<Superscript>234</Superscript>U/<Superscript>235</Superscript>U activity ratios as a probe for the <Superscript>238</Superscript>U/<Superscript>235</Superscript>U half-life ratio

High-resolution alpha-particle spectrometry was performed on three uranium materials enriched in ²³⁵U. Besides the ²³⁵U peaks, separate peaks belonging to impurity traces of ²³⁴U could be quantified. Relying on the isotopic composition of the uranium, as determined by mass spectrometry, the ratio of the half-lives of ²³⁸U and ²³⁵U was determined via the activity ratio of ²³⁴U and ²³⁵U in the materials. As an intermediate link, the ²³⁴U/²³⁸U half-life ratio was taken from published mass spectrometric analyses of ‘secular equilibrium’ uranium material. The resulting half-life ratio T _1/2(²³⁸U)/T _1/2(²³⁵U) = 6.351±0.031 is in agreement with the commonly adopted half-life values determined by Jaffey et al.     

Uranium analysis in urine by inductively coupled plasma dynamic reaction cell mass spectrometry

Urine uranium concentrations are the best biological indicator for identifying exposure to depleted uranium (DU). Internal exposure to DU causes an increased amount of urine uranium and a decreased ratio of ²³⁵U/²³⁸U in urine samples, resulting in measurements that vary between 0.00725 and 0.002 (i.e., natural and depleted uraniums ²³⁵U/²³⁸U ratios, respectively). A method based on inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-MS) was utilized to identify DU in urine by measuring the quantity of total U and the ²³⁵U/²³⁸U ratio. The quantitative analysis was achieved using ²³³U as an internal standard. The analysis was performed both with and without the reaction gas oxygen. The reaction gas converted ionized ²³⁵U⁺ and ²³⁸U⁺ into ²³⁵UO₂⁺ (m/z=267) and ²³⁸UO₂⁺ (m/z=270). This conversion was determined to be over 90% efficient. A polyatomic interference at m/z 234.8 was successfully removed from the ²³⁵U signal under either DRC operating conditions (with or without oxygen as a reaction gas). The method was validated with 15 urine samples of known uranium compositions. The method detection limit for quantification was determined to be 0.1 pg U mL^–1 urine and an average coefficient of variation (CV) of 1–2% within the sample measurements. The method detection limit for determining ²³⁵U/²³⁸U ratio was 3.0 pg U mL^–1 urine. An additional 21 patient samples were analyzed with no information about medical history. The measured ²³⁵U/²³⁸U ratio within the urine samples correctly identified the presence or absence of internal DU exposure in all 21 patients.The opinions and assertions expressed herein are those of the authors and are not to be construed as official or as representing the views of the Armed Forces Institute of Pathology, the Department of the Army, or the Department of Defense     

Non-destructive determination of nuclear fuel burn-up by measuring the gamma radiation of fission products in irradiated uranium oxide

The burn-up of²³⁵U was determined in two uranium oxide samples (0.713 and 89.9%²³⁵U in mixture) irradiated simultaneously with a cobalt monitor, from the amounts of⁹⁵Zr,¹⁰³Ru,¹³⁷Cs,¹⁴⁰Ba and¹⁴⁴Ce obtained by measuring the intensities of the corresponding gamma radiations. The samples were irradiated for 23 days, and the fission products were measured after cooling for 100 days, nondestructively, by means of a Ge(Li) spectrometer. The integrated neutron flux was determined by measuring the produced⁶⁰Co in the cobalt monitor. The burn-up in both samples was determined by measuring the intensity of eight gamma energies (0.5–1.6 MeV). The determined values are in good agreement. The standard deviation of the mean value ( ) is 5%. The atom per cent fission of²³⁵U in both samples, calculated according to , differs by 1%. The measured σ _f for²³⁵U is in good agreement with the data reported in the literature.     

