Temperature and ionic strength influence on U(VI/V) and U(IV/III) redox potentials in aqueous acidic and carbonate solutions

Redox potentials: E(UO ₂ ²⁺ /UO ₂ ⁺ )=60±4 mV/NHE, E(U⁴⁺/U³⁺)=–630±4mV/NHE measured at 25°C in acidic medium (HClO₄ 1M) using cyclic voltametry are in accordance with the published data. From 5°C to 55°C the variations of the potentials of these systems (measured against Ag/AgCl electrode) are linear. The entropies are then constant: [S(UO ₂ ²⁺ /UO ₂ ⁺ )–S(Ag/AgCl)]/F=0±0.3 mV/°C, [S(U⁴⁺/U³⁺)–S(Ag/AgCl)]/F=1.5±0.3 mV/°C. From 5°C to 55°C, in carbonate medium (Na₂CO₃=0.2M), the Specific Ionic Interaction Theory can model the experimental results up to I=2M (Na⁺, ClO ₄ ^– , CO ₃ ^2– ): E(UO₂(CO₃) ₃ ^4– /UO₂(CO₃) ₃ ^5– )=–778±5 mv/NHE (I=0, T=25°C, (25°C)=(UO₂(CO₃) ₃ ^4– , Na⁺)–(UO₂(CO₃) ₃ ^5– , Na⁺)=0.92 kg/mole, S(UO₂(CO₃) ₃ ^4– /UO₂(CO₃) ₃ ^5– =–1.8±0.5 mV/°C (I=0), =(Cl^–, Na⁺)=(1.14–0.007T) kg/mole. The U(VI/V) potential shift, between carbonate and acidic media, is used to calculate (at I=0,25°C):

Isotope exchange and separation factor of238U/235U for the system U(III)/U(IV) in aqueous/organic phases

A study of the isotope exchange reaction U(III)_org/U(IV)_aq in the extraction system: 7M HCl — tributyl phosphate (TBP) — toluene has been performed. For 20 s of contact the results show a separation factor²³⁵U/²³⁸U of 1.014. This large separation factor is explained by the oxidation reaction of²³⁵U(III) and²³⁸U(III).     

Plutonium, 137Cs and U in some pond and lake sediments from areas surrounding the Semipalatinsk Nuclear Test Site: With emphasis on anomalously high U accumulation

Sediment core samples were collected up to a depth of 25–40 cm from three ponds (P. Korosteli, P. Mihairov and P. Alkat) and two lakes (L. Kanoneruka and L. Semanaika) located in widely separated regions outside the former Semipalatinsk Nuclear Test Site (SNTS) in Kazakhstan. The ¹³⁷Cs, Pu and U concentrations with depth were determined in samples divided at 1 cm intervals from the top of each core. These sediment cores were dated by the excess ²¹⁰Pb method. The reservoirs with low sedimentation rates of 0.038–0.41 g·cm^–2·y^–1 permitted, but not in detail, the estimation of the depositional history of close-in fallout of ¹³⁷Cs and Pu within these regions. The sediments accumulating an anomalously high ²³⁸U concentration of 250–400 Bq/kg were also found for two of the five reservoirs, in which their ²³⁴U/²³⁸U and ²³⁵U/²³⁸U activity ratios were 1.3–2.0 and around 0.047 (nearly the same as that of natural U), respectively. Such U enrichment at the subsurface with a thin layer of lower-U sediment at the surface is mainly due to infiltration of lake water containing U from the ground water flowing into the lake or pond, followed by reduction of U(VI) to U(IV) at the redox boundary.The authors would like to express their gratitude to research staff of the Kazakh Scientific Research Institute for Radiation Medicine and Ecology for sediment and soil sampling. This work was supported by a Grant in Aid for Scientific Research from the Ministry of Education and Culture of Japan, Monbusuo International Scientific Research Program during the period of 1995–2003, represented by Profs. M. Hoshi and M. Yamamoto.     

Selective extraction of U(VI), Th(IV), and La(III) from acidic matrix solutions and environmental samples using chemically modified Amberlite XAD-16 resin

