Rapid dissolution of plutonium in soil by fusion with ammonium hydrogen sulfate followed by plutonium determination by ion exchange and alpha spectrometry

A method was developed for the rapid dissolution of plutonium in soil by fusion with ammonium hydrogen sulfate, and the determination of plutonium content by ion exchange separation and alpha spectrometry. By this method, plutonium in environmental soil containing plutonium oxide in a soluble and/or insoluble form could successfully be determined.     

A new method of plutonium speciation in sea water

A new method of plutonium speciation in large volume of sea water was developed by using adsorption of Pu(IV)-Xylenol Orange chelate and Pu-Arsenazo chelate on XAD-2 resin, respectively. The tetravalent plutonium ion reacts selectively with Xylenol Orange in acid solution and that adsorbed on XAD-2 resin. Total plutonium can be collected onto the resin in the form of its Arsenazo-III complex. The determination of plutonium then was carried out by alpha-ray spectrometric method after decomposition of organic complexes and ion exchange separation. The present method is confirmed for convenient and rapid preconcentration procedure for plutonium shipboard chemistry.     

Combined application of alpha-track and fission-track techniques for detection of plutonium particles in environmental samples prior to isotopic measurement using thermo-ionization mass spectrometry

The fission track technique is a sensitive detection method for particles which contain radio-nuclides like ²³⁵U or ²³⁹Pu. However, when the sample is a mixture of plutonium and uranium, discrimination between uranium particles and plutonium particles is difficult using this technique. In this study, we developed a method for detecting plutonium particles in a sample mixture of plutonium and uranium particles using alpha track and fission track techniques. The specific radioactivity (Bq/g) for alpha decay of plutonium is several orders of magnitude higher than that of uranium, indicating that the formation of the alpha track due to alpha decay of uranium can be disregarded under suitable conditions. While alpha tracks in addition to fission tracks were detected in a plutonium particle, only fission tracks were detected in a uranium particle, thereby making the alpha tracks an indicator for detecting particles containing plutonium. In addition, it was confirmed that there is a linear relationship between the numbers of alpha tracks produced by plutonium particles made of plutonium certified standard material and the ion intensities of the various plutonium isotopes measured by thermo-ionization mass spectrometry. Using this correlation, the accuracy in isotope ratios, signal intensity and measurement errors is presumable from the number of alpha tracks prior to the isotope ratio measurements by thermal ionization mass spectrometry. It is expected that this method will become an effective tool for plutonium particle analysis. The particles used in this study had sizes between 0.3 and 2.0 μm.     

A titrimetric method for the sequential determination of thorium and plutonium

A method for the sequential determination of thorium and plutonium has been developed. In the sample solution containing thorium and plutonium, thorium is first determined by complexometric titration with EDTA and then in the same solution plutonium is determined by redox titration employing potentiometry. Prior to the determination of plutonium, EDTA is destroyed by fuming with concentrated HClO₄. Thorium is determined at 10 mg level and plutonium at 1 mg level with precision and accuracy of better than ±0.5%.     

Determination of plutonium by secondary coulometric titration with internally generated iron(II)

The method for plutonium determination based on secondary controlled-potential coulometry, as described by SHULTS, is applied for analysis in the range of 0.1–5 mg plutonium. The method involves the oxidation of plutonium to Pu(VI) with perchloric acid followed by its reduction by an internally generated ferrous mediator. This is a two step procedure, involving the reduction of Pu(VI) and Fe(III) to a mixture of Pu(III) and Fe(II), followed by the oxidation of Pu(III) and Fe(II) to Pu(IV) and Fe(III), respectively. The net results is the reduction of Pu(VI) to Pu(IV), measured as the difference between the currents consumed during the reduction and oxidation steps. The original method of SHULTS involves 10–25 mg plutonium for each determination. Since the present method is intended for the analysis of smaller amounts of plutonium, the oxidation procedure described in the original version had to be modified. The method is found to work satisfactorily with a precision better than 0.1% at 5 mg level and 1.2% for 0.1 mg plutonium.     

