Use of combined alpha-spectrometry and fission track analysis for the determination of240Pu/239Pu ratios in human tissue

Plutonium and other actinides were determined in human autopsy tissues of occupationally exposed workers who were registrants of the United States Transuranium and Uranium Registries (USTUR). In this study, Pu was purified and isolated from Am, U and Th, after drying and wet-ashing of the tissues, and the addition of²³⁸Pu as a radiotracer. After electrodeposition onto vanadium planchets the^239+240Pu activity was determined by alpha-spectrometry. A fission track method was developed to determine²³⁹Pu in the presence of²³⁸Pu and²⁴⁰Pu, using Lexan^TM polycarbonate detectors. Combining the two techniques allowed the determination of the²⁴⁰Pu/²³⁹Pu activity and atom ratios. Data from selected USTUR cases are presented.     

Determination of actinide nuclides in water samples from the primary circuit of a research reactor

Primary coolant samples from a research have been analyzed for^239,240Pu,²³⁸Pu,²³⁸U,²³⁷Np and²³⁹Np. The determination of²³⁷Np and²³⁸U was carried out with the help of isotope dilution neutron activation analysis with²³⁹Np or²³⁸Np as tracer. For determination of^239,240Pu and²³⁸Pu alpha spectroscopic isotope dilution analysis with²³⁸Pu as tracer was used.²³⁹Np was determined with the help of isotope dilution analysis using²³⁸Np as tracer. Nuclides were isolated by chemical separation on anionite resin. Before measurement, Pu isotopes were electrolytically deposited on stainless steel plates. Activity ratios referred to²³⁸U were reported. They are helpful for identification of the sources of actinide activity in reactor effluents.     

Reversed-phase partition chromatographic separation of minor actinides with bis(2-ethylhexyl) sulfoxide from acidic nitrate PUREX waste solutions

The uptake behavior of U(VI), Pu(IV), Am(III) and a few long-lived fission products from nitric acid media by bis(2-ethylhexyl) sulfoxide (BESO) adsorbed on Chromosorb has been studied U(VI), Pu(IV) and Zr(IV) are taken up appreciably as compared to trivalent actinides/lanthanides including some coexisting fission product contaminants which are weakly sorbed on the column. Chromosorb could be loaded with (1.12±0.03) g of BESO per g of the support. Maximum sorption is observed around 4–5 mol·dm^–3 HNO₃ for both U(VI) and Pu(IV), which are sorbed as their disolvates. The elution of (U(VI) and Pu(IV) from the metal loaded sorbent has also been optimized. Desorption of U(VI) is easily accomplished with dilute nitric acid (ca. 0.01 mol·dm^–3)while Pu(IV) is reductively stripped with 0.1 mol·dm^–3 NH₂OH·HCl. Effective sequential separation of U(VI), Pu(IV) and Am(III) from their several admixtures could be readily achieved from real medium and low level active acidic process raffinates.     

In-line determination of heavy elements by gamma ray-induced energy-dispersive K-line XRF

In-line determination of heavy elements, especially in nuclear fuel reprocessing solutions by means of XRF analysis and -emitting radionuclides as excitation sources for the K-lines has been investigated.⁵⁷Co,¹³³Ba and¹⁹²Ir are used as radionuclide sources. U, Np, and Pu can be determined from the lower ppm range up to the saturation concentration of about 400 g/l. In case of Pu concentrations >100 mg/l the detection limits for U and Np increase. A matrix effect due to the composition of the solution is observed, which depends only on the density of the solution. At higher activities of fission products in the solution, an increase of the background count rate but no interferences are observed. This allows determination of heavy elements in fission product solutions.     

Cumulative yields of short-lived ruthenium isotopes in the thermal neutron induced fission of233U,235U and239Pu

Cumulative yields of short-lived ruthenium isotopes in the thermal neutron induced fission of²³⁵U,²³⁵U and²³⁹Pu have been determined using a fast radiochemical separation technique followed by gamma spectrometry. The cumulative yields of¹⁰⁷Ru and¹⁰³Ru in²³³U (n_th, f) and¹⁰⁷Ru and¹⁰⁹Ru in²³⁹Pu (n_th, f) are determined for the first time. The measured cumulative yields are converted to chain yields assuming normal charge distribution systematics for comparison with the literature data on chain yields.     