Background levels of238U and226Ra in atmospheric aerosols

The²³⁸U and²²⁶Ra contents of small-volume aerosols are determined by a chemical analysis technique. Mean activity concentrations of²³⁸U and²²⁶Ra in aerosols over approximately ten years are 0.29·10^–5 and 0.93·10^–5 Bq/m³, respectively. The yearly variation of²³⁸U and²²⁶Ra in aerosols is small. The concentrations of²²⁶Ra are always larger than those of²³⁸U in the same sampling time. The correlation of²³⁸U and²²⁶Ra cannot be recogonized (r=0.18). The concentrations of summer samples are greater than those of winter samples for²³⁸U. One of the causes of seasonal difference may be due to the fact that the components of aerosols are different according to soil size, soil components, weathering states, etc.     

Die Bestimmung des234U/238U-Verhältnisses in Proben von natürlichem Wasser

Zusammenfassung Eine zur Bestimmung des Isotopenverhältnisses²³⁴U/²³⁸U in natürlichem Wasser geeignete Methodik wurde beschrieben. Die Anwendungs-bedingungen des einfachsten-Spektrometers, des Szintillations-Spektrometers sowie die Hauptschritte des Verfahrens werden angegeben und einige mit der beschriebenen Methode an verschiedenen Wasserproben bestimmten Isotopenverhältnisse werden angeführt.

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The determination of the²³⁴U/²³⁸U ratio in samples of natural water

Summary A method suitable for the determination of the isotope ratio²³⁴U/²³⁸U in natural waters, is described. Conditions of the use of the most simple-spectrometer, the scintillation spectrometer, are discussed. The principal steps of the procedure are given, and the isotope ratios of various water samples determined with the method described are presented.

     

Kinetics and Mechanism of Catalytic Reduction of U(VI) with Hydrazine on Platinum Catalysts in Nitric Acid Media

The kinetics of U(IV) produced by hydrazine reduction of U(VI) with platinum as a catalyst in nitric acid media was studied to reveal the reaction mechanism and optimize the reaction process. Electron spin resonance (ESR) was used to determine the influence of nitric acid oxidation. The effects of nitric acid, hydrazine, U(VI) concentration, catalyst dosage and temperature on the reaction rate were also studied. In addition, the simulation of the reaction process was performed using density functional theory. The results show that the influence of oxidation on the main reaction is limited when the concentration of nitric acid is below 0.5 mol/L. The reaction kinetics equation below the concentration of 0.5 mol/L is found as: -dc(UO₂²⁺)/dt)=kc^0.5323(UO₂²⁺)c^0.2074(N₂H₅⁺)c^-0.2009(H⁺). When the temperature is 50 ℃, and the solid/liquid ratio r is 0.0667 g/mL, the reaction kinetics constant is k=0.00199 (mol/L)^0.4712/min. Between 20 ℃ and 80 ℃, the reaction rate gradually increases with the increase of temperature, and changes from chemically controlled to diffusion-controlled. The simulations of density functional theory give further insight into the influence of various factors on the reaction process, with which the reaction mechanisms are determined according to the reaction kinetics and the simulation results.     

Uracil and the tautomer 4-hydroxyuracil: An ab initio study with geometry optimization

Ab initio STO -3G geometries and relative energies for uracil (U) and the tautomer 4-hydroxyuracil (U*) were obtained with the HONDO program utilizing the rapidly convergent method of Murtaugh and Sargent for geometry optimization. ΔE for U?U* is 6.61 kcal/mole. The reaction field continuum model for solvent effect indicates a preferential stabilization of U* by 1.0 kcal/mole. The calculated gas phase K_t and solution K_t for U?U* are 1.44×10^?5 and 1.3×10^?4, respectively.     