An improved method for the potentiometric determination of plutonium using cerium/IV/ as an oxidant

An improved method for the determination of plutonium in an aliquot using cerium/IV/ as an oxidant is reported. Plutonium is oxidized quantitatively to plutonium/VI/ in nitric acid medium by cerium/IV/, the excess of which is chemically destroyed in a single step by hydrochloric acid. Plutonium/VI/ is then reduced to plutonium/IV/ with a known amount of Fe/II/, the excess of which is back titrated potentiometrically with standard dichromate. Results of analysis of 3–5 mg amounts of plutonium in aliquots containing standard plutonium nitrate solution are reliable within 0.2%. Effect of the presence of some relevant foreign ions has been studied. The application of the method for the analysis of mixtures containing various amounts of uranium and plutonium has been examined.     

Recovery of plutonium from graphite crucibles generated in inert gas/vacuum fusion technique

A simple and rapid method has been developed for the separation and purification of plutonium from solid analytical waste (containing uranium, plutonium, nickel and graphite) generated during the analysis of the nuclear fuels for their oxygen and nitrogen contents by inert gas fusion technique. The method is based on crushing the graphite crucibles, electromagnetic separation of plutonium-nickel alloy, dissolution in nitric acid and ion exchange purification of plutonium. Recovery of plutonium is better than 98%. The method may be extendable for the recovery of any other valuable materials from such analytical waste.     

A ratio derivative spectrophotometric method for the simultaneous determination of uranium and plutonium

A ratio derivative spectrophotometric method has been developed for the simultaneous determination of uranium and plutonium at mg levels in 1M HNO₃ medium. In this method the overlapping spectra of uranium and plutonium are well resolved by making use of the first derivative of the ratios of their direct absorption spectra. The derivative ratio absorbances of uranium and plutonium are measured at 411.2 and 473.8 nm, respectively for their quantification. The method is simple, fast and does not require separation of uranium and plutonium. Another salient feature of the method is that it does not lead to generation of analytical waste thereby minimising the efforts required for the recovery of plutonium. Uranium in the conc. range of 10–25 mg/g and plutonium in the conc. range of 0.5 to 2 mg/g (U/Pu ratio varying from about 10 to 25) were determined in the same aliquot with a precision and accuracy of about 0.5% and 1%, respectively.     

Potentiometric determination of plutonium by sodium bismuthate oxidation

A potentiometric method for the determination of plutonium is described, in which the plutonium is quantitatively oxidized to plutonium(VI) with sodium bismuthate in nitric acid medium, the excess of oxidant is destroyed chemically and plutonium(VI) is reduced to plutonium(IV) with a measured excess of iron(II), the surplus of which is back-titrated with dichromate. For 3–5 mg of plutonium the error is less than 0.2%. For submilligram quantities of plutonium in presence of macro-amounts of uranium the error is below 2.0%.     

Extraction of plutonium from sulphuric acid by TOA in toluene

The extraction of plutonium(VI) and plutonium(III) from sulphuric acid by TOA in toluene has been studied as a function of the acid and tri-octyl amine concentration. A comparison of the extraction properties of plutonium with those of uranium(VI) and uranium(IV) has been made. It was found that the extraction properties of plutonium(VI) are very similar to those of uranium(VI) and that TOA is a relatively poor extractant for plutonium(III). Uranium(IV) shows better extraction properties than plutonium(III). The results obtained are considered in the light of the stabilities of the complexes formed by these elements in the organic and aqueous phase. A method of separation of both elements by solvent extraction based on changing their oxidation states is suggested.     

Age determination of plutonium material in nuclear forensics by thermal ionisation mass spectrometry

Age is a key parameter when deducing the history of plutonium material, i.e. the plutonium produced in the nuclear reactors. This is of vital importance, when a smuggled plutonium sample has been seized and the origin has to be determined. A methodology is described which allows accurately to determine the age of plutonium material by thermal ionisation mass spectrometry using independent parent/daughter relations. This has been demonstrated for Reference Materials of known ages as well as for real samples. The already established method using gamma spectrometry is compared to this.     

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.     