Uncertainty of decay heat calculations originating from errors in the nuclear data and the yields of individual fission products

The calculation of the abundance pattern of the fission products with due account taken of feeding from the fission of²³⁵U,²³⁸U, and²³⁹Pu, from the decay of parent nuclei, from neutron capture, and from delayed-neutron emission is described. By means of the abundances and the average beta and gamma energies the decay heat in nuclear fuel is evaluated along with its error derived from the uncertainties of fission yields and nuclear properties of the individual fission products.     

Sequential isotopic determination of plutonium,thorium, americium and uranium in the air filter and drinking water samples around the WIPP site

The simultaneous determination of actinides in air filter and water samples around the WIPP site have been demonstrated. The analytical method is based on the selective separation and purification by anion exchange and Eichrome-TEVA, TRU and DGA-resin followed by determination of actinides by alpha spectrometry. Counting sources for alpha spectrometric measurements were prepared by microcoprecipitation on neodymium fluoride (NdF₃). Radiochemical yields were determined using ²⁴²Pu, ²²⁹Th, ²⁴³Am and ²³²U as tracers. The validation of the method is performed through the analysis of reference materials or participating in laboratory intercomparison programs. The plutonium concentrations in aerosols varied seasonally, being highest in spring and summer due to the spring-time enhanced wind-storm transportation of radioactive aerosols from the stratosphere to the troposphere. The ²³⁸Pu/^239+240Pu activity ratio in the aerosol samples is typically close to that of global fallout from historic above-ground nuclear weapons testing. The results presented here indicate that the source of plutonium in the WIPP environment results mainly from global nuclear fallout and there is no evidence of increases in radiological contaminants in the region that could be attributed to releases from the WIPP.     

Sequential separation of transuranic elements and fission products from uranium metal ingots in electrolytic reduction process of spent PWR fuels

A sequential separation procedure has been developed for the determination of transuranic elements and fission products in uranium metal ingot samples from an electrolytic reduction process for a metallization of uranium dioxide to uranium metal in a medium of LiCl-Li₂O molten salt at 650 °C. Pu, Np and U were separated using anion-exchange and tri-n-butylphosphate (TBP) extraction chromatography. Cs, Sr, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Zr and Mo were separated in several groups from Am and Cm using TBP and di(2-ethylhexyl)phosphoric acid (HDEHP) extraction chromatography. Effect of Fe, Ni, Cr and Mg, which were corrosion products formed through the process, on the separation of the analytes was investigated in detail. The validity of the separation procedure was evaluated by measuring the recovery of the stable metals and ²³⁹Pu, ²³⁷Np, ²⁴¹Am and ²⁴⁴Cm added to a synthetic uranium metal ingot dissolved solution.     

Voltamperometric determination of uranium and plutonium in alkaline solutions

The simultaneous determination of U(VI), Pu(VI), Pu(V) in 0.5–4.0 M NaOH has been elaborated by means of classical and differential pulse voltamperometry. U(VI) is determined with a dropping mercury electrode (DME) at the half-wave potential of E_1/2=–0.89 V vs. Ag/AgCl reference electrode due to reduction to U(V). The limiting current or peak heights are proportional to uranium(VI) concentration in the range of 1.3.10^–7–3·10^–4 M U(VI). Deviation from proportionality is observed for higher concentrations due to polymerization of uranates. Pu(VI) and Pu(V) are determined with a platinum rotating electrode at E_1/2=–0.02 V due to the reaction Pu(VI)+e^–»Pu(V) and with DME at E_1/2=–1.1 V due to the reduction to Pu(III). The limiting currents of both Pu(VI) and Pu(V) are proportional to their concentrations in the range of 4·10^–6–1.2·10^–3 M Pu. The determination of U(VI), Pu(VI), Pu(V) is not interfered by the presence of the following salts: 2M NaNO₃, 2M NaNO₂, 1.5M NaAlO₂, 0.5M NaF and ions of Mo(VI), W(VI), V(V), Cu(II). The presence of CrO ₄ ^2– and FeO ₂ ^– ions disturbs the determination of U(VI) in 1–4M NaOH, however, contribution of the reaction Fe(III)+e^–»Fe(II) to uranium reduction peak can be calculated from the height of the second peak Fe(II)+2 e^–»Fe(0).     