A new grafted polymer has been developed by the chemical modification of Amberlite XAD-16 (AXAD-16) polymeric matrix with [(2-dihydroxyarsinoylphenylamino)methyl]phosphonic acid (AXAD-16-AsP). The modified polymer was characterized by a combination of ¹³C CPMAS and ³¹P solid-state NMR, Fourier transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis (TGA). The distribution studies for the extraction of U(VI), Th(IV), and La(III) from acidic solutions were performed using an AXAD-16-AsP-packed chromatographic column. The influences of various physiochemical parameters on analyte recovery were optimized by both static and dynamic methods. Accordingly, even under high acidities (>4 M), good distribution ratio (D) values (10²–10⁴) were achieved for all the analytes. Metal ion desorption was effective using 1 mol L^–1 (NH₄)₂CO₃. From kinetic studies, a time duration of <15 min was sufficient for complete metal ion saturation of the resin phase. The maximum metal sorption capacities were found to be 0.25, 0.13, and 1.49 mmol g^–1 for U(VI); 0.47, 0.39, and 1.40 mmol g^–1 for Th(IV); and 1.44, 1.48, and 1.12 mmol g^–1 for La(III), in the presence of 2 mol L^–1 HNO₃, 2 mol L^–1 HCl, and under pH conditions, respectively. The analyte selectivity of the grafted polymer was tested in terms of interfering species tolerance studies. The system showed an enrichment factor of 365, 300, and 270 for U(VI), Th(IV), and La(III), and the limit of analyte detection was in the range of 18–23 ng mL^–1. The practical applicability of the polymer was tested with synthetic nuclear spent fuel and seawater mixtures, natural water, and geological samples. The RSD of the total analytical procedure was within 4.9%, thus confirming the reliability of the developed method.     

Solvent Extraction Separation of Th(IV) and U(VI) with PC-88A

Liquid-liquid extraction of Th(IV) and U(VI) has been investigated by commercial extractant PC-88A in toluene. The optimum conditions for extraction of these metals have been established by studying the various parameters like acid concentration/pH, reagent concentration, diluents and shaking time. The extraction of Th(IV) was found to be quantitative with 0.1–1.0M HNO₃ acid and in the pH range 1.0–4.0 while U(VI) was completely extracted in the pH range 1.0–3.5 with 2.5·10^–2M and 2.·10^–2M PC-88A in toluene, respectively. The probable extracted species have been ascertained by log D-log C plot as ThR₄·4HR and UO₂R₂·2HR, respectively. The method permits separation of Th(IV) and U(VI) from associated metals with a recovery of 99.0%.     

The Spontaneous Fission Decay Constant of 238U Using SSNTD

This work reports the results of 5 measurements of the ²³⁸U decay constant for spontaneous fission, _f carried out using solid state nuclear track detectors (SSNTD), resulting in a mean value of _f = (8.35±0.24)· 10^–17 y^–1. The neutron fluence of the irradiations needed for these measurements were monitored with thin films of natural uranium.     

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).     

Effect of the Electrode Potential on the Oxygen Reaction Rate in the Electrode System O2, Au/La0.88Sr0.12Ga0.82Mg0.18O2.85

The polarization dependences of a porous gold electrode in contact with a solid electrolyte of the composition La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85 are studied at 600–800°C and oxygen pressures of 2 × 10⁻²-1 atm. It is shown that the rate of cathodic reduction of oxygen out of the gas phase depends on the preliminary treatment of the sample. The activation energy is equal to 110–135 kJ mol⁻¹ at a low polarization. After increasing the polarization, the activation energy for the cathodic reduction of oxygen equals 75–85 kJ mol⁻¹ and depends on the oxygen pressure as a power function with a power index of 1/4. The rate of the anodic evolution of oxygen is dependent neither on the preliminary treatment of the sample nor on the oxygen pressure in the gas phase and the polarization curve has a characteristic segment, which corresponds to a limiting overvoltage.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 954–962.Original Russian Text Copyright © 2005 by Shkerin, Sokolova, Beresnev.     

High accuracy determination of235U in nondestructive assay standards by gamma spectrometry

High precision gamma spectrometry measurements have been made on five sets of uranium isotope abundance reference materials for nondestructive assay (NDA). These sets are intended for international safeguards use as primary reference materials for the determination of the²³⁵U abundance in homogeneous uranium bulk material by gamma spectrometry. The measurements were made to determine the count rate uniformity of the²³⁵U 185.7 keV gamma-ray as well as the²³⁵U isotope abundance for each sample. Since the samples were packaged such that the U₃O₈ is infinitely thick for the 185.7 keV gamma-ray, the measured count rate was not dependent on the material density. In addition, the activity observed by the detector was collimated to simulate calibration conditions used to measure bulk material in the field. The sample-to-sample variations observed within the 5 sets of samples ranged between 0.005–0.11% (1s) with standard deviations of the mean ranging from 0.01–0.02%. This observed variation appears to be due predominantly to counting statistics and not to material inhomogeneity and/or packaging. The results of this study indicate that accuracy of²³⁵U determinations via gamma spectrometry, in the range of few hundredths of a percent (2), is achievable. The main requirement for achieving this level of accuracy is a set of standards whose²³⁵U isotope abundances are known to within 0.01% (2).     