On the concentration and determination of plutonium in natural waters by adsorption on MnO2 filters

A new method of analysis of the efficiency of four filters of MnO₂ in series which takes into account the reactions induced in plutonium by the sorbent is described. The system of differential equations describing the behaviour of plutonium in water as it passes through the filters is solved and the parameters of the filters are determined for a best fitting of the solutions corresponding to the experimental uncertainties. The method is checked by numerical simulation and then applied to water solutions with a known plutonium concentration and to some experimental results given by other authors. In all occassions the results are consistent with the possibility of determining the contents of plutonium in sea and continental waters with uncertainties of the order of 10%.     

Age determination of plutonium material in nuclear forensics by thermal ionisation mass spectrometry

Age is a key parameter when deducing the history of plutonium material, i.e. the plutonium produced in the nuclear reactors. This is of vital importance, when a smuggled plutonium sample has been seized and the origin has to be determined. A methodology is described which allows accurately to determine the age of plutonium material by thermal ionisation mass spectrometry using independent parent/daughter relations. This has been demonstrated for Reference Materials of known ages as well as for real samples. The already established method using gamma spectrometry is compared to this.     

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.     

Determination of plutonium in sediments by solvent extraction and α-spectrometry

A simple technique for the determination of environmental levels of plutonium in a highly complex matrix (sediments containing very high amounts of iron and other metals) is reported. The sediments, collected from the Hudson River Estuary with an Emory dredge, were hand-homogenized before a sample aliquot was taken. Samples were airdried, weighed, spiked with ²⁴²Pu tracer, and heated at 400°C for 24 h. Plutonium was leached from the sediment with an acid mixture. The leachate was filtered, and plutonium coprecipitated with iron by adding ammonia solution. After dissolution, plutonium was extracted with 20% trilaurylamine in xylene, the extracts were thoroughly acid-washed to remove uranium and thorium traces, and plutonium was then back-extracted with 2 M sulfuric acid prior to electrodeposition onto a platinum planchet. The isotopic composition of plutonium was determined by α-spectrometry. Tracer yield and plutonium concentrations determined on aliquots of the same samples by this method and by an ion-exchange technique were not significantly different.     

Automated radiochemical procedure for plutonium and americium measurement

A radiochemical separation method for plutonium and americium from aqueous medium has been developed using a pre-packed resin column, a peristaltic pump, and the necessary tubing and valves for flow injection technique. All the radioanalytical operations were conducted in-line. Samples made of plutonium and americium tracers in water were analyzed by this technique and counted by alpha spectroscopy. The results show that plutonium and americium can be measured simultaneously using this technique.     

Determination of plutonium oxidation states in dilute nitric acid by complementary tristimulus colorimetry

The preparation of reference standards for use in complementary tristimulus colorimetry for plutonium is described. Plutonium(III) and (VI) are prepared by hydrazine reduction and silver(II) oxidation, respectively, of plutonium(IV). Plutonium(V) is prepared by reduction of plutonium(VI) with ascorbic or sulphurous acid. A method for computerizing tristimulus colorimetry is presented, and the technique is extended to three dimensions ("quadristimulus colorimetry").     

A spectrophotometric method for the determination of neptunium and plutonium in process solutions

A method is described for the determination of neptunium and plutonium in process solutions. This involves the separation of these elements followed by their spectrophotometric determination as Arsenazo III complexes. Neptunium(IV) and plutonium(IV) are separated using TTA extraction method and the separated Np(IV) and Pu(IV) are then determined as their Arzenazo III complexes in 5M HNO₃. A few solutions obtained by dissolving irradiated fuels were analysed for plutonium and neptunium using this method and the results were compared with those obtained by other methods. An attempt was made to use Arsenazo III to determine uranium in the plant solutions.     

Recovery and purification of plutonium in lean plutonium product stream obtained during reprocessing of fast reactor spent fuels

A method has been developed for final purification of plutonium from uranium and fission products of high beta gamma activity. This method involves selection of a suitable ion exchange resin for the purification of plutonium in order to deliver a quality PuO₂ product. The effect of the concentration of uranium and plutonium, effect of increased loading of uranium and number of bed volumes for effective washing, which are some of the parameters that generally affect the recovery and purification of plutonium were investigated. An excellent decontamination factor for fission products has been achieved by this anion exchange process which in turn delivered an excellent PuO₂ product quality in terms of purity and associated beta gamma activity with low personnel radiation exposure.