Quantitative and isotopic analysis of released and retained krypton and xenon fission gases from irradiated metallic fuels

We quantitatively measured the amounts and isotopic distributions of the released and retained fission gases (Kr and Xe) from two irradiated metallic fuels (U–10Zr and U–10Zr–5Ce) at approximately 2.9 at.% burnup, using a gas chromatography and a quadrupole mass spectrometer. The obtained Xe/Kr ratios indicate that the released and retained fission gases from the irradiated metallic fuels came primarily from the fission of ²³⁵U, instead of that of heavy isotopes such as ²³⁹Pu and ²⁴¹Pu. The calculated (⁸³Kr + ⁸⁴Kr)/⁸⁶Kr and (¹³¹Xe + ¹³²Xe)/¹³⁴Xe ratios suggest that no fuel rods became defective during the irradiation process.     

Fine structure of mass and charge distribution in low energy fission

Studies of finer details in mass and charge distribution fission leads to a better understanding of the fission process. Experimental determination of independent and cumulative yields using radiochemical techniques as well as mass spectrometers and fission product recoil separators form the basis of such studies. It has been established that closed shells as well as an even number of nucleons influence both mass and charge distributions. The magnitudes of these effects may be estimated from existing experimental yield data and various fission models. Using our measurements of several fission yields and those existing in the literature we have calculated even-odd proton and neutron effects for various low energy fissioning systems. Where enough data existed, direct calculations were made, whereas for other cases the Z_p-model of WAHL has been used. It is found that the even-odd proton effect is well established and pronounced in thermal neutron fission of²³⁵U and²³³U. Lesser effects were found for reactor neutron induced fission of²³²Th, thermal neutron fission of²³⁹Pu and spontaneous fission of²⁴⁵Cm and²⁴⁹Cf. No effect seems to exist in the thermal neutron fission of²⁴¹Pu and the spontaneous fission of²⁵²Cf. The even-odd neutron effect is found to be much lower than the corresponding proton effect in²³⁵U and²³³U fissions and is nonexistent in the rest of the fissioning systems.     

Dosimetric measurement of the disintegration rate of fission products

Investigations on the disintegration rate of fission products of²³⁸U and²³⁹Pu are presented. The intensity of the - and -radiation of fission products were measured continuously in an interval of 1–1300 hours following the fission, offering the possibility for determining the general and specific characteristics of the individual fission products. A universal measuring procedure was elaborated for the rapid in situ determination of the dosimetric features of fission products, which is suitable for the accurate evaluation and prediction of external absorbed dose even in case of fission products of various origin and unknown composition.     

Simultaneous determination of uranium and plutonium isotopes in soils by means of single alpha-spectrometry

A simple, rapid and reliable method was developed for the simultaneous determination of uranium and plutonium isotopes by alpha-spectrometry using a single source. A new uranium tracer²³⁰U was applied as well as the²³⁶Pu tracer to determine overall yields of uranium and plutonium isotopes throughout the entire procedure employed. The analytical procedure consists of sample leaching with 8N HNO₃ solution, purification by solvent extraction, simultaneous electrodeposition of U and Pu, and subsequent alpha-spectrometry with a silicon detector. In the solvent extraction using TOA/xylene from 8N HNO₃ solution, the preferential extractability of Pu rather than U permits to purify simultaneously the trace amounts of Pu and the macro amounts of U, as in the case of ordinary soil samples, resulting in favourable peak heights for both isotopes. From a single alpha-spectrum, the determinations of²³⁸U,²³⁴U (and their ratio of²³⁴U/²³⁸U),^239+240Pu, and²³⁸Pu contents were conveniently carried out after correcting the overall yields obtained from²³⁰U and²³⁶Pu activities in the same spectrum. This analytical method was satisfactorily applied to the determination of U and Pu isotope contents in some soils.     