Glucose and glycerol concentrations and their tracer enrichment measurements using liquid chromatography tandem mass spectrometry

The present study describes a new liquid chromatography tandem mass spectrometry method for high‐throughput quantification of glucose and glycerol in human plasma using stable isotopically labeled internal standards and is suitable for simultaneous measurements of glucose and glycerol enrichments in connection to in vivo metabolic studies investigating glucose turnover and lipolytic rate. Moreover, in order to keep up with this new fast analysis, simple derivatization procedures have been developed. Prior to analysis, glucose and glycerol were derivatized using benzoyl chloride in order to form benzoylated derivatives via new simplified fast procedures. For glucose, two internal standards were evaluated, [U‐¹³C₆]glucose and [U‐¹³C₆, D₇]glucose, and for glycerol, [U‐¹³C₃, D₈]glycerol was used. The method was validated by means of calibration curves, quality control samples, and plasma samples spiked with [6,6‐D₂]glucose, [U‐¹³C₆]glucose, and [1,1,2,3,3‐D₅]glycerol in order to test accuracy, precision, and recovery of the method. Moreover, post preparative and freeze‐thaw sample stability were tested. The correlation of calibration curves for the glucose concentration were r² = 0.9998 for [U‐¹³C₆]glucose and r² = 0.9996 for [U‐¹³C₆, D₇]glucose, and r² = 0.9995 for the glycerol concentration. Interday accuracy for glucose using [U‐¹³C₆]glucose and glycerol determined in spiked plasma were respectively 103.5% and 106.0%, and the coefficients of variation were 2.0% and 9.7%, respectively. After derivatization, plasma samples were stable for at least 14 days. In conclusion, we have developed and validated a novel, accurate, and sensitive high‐throughput liquid chromatography tandem mass spectrometry method for simultaneous determination of glucose and glycerol concentrations and enrichment of infused tracers most commonly used in human metabolic kinetic studies. Copyright © 2014 John Wiley & Sons, Ltd.     

Measurement of the neutron capture cross-section of 238U using the neutron activation technique

The ²³⁸U(n, ??)²³⁹U reaction cross-section at average neutron energy of 3.7?±?0.3?MeV from the ⁷Li(p, n)⁷Be reaction has been determined using activation and off-line ??-ray spectrometric technique. The ²³⁸U(n, ??)²³⁹U and ²³⁸U(n, 2n)²³⁷U reaction cross-sections at average neutron energy of 9.85?±?0.38?MeV from the same ⁷Li(p, n)⁷Be reaction have been also determined using the above technique. The experimentally determined ²³⁸U(n, ??)²³⁹U and ²³⁸U(n, 2n)²³⁷U reaction cross-sections were compared with the evaluated data of ENDF/B-VII, JENDL-4.0, JEFF-3.1 and CENDL-3.1. The experimental values were found to be in general agreement with the evaluated value based on ENDF/B-VII, and JENDL-4.0 but not with the JEFF-3.1 and CENDL-3.1. The present data along with literature data in a wide range of neutron energies were interpreted in terms of competition between different reaction channels including fission. The ²³⁸U(n, ??)²³⁹U and ²³⁸U(n, 2n)²³⁷U reaction cross-sections were also calculated theoretically using the TALYS 1.2 computer code and were also found to be in agreement experimental data.     

Limit of the INAA procedure for copper determination based on the64Cu 511 keV line

The²³⁵U/²³⁸U ratio is determined by neutron activation analysis counting the ϕ-rays of short half-lives fission products and²³⁹U. The effect of the neutron spectrum hardening using a⁶LiD converter is also demonstrated. The²³⁵U/²³⁸U ratio is determined using short irradiation, waiting and counting times.     

