND SOLVATOCHROMISM

ABSTRACT

This work presents unusual spectral behavior of poly(tricyanovinyl dimethylaniline) (1) in dilute solutions. A new conjugated polymer(1) was prepared from p-(tricyanovinyl)N,N-dimethylaniline via the use of a methylglucopyranoside reagent. It is observed that dilute solutions of 1 exhibit spectral features associated with aggregation. The associative interaction is studied by changing the salt concentration of LiBr in DMF solution, by changing the concentration of 1, and by varying the solvents. The association modifies the visible spectrum of 1 in dilute solution. Spectra of 1 in DMF solution exhibit an intense absorption maximum at 429 nm, which can be assigned to the side group, with tailing past 700 nm. With increasing concentration, a new absorption band arises between 480 nm and 700 nm. LiBr dissociates the aggregate to decrease the additional spectral features. The visible spectrum of 1 varies in different solvents. The spectrum of 1 in chloroform solution exhibits two maxima at 490 nm and 550 nm. The associative interaction presumably arises from a dipole–dipole interaction among pendant side groups. In DMF solution of 1 in the presence of p-chloranil, the spectrum shows a maximum at 429 nm with a distinct shoulder near 520 nm which does not orginate from 1 and p-chloranil(CA) itself.     

The effect of physicochemical parameters on the separation recovery of plutonium and uranium from aqueous solutions by cation exchange

The effect of physicochemical parameters such as pH, salinity (e.g. [NaCl]) and competitive cation (e.g. Ca²⁺ and Fe³⁺) concentration on the separation recovery of plutonium and uranium from aqueous solutions by cation exchange has been investigated. The investigation was performed to evaluate the applicability of cation exchange as separation and pre-concentration method prior to the radiometric analysis of uranium and plutonium isotopes in natural water samples. Application of the method to test solutions of constant radionuclide concentration and variable composition (0.1, 0.5 and 1 M NaCl; 0.1 and 0.5 M Ca(NO₃)₂; 0.1 and 1 mM FeCl₃; 10) has generally shown that: (1) the optimum pH is 4.5 for uranium and plutonium, (2) increasing salinity results in slightly lower for uranium and significantly higher chemical recovery plutonium and (3) the presence of Ca(II) cations doesn’t significantly affect the chemical recovery of both radionuclides. Contrary, the presence of Fe(III) cations ([Fe(III)] > 0.1 mM) results in significantly lower chemical recovery for both radionuclides (<50%). The later is attributed to the formation of Fe(III) colloids, which present increased chemical affinity for uranium and plutonium and hence compete with the radionuclide binding by the resin. Nevertheless, the results indicate that the method could be successfully applied to a wide range of natural waters.     

Mycoremediation: the study of transfer factor for plutonium and americium uptake from the ground

In our scientific research we have monitored mycoremediation’s properties of oyster mushrooms in cultivation on the soil what is contaminated by solutions with radioactive isotopes of ²³⁹Pu and ²⁴¹Am with known activity. We monitored specific activities of absorbed radionuclides in fruiting bodies and chemical forms of radionuclides which were compared to calculated specific activities of two background samples of oyster mushrooms intended for consumer purpose. We determined distributive coefficients between the ground and the fruiting body of oyster mushrooms. The average value which was obtained for the transfer factor for plutonium was 0.72 and for americium 3.97. To evaluate a quantity of absorbed radionuclides we used a method of liquid extraction. The emitting alpha radiation of alpha radionuclides was detected by spectrometry. For defining individual fractions of plutonium and americium that are contained in mushroom bodies was used the sequential leaching method.     

Studies on the sorption of Pu(IV) on alumina microspheres from nitric acid-oxalic acid solutions

Sorption of Pu(IV) on alumina microspheres prepared by the sol-gel procedure has been investigated for the recovery of plutonium from nitric acid-oxalic acid solutions. Distribution ratio for Pu(IV) between alumina microspheres and nitric acid-oxalic acid have been determined. The influence of the mode of preparation and heat treatment of these microspheres, on the sorption of Pu(IV) have been investigated. Pu(IV) breakthrough capacities have been determined using a 5 ml bed of alumina with solutions of Pu(IV) in 1M HNO₃+0.05M H₂C₂O₄ and 0.5M HNO₃+0.05M H₂C₂O₄. The elution behavior of Pu(IV) loaded on these microspheres were studied using nitric acid solutions containing different oxidising and reducing agents. Investigations were also carried out to fix the activity in the alumina matrix by heat treatment.     