A multi-method approach for determination of radionuclide distribution in trinitite

The spatial distribution of radiation within trinitite thin sections have been mapped using alpha track radiography and beta autoradiography in combination with optical microscopy and scanning electron microscopy. Alpha and beta maps have identified areas of higher activity, and these are concentrated predominantly within the surficial glassy component of trinitite. Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses conducted at high spatial resolution yield weighted average ²³⁵U/²³⁸U and ²⁴⁰Pu/²³⁹Pu ratios of 0.00718 ± 0.00018 (2σ) and 0.0208 ± 0.0012 (2σ), respectively, and also reveal the presence of some fission (¹³⁷Cs) and activation products (^152,154Eu). The LA-ICP-MS results indicate positive correlations between Pu ion signal intensities and abundances of Fe, Ca, U and ¹³⁷Cs. These trends suggest that Pu in trinitite is associated with remnants of certain chemical components from the device and surrounding Trinity test-related structures at ground zero. In contrast, negative correlations between Pu ion signals and SiO₂ and K₂O contents were observed within the glassy matrix of trinitite. This LA-ICP-MS result was corroborated by combined back-scattered electron imaging and alpha radiography, and indicates that Pu was not incorporated into unmelted crystalline grains of precursor minerals (i.e., quartz-SiO₂ and K-feldspar-KAlSi₃O₈) present within the desert sand at the Trinity site. The results from this study indicate that the device-related radionuclides were preferentially incorporated into the glassy matrix in trinitite.     

Development of a complex method for the determination of actinoides

A combined radiochemical separation method has been developed that enables the simultaneous determination of ²³⁴U, ²³⁵U, ²³⁸U, ²³⁷Np, ^239,240Pu, ²³⁸Pu, ²⁴¹Am, ²⁴²Cm, and ²⁴⁴Cm in medium and low level liquid radioactive wastes. The main steps of the method are sample destruction, co-precipitation on iron(II)-hydroxide and calcium-oxalate, separation by extraction chromatography using supported dipentyl-pentyl phosphonate (UTEVA) and supported N,N-octylphenyl-di-i-butylcarbamoylmethyl phosphine oxide with tributyl phosphate (TRU), and α source preparation. The key parameter of the method is the adjustment of the oxidation states of the actinoides before adding the sample onto the UTEVA column. It has been determined that (NH₄)₂S₂O₈ can be used for oxidation state adjustment resulting sufficient chemical yields.     

New approaches to reprocessing of oxide nuclear fuel

Dissolution of UO₂, U₃O₈, and solid solutions of actinides in UO₂ in subacid aqueous solutions (pH 0.9–1.4) of Fe(III) nitrate was studied. Complete dissolution of the oxides is attained at a molar ratio of ferric nitrate to uranium of 1.6. During this process actinides pass into the solution in the form of U(VI), Np(V), Pu(III), and Am(III). In the solutions obtained U(VI) is stable both at room temperature and at elevated temperatures (60 °C), and at high U concentrations (up to 300 mg mL^?1). Behavior of fission products corresponding to spent nuclear fuel of a WWER-1000 reactor in the process of dissolution the simulated spent nuclear fuel in ferric nitrate solutions was studied. Cs, Sr, Ba, Y, La, and Ce together with U pass quantitatively from the fuel into the solution, whereas Mo, Tc, and Ru remain in the resulting insoluble precipitate of basic Fe salt and do not pass into the solution. Nd, Zr, and Pd pass into the solution by approximately 50 %. The recovery of U or jointly U + Pu from the dissolution solution of the oxide nuclear fuel is performed by precipitation of their peroxides, which allows efficient separation of actinides from residues of fission products and iron.     