Improvement in precision of extremely low <Superscript>236</Superscript>U/<Superscript>238</Superscript>U isotope ratio determination by using mass spectrometer with narrow dynamic range

The precision in measurement of trace level uranium isotopic ratio, i.e., ²³⁶U/²³⁸U or ²³⁴U/²³⁸U, on single Faraday detector with narrow dynamic range is very hard to achieve. this is mainly due to the narrow dynamic range of a single detector systems. A significant improvement in mass spectrometric determination of ²³⁶U/²³⁸U ratio has been achieved by employing an alternate method using a single Faraday detector of narrow dynamic range. The method makes use of the precise measurements of the ²³⁶U/²³⁴U ratio, ²³⁴U/²³⁵U ratio and ²³⁵U/²³⁸U ratio, which are used to calculate the ²³⁶U/²³⁸U ratio using the equation ²³⁶U/²³⁸U=²³⁶U/²³⁴Uײ³⁴U/²³⁵Uײ³⁵U/²³⁸U. Despite the fact that correlation of the data tends to increase the uncertainty in the result, our results show a significant improvement, i.e., more than 8 times better precision in measuring the ²³⁶U/²³⁸U ratio with this method (σ=3.98×10⁻⁰⁸) as compared to direct measurement of ²³⁶U/²³⁸U (σ=3.104×10⁻⁰⁷). The method widens the applicability of the single collector system with narrow dynamic range and it will potentially be helpful to improve the precision in the case of the static multi-collector system also. The objective of the present study was to compare the results of the same sample analyzed with the present alternate method and the direct method for precision.     

Simulatenous determination of uranium and plutonium in inactive purex process solution by X-ray fluorescence

By intensity measurements of the uranium and plutoniumL _α1-lines these elements can be determined simultaneously either in aqueous or in organic Purex process solutions. Thorium was used as an internal standard. The sensitivity of the method is about 10⁵ cpm/mg U, Pu/ml and the detection limits are around 2–3 μg U, Pu/ml. The analytical range extends from 0.003 mg U, Pu/ml up to 10 mg U, Pu/ml. A time-saving routine procedure is described. Interferences detected at extreme U/Pu concentration ratios are discussed and explained.     

Ab initio molecular treatment of electron capture processes in the B3++He collision

The potential energy curves and the coupling matrix elements of the¹¹ and¹ states involved in the collision of the B³⁺(1s ²) multicharged ion on a He target have been calculated by means of an ab initio method with configuration interaction. The total and partial capture cross-sections have been determined, using a semi-classical method. The results are in good agreement with experiment, exhibiting a strong influence of rotational coupling even at low energies.     

Measurement of production date (age) of nanogram amount of uranium

JRC-Karlsruhe obtained a swipe sample from a highly enriched uranium seizure, which had taken place in 2011. Due to the very low amount of uranium (nanograms) a new method needed to be developed to determine the U production date (age). The particles on the swipe were collected on a pyrolytic graphite planchet using a vacuum impactor and they were subsequently leached with ccHNO₃. The “bulk” U isotopic composition (²³⁵U: 72.51?±?0.03 wt%) and the production date (December 1992?±?1 year) determined by MC-ICP-MS indicated that the material showed similarity with two other HEU cases seized earlier in Europe.

     

(18‐Crown‐6)‐μ‐oxo‐hexa­kis(tetra­hydro­borato)diuranium(IV): an unprecedented asymmetric dinuclear complex

In the title compound, (1,4,7,10,13,16‐hexa­oxacyclo­octa­decane‐1κ⁶O)‐μ‐oxo‐1:2κ²O:O‐hexa­kis(tetra­hydro­borato)‐1κ³H;2κ²H;2κ²H;2κ³H;2κ³H;2κ³H‐diuranium(IV), [U₂(BH₄)₆O(C₁₂H₂₄O₆)], one of the U atoms (U1), located at the centre of the crown ether moiety, is bound to the six ether O atoms, and also to a tridentate tetra­hydro­borate group and a μ‐oxo atom in axial positions. The other U atom (U2) is bound to the same oxo group and to five tetra­hydro­borate moieties, three of them tridentate and the other two bidentate. The two metal centres are bridged by the μ‐oxo atom in an asymmetric fashion, thus giving the species (18‐crown‐6)(κ³‐BH₄)U=(μ‐O)—U(κ³‐BH₄)₃(κ²‐BH₄)₂, in which the U1=O and U2—O bond lengths to the μ‐O atom [1.979 (5) and 2.187 (5) Å, respectively] are indicative of the presence of positive and negative partial charges on U1 and U2, respectively.     