Redox determination of uranium in presence of plutonium in low phosphoric acid medium and the recovery of plutonium

Quantitative determination of uranium in (U, Pu)O₂ fuels is usually done by the DAVIES-GRAY method. High concentrations of phosphoric acid in the analytical waste generated by this method make the revocery of plutonium rather complex. Studies on the recovery of plutonium from nitric acid medium containing different concentrations of H₃PO₄ by conventional anion-exchange procedure reveal that more than 90% of the plutonium can be easily recovered when the phosphoric acid concentration is less than 0.5 M in the solution. A method was developed for the determination of uranium in the presence of plutonium, which involves the reduction of U(VI) to U(IV) by Fe(II) in a medium of 3.5M H₃PO₄ +4.5M H₂SO₄ instead of 10–11M H₃PO₄ so as to have the H₃PO₄ concentration 0.6M in the waste. A number of determinations of uranium in UO₂(NO₃)₂ working standard solutions and (U, Pu) synthetic solutions with uranium at the 3–7 mg level were carried out by this method. The precision obtained was better than ±0.2% and the accuracy was also within the precision limits. The resulting analytical waste generated was directly subjected to anion exchange separation for the recovery of plutonium which was found to be more than 90%.     

Light absorption in solutions of cetyltrimethylammonium and cetylpyridinium bromides

Absorption of monochromatic light in solutions of cetyltrimethylammonium (CTAB) and cetylpyridinium (CPB) bromides has been studied in the wavelength λrange of 190–1000 nm. The investigation has been performed at 30°C and surfactant concentrations ranging from 5 × 10^?5 to 3.5 × 10^?3 M. Spectra of solutions of LiBr, KBr, and CTAB in the premicellar concentration region have been shown to coincide with each other. They are unimodal, and the heights of their maxima at λ_max ≈ 193 nm depend on Br^? concentration alone. In contrast to CTAB solutions, the UV spectra of CPB solutions are characterized by the presence of two absorption maxima near λ_max1 = 191 nm and λ_max2 = 259 nm, as well as a shoulder at 210–218 nm. Their existence is caused by the presence of both Br^? anions and CP⁺ cations in the solutions. The dependences of the integral absorption in the examined wavelength range on CPB concentration exhibit inflections both in the premicellar region and upon the transition to micellar solutions, with these inflections characterizing the critical dimerization and micellization concentrations, respectively. For CTAB, this regularity has only been observed at the critical micellization concentration. The data on the concentration dependence of the light absorption have resulted in the proposal of a method for determining the degree β of counterion binding by micelles of ionic surfactants. The β values calculated for CTAB and CPB are equal to 0.89 ±0 0.1.     

Individual determination of uranium and plutonium in a single aliquot

Studies on the individual potentiometric determination of uranium and plutonium in a single aliquot have been initiated recently in our laboratory. It was required to adapt the reported procedures (for the precise determination of uranium and plutonium individually when present together in a sample) at various stages to make them suitable for the successive application of the procedures to the same aliquot. Two alternative schemes are proposed in the present work. In the first, plutonium is determined by HClO₄ oxidation followed by the determination of total uranium and plutonium by Zn(Hg) reduction. In the second, plutonium is determined by AgO oxidation following the determination of total uranium and plutonium by Zn(Hg) reduction. Amount of uranium is computed in both cases from the difference of two determinations. Precision for the assay of plutonium and uranium was found to be ±0.25% and ±0.35%, respectively, at milligram levels.     

Glutaraldehyde - “Pure and Impure.” A Spectroscopic Investigation of Two Commercial Glutaraldehyde Solutions and Their Reaction Products with Amino Acids

Abstract

The composition of two glutaraldehyde solutions with different grades of purity was studied by HPLC, UV, J-H and ¹³C NMR spectroscopy. The reactions between various amino acids and the two glutaraldehyde solutions were investigated by UV spectrophotometry. The impurities in the most impure glutaraldehyde solution could be characterized with UV giving a 235 nm absorption, with HPLC as two peaks with retention times 3.36 and 5.78 min and with ¹³C NMR as small signals in the 102.7-94.9 ppm area. It is proposed that the two glutaraldehyde solutions give different reaction products with amino acids.