Radiolysis and corrosion of238Pu-doped UO2 pellets in chloride brine

Deaerated 5 M NaCl solution is irradiated in the presence of UO₂ pellets with α-radiation from²³⁸Pu. Experiments are conducted with²³⁸Pu doped pellets and others with²³⁸Pu dissolved in the brine. The radiolysis products and yields of mobilized U and Pu from the oxidative dissolution of UO₂ are determined. Results found for radiolysis products and for the oxidation/dissolution of pellets immersed in Pu containing brine are similar to results for Pu doped pellets, where the radiation chemical processes occur only in the liquid layer of some 10 σm thickness adjacent to the pellet. The yield of radiolysis products is comparable to earlier results, that of mobilized U from the pellets is < 1% of the total amount of oxidized species. Thus, the radiation chemical yield (G-value) for mobilized hexavalent U is < 0.01 ions/100 eV. In spite of the low radiation yield for the corrosion, the rate of UO₂dissolution is higher than expected for the concentrations of long-lived oxidizing radiolysis compounds found in the solutions.     

Distribution and behavior of some radionuclides associated with the Trinity nuclear test

The activities of ¹³³Ba, ¹³⁷Cs, ¹⁵²Eu, ¹⁵⁴Eu, ¹⁵⁵Eu, ²³⁹Pu, and ²⁴¹Am were determined by gamma spectroscopy on the largest sample set (n = 49) of bulk trinitite to date. The range in activity for all isotopes is large. For example, the activity of ²⁴¹Am (normalized to the time of detonation) ranges between 1 and 42 Bq/g. Comparison of activities for isotopes derived from the device, ²⁴¹Am versus ¹³⁷Cs, ¹⁵⁵Eu, and ²³⁹Pu, indicate positive trends. Correlations were not observed between the activities of the soil-derived activation products ¹⁵²Eu and ¹⁵⁴Eu and the radioisotopes from the device. The calculated ratio of fission products (¹⁵⁵Eu/¹³⁷Cs) is 0.012 ± .006 (1σ, n = 3), which is lower than predicted for the thermal neutron-induced fission of ²³⁹Pu (~0.03). This discrepancy may be attributed to the spontaneous fission of the natural U tamper resulting in mixing between fission products from ²³⁹Pu and ²³⁵U. The spatial distribution of the trinitite samples relative to ground zero has been modeled based on the activity of ¹⁵²Eu. The calculated distances do not correlate with any of the activities for the radioisotopes investigated here, and suggest a relatively homogeneous distribution. However, trinitite samples with the highest activities for ¹³⁷Cs, ²³⁹Pu, and ²⁴¹Am yield the shortest calculated distances of 50–60 m away from ground zero.     

A rapid separation of radioactive cesium by nitrobenzene extraction using the chromium complex [Cr(aniline)2(NCS)4]−

A rapid separation of radioactive cesium by the solvent extraction method was investigated. Cesium ions are quantitatively extracted with [Cr(NH₂C₆H₅)₂(NCS)₄]⁻ into nitrobenzene. EDTA is an effective masking agent for other polyvalent cations. The extracted cesium can be back-extracted into the aqueous phase by shaking with 6N HCl. The method was applied to samples of a natural mixture of fission products and a reactor coolant. The decontamination factors for other predominant isotopes in fission products were 10²∼10⁴. The separation of^137m Ba from a mixture of¹³⁷Cs and^137m Ba is also described.     

Development of a SIMS Method for Isotopic Measurements in Nuclear Forensic Applications

 Methodologies based on secondary ion mass spectrometry (SIMS) for isotopic measurements in nuclear forensic applications relevant to the age determination of Pu particles and isotopic composition of oxygen for geolocation assignment are described. For the age determination of Pu particles, a relative sensitivity factor (RSF) to correct for the different ionisation efficiencies of U and Pu, was obtained by analysing standard Pu materials with known ages. An RSF of 2.41±0.05 was obtained for PuO₂ from measurements on samples with different Pu/U ratios. In a sample of known origin, using this RSF value, the age calculated from the ²³⁸Pu/²³⁴U and ²⁴⁰Pu/²³⁶U ratios agreed well with the reported age of 2.3 years. For geolocation assignment, a new approach based on the measurement of differences in the natural abundance of ¹⁸O and ¹⁶O isotopes and their ratio was developed. The instrumental mass discrimination of the ¹⁸O/¹⁶O ratio was determined using three O-isotope samples of different chemical composition. The measured precision (the standard error of 100 cycles/analysis) obtained for the oxygen isotopic measurement on the samples was typically ±1.1‰.