Plutonium, 137Cs and U in some pond and lake sediments from areas surrounding the Semipalatinsk Nuclear Test Site: With emphasis on anomalously high U accumulation

Sediment core samples were collected up to a depth of 25–40 cm from three ponds (P. Korosteli, P. Mihairov and P. Alkat) and two lakes (L. Kanoneruka and L. Semanaika) located in widely separated regions outside the former Semipalatinsk Nuclear Test Site (SNTS) in Kazakhstan. The ¹³⁷Cs, Pu and U concentrations with depth were determined in samples divided at 1 cm intervals from the top of each core. These sediment cores were dated by the excess ²¹⁰Pb method. The reservoirs with low sedimentation rates of 0.038–0.41 g·cm^–2·y^–1 permitted, but not in detail, the estimation of the depositional history of close-in fallout of ¹³⁷Cs and Pu within these regions. The sediments accumulating an anomalously high ²³⁸U concentration of 250–400 Bq/kg were also found for two of the five reservoirs, in which their ²³⁴U/²³⁸U and ²³⁵U/²³⁸U activity ratios were 1.3–2.0 and around 0.047 (nearly the same as that of natural U), respectively. Such U enrichment at the subsurface with a thin layer of lower-U sediment at the surface is mainly due to infiltration of lake water containing U from the ground water flowing into the lake or pond, followed by reduction of U(VI) to U(IV) at the redox boundary.The authors would like to express their gratitude to research staff of the Kazakh Scientific Research Institute for Radiation Medicine and Ecology for sediment and soil sampling. This work was supported by a Grant in Aid for Scientific Research from the Ministry of Education and Culture of Japan, Monbusuo International Scientific Research Program during the period of 1995–2003, represented by Profs. M. Hoshi and M. Yamamoto.     

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.     

Radiolysis of U(VI)-arsenazo-1 complex in aqueous solutions

The effect of absorbed dose on the decolouration of U(VI)-arsenazo-1 complex solutions has been investigated at pH 8.3. G-values were determined as a function of complex concentration as well as of OH, e _aq ^– scavengers. Using competition kinetics, rate constants were determined and the degradation mechanism discussed.     

Radiation chemistry of CF2 Cl2 in the gas and liquid phases: Effect of doses rate

The dose rate dependence of CF₂ Cl₂ decomposition was studied in both, gas and liquid phase, for the range of 2.95·10^{1 7}–1.9·10^{1 9} eV·g^–1·h^–1. The major products were found to be CF₃Cl, CFCl₃, CF₂Cl–CF₂Cl and CF₂Cl–CFCl₂. The decomposition of CF₂Cl₂ was found to decrease with decreasing dose rate for the liquid phase, while an opposite trend was found for gas phase radiolysis. A new mechanism which explains these contrasting findings was suggested. The contribution of radical and of ionic (or molecular) processes to the yields of the various products was estimated.     

Pseudohalogen compounds of astatine: Synthesis and characterization of At/I/-tricyanomethanide-and At/I/-azide-compounds

Reactions of At//⁺, At^o.H₂O, AtCl ₂ ^– and AtBr₂ with the pseudohalogenides tricyanomethanide and azide are described. Information on the compound formation of astatine with C/CN/ ₃ ^– and N ₃ ^– could be obtained on the basis of electromigration investigations under variation of the conditions /composition of the electrolyte, pH, exchange reactions of ligands/. For the reaction: [At/H₂O/C/CN/₃]+C/CN/ ₃ ^– [At/C/CN/₃/₂]+H₂O at 301 K and u=0.075 mol.l^–1 K₂=/675±25/ [1.mol^–1] and u^o=–/3.50±0.10/×10^–4 [cm².s^–1.V^–1]. According to this astatine/I/-tricyanomethanide is classified between AtI ₂ ^– and At/SCN/ ₂ ^– . First investigations in azid-containing systems confirm the formation of astatine/I/-azide-compounds. Their composition is probably At/N₃/ ₂ ^– . There is no dependence of the ion mobility of astatine/I/-azide in the investigated range on azide concentration which is due to its high stability.     

Mechanism and kinetics of crystallization of α-Fe in amorphous Fe81B13Si4C2 alloy

The non-isothermal crystallization of α-Fe from Fe₈₁B₁₃Si₄C₂ amorphous alloy was investigated. The kinetic parameters of crystallization process were determined by Kissinger and Kissinger–Akahira–Sunose (KAS) methods. It was established that the kinetic parameters of transformation do not change with the degree of crystallization in the range of 0.1–0.7. The kinetic model of the crystallization process was determined using the Malek's procedure. It was established that the primary crystallization α-Fe phase from amorphous alloy can be described by Šesták–Berggren autocatalytic model with kinetic triplet E_a = 349.4.0 kJ mol⁻¹, ln A = 50.76 and f(α) = α^0.72(1 − α)^1.02.     