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.     

Oligonucleotide Analogues with Integrated Bases and Backbone. Part 15

The self‐complementary (Z)‐configured U*[c_e]A⁽*⁾ dinucleotide analogues 6, 8, 10, 12, 14 , and 16 , and the A*[c_e]U⁽*⁾ dimers 19, 21, 23, 25, 27 , and 29 were prepared by partial hydrogenation of the corresponding ethynylene linked dimers. Photolysis of 14 led to the (E)‐alkene 17 . These dinucleotide analogues associate in CDCl₃ solution, as evidenced by NMR and CD spectroscopy. The thermodynamic parameters of the duplexation were determined by van't Hoff analysis. The (Z)‐configured U*[c_e]A⁽*⁾ dimers 14 and 16 form cyclic duplexes connected by Watson–Crick H‐bonds, the (E)‐configured U*[c_e]A dimer 17 forms linear duplexes, and the U*[c_e]A⁽*⁾ allyl alcohols 6, 8, 10 , and 12 form mixtures of linear and cyclic duplexes. The C(6/I)‐unsubstituted A*[c_e]U allyl alcohols 19 and 23 form linear duplexes, whereas the C(6/I)‐substituted A*[c_e]U* allyl alcohols 21 and 25 , and the C(5′/I)‐deoxy A*[c_e]U⁽*⁾ dimers 27 and 29 also form minor amounts of cyclic duplexes. The influence of intra‐ and intermolecular H‐bonding of the allyl alcohols and the influence of the base sequence upon the formation of cyclic duplexes are discussed.     

Theoretical Study of Chemical Binding of Noble Gas Atom and Transition Metal Complexes: Ng–NiCO, Ng–NiN2, Ng–CoCO (Ng = He–Xe)

Ab initio multireference and coupled cluster methods (MR-SDCI(+Q), CASPT2, CCSD(T)) and density functional theory methods (B3LYP, MPWPW91) have been applied to examine geometrical structures and vibrational frequencies of noble gas (Ng) – transition metal compounds, Ng–NiCO, Ng–NiN₂, and Ng–CoCO (Ng = He, Ne, Ar, Kr, Xe). It is shown that the respective compounds can have a larger binding energy than a typical van der Waals interaction energy. The binding mechanism is explained by a partial electron transfer from a noble gas atom to the low-lying 4s and 3d vacant orbitals of the transition metal atom. Theoretical calculations show that the binding of noble gas atom results in a large shift of the bending frequency: 361.1cm^–1 (NiCO) to 403.5cm^–1 (Ar–NiCO); 308.5cm^–1 (NiN₂) to 354.8cm^–1 (Ar–NiN₂); 373.0cm^–1 (CoCO) to 422.6cm^–1 (Ar–CoCO). The corresponding experimental frequencies determined in solid argon are 409.1cm^–1 (NiCO), 357.0cm^–1 (NiN₂), and 424.9cm^–1 (CoCO), which are much closer to the corresponding frequency of Ar–NiCO, Ar–NiN₂, and Ar–CoCO, respectively.     

Feasibility study of <Superscript>233</Superscript>Pa and <Superscript>233</Superscript>U determination in neutron irradiated thorium for future applications in thorium–uranium nuclear fuel cycle

With regard to the use of thorium fuel for future nuclear energy production, two methods of ²³³U assay were studied in neutron irradiated thorium and in a mixture of thorium and uranium. The former was based on gamma-spectrometry determination of the ²³³Pa radionuclide, a precursor of ²³³U. The latter was direct determination of ²³³U by neutron activation analysis with counting of delayed neutrons. The mass of ²³³U determined by both methods is compared with that calculated using Maple9.5 software package.