Radiation induced electron exchange reaction of thallium/I/-thallium/III/ at low sulfate ion concentration in perchloric acid solution

To understand the behaviour of Tl/II/ and the bridging group SO ₄ ^2– in radiation induced electron exchange reactions we have investigated the rate constants and mechanisms of reaction of Tl/II/ with Tl/I/ and Tl/III/ in perchloric acid solutions. The results indicated that Tl/II/ is an intermediate in the -ray induced electron exchange process of T1/I/–T1/III/. Sulfate ions at [SO ₄ ^2– ]>-0.02M serve as bridging groups and play an important role in accelerating the T1/II/–T1/I/ reaction. A cooperative effect was found between hydrogen peroxide and sulfate ion at low sulfate ion concentration, [SO ₄ ^2– ]0.02M in perchloric acid solution.     

Kinetic studies on the extraction of U(IV) by TBP in kerosene from nitrate medium

The kinetics of extraction of U(IV) by TBP in kerosene was investigated using a stirred Lewis cell. The effect of the different parameters affecting the extraction rate as well as temperature were separately investigated. The rate equation deduced from the experimental results show that the extraction of U(IV) is first order dependent on TBP concentration while it is of zero order with respect to U(IV), H⁺, NO ₃ ^– and HNO₃ concentrations. The data obtained show that the extraction process is governed by chemical reactions taking place at teh interface.     

Synthesis of hexylthiols C6H13SH−1/1, 2, 3, 4−14C1/4/' /1-thiol[35S]/ and C6H13SH−2/1, 2, 3, 4−14C1/4/, /2-thiol[35S]/

A synthesis of¹⁴C and³⁵S double labelled hexylthiols: C₆H₁₃SH–1/1, 2, 3, 4–¹⁴C_1/4/, /1-thiol[³⁵S]/ and C₆H₁₃SSH–2/1, 2, 3, 4–¹⁴C_1/4/, /2-thiol[³⁵S]/ based on H₂ ³⁵S and C₆H₁₂–/1, 2, 3, 4–¹⁴C_1/4/ has been developed and described.     

Ultratrace characterization of AlSiCu sputter targets for Th,U and 35 other elements by neutron activation analysis

Instrumental and radiochemical neutron activation analysis has been applied to a comprehensive trace characterization of AlSiCu sputter targets. By instrumental neutron activation analysis via long-lived indicator radionuclides, up to 33 elements were assayed with detection limits between 0.01 and 200 ng·g^–1. The high activity of⁶⁴Cu and²⁴Na produced from the matrix significantly limits the instrumental performance via short- and medium-lived indicator dionuclides. For this reason, a radiochemical separation was developed based on adsorption of²⁴Na on hydrated antimony pentoxide and extraction of⁶⁴Cu by diethylammonium diethyldithiocarbamate from HCl medium. By this radiochemical method, As, Ga, K, La, Mn, Mo, Re, Sb, U and W could be assayed via medium-lived radionuclides and the achievable limits of detection were between 0.1 and 25 ng·g^–1. Further improvement of detection limits for U and Th was achieved by a selective radiochemical separation of²³⁹Np and²³³Pa on a Dowex 1×8 column in HF and HF/NH₄F medium providing limits of detection for U and Th of 0.06 and 0.02 ng·g^–1, respectively. These techniques were applied to the analysis of two AlSiCu sputter target materials. Results are compared with those of glow discharge mass spectrometry.     

Selective Preconcentration of U(VI) and Th(IV) in Trace and Macroscopic Levels Using Malonamide Grafted Polymer from Acidic Matrices

A novel polymeric sorbent for selective extraction of U(VI) and Th(IV) from highly acidic wastes was prepared by modifying Merrifield chloromethylated resin with N,N,N′,N′-tetrahexylmalonamide. The functionalized resin was characterized by FT-IR spectroscopy, CPMAS NMR spectroscopy, CHN elemental analysis and thermo-gravimetric analysis. Various physiochemical parameters responsible for quantitative extraction of metal ions were studied by static and dynamic methods. The resin exhibited very good extractability over a wide range of acidity (0.01–10 M) with a faster exchange rate (saturation possible within 20 min) and high sorption capacities (0.645 and 0.558 mmol g⁻¹) for U(VI) and Th(IV), respectively. Quantitative metal desorption was achieved by using 0.5 M (NH₄)₂CO₃ for both analytes. The significant feature of the resin is the possibility of sequential separation and the ability to elute only U(VI) with water, thus offering the possibility of sequential separation of U(VI) and Th(IV). Interference studies with commonly encountered metal ions, rare earth ions and electrolytes were conducted. Enrichment factors of 400 and 350 with a limit of quantification of 20 ng mL⁻¹ and 50 ng mL⁻¹ were achieved for the two analytes. All the analytical data were within 3.8% RSD, reflecting the reproducibility and reliability of the method.