Natural radioactivity and radiation hazards in some building materials used in Isparta,Turkey

The activity concentrations of uranium, thorium and potassium can vary from material to material and it should be measured as the radiation is hazardous for human health. Thus first studies have been planned to obtain radioactivity of building material used in the Isparta region of Turkey. The radioactivity of some building materials used in this region has been measured using a γ-ray spectrometry, which contains a NaI(Tl) detector connected to MCA. The specific activity for ²²⁶Ra, ²³²Th and ⁴⁰K, from the selected building materials, were in the range 17.91–58.88, 6.77–19.49 and 65.72–248.76 Bq/kg, respectively. Absorbed dose rate in air (D), annual effective dose (AED), radium equivalent activities (Ra_eq), and external hazard index (H_ex) associated with the natural radionuclide are calculated to assess the radiation hazard of the natural radioactivity in the building materials. It was found that none of the results exceeds the recommended limit value.     

Extrapolation studies on adsorption of thorium and uranium at different solution compositions on soil sediments

Study on adsorption of thorium and uranium radionuclides by a soil sediment as a function of ionic composition of Ca, Mg and Na has been carried out. Experimentally determined slopes represents an average of adsorption on soil sediments having different relative affinities for thorium, uranium, calcium and magnesium. Both thorium and uranium were found to be adsorbed to ion-exchange sites together with calcium and magnesium cations as effective competitors An extrapolated equation for the distribution coefficientK _d was formed for both radionuclides thorium and uranium at the specified site where the soil sediments were sampled. The combined cation concentration of both calcium and magnesium in solution correlates linearly with the measuredK _d ^Th,U values.     

Studies on halogen derivatives of phenylazochromotropic acid: II. Spectrophotometric microdetermination of thorium

A new rapid and accurate method for the spectrophotometric microdetermination of thorium using o, p-dichloro-, p-bromo-, and p-iodophenylazochromotropic acids is given. The optimum conditions favoring the formation of the complexes are extensively investigated. The molecular structure was found to be 1:1 and 1:2 Beer's law is obeyed up to 16.24, 18.56, and 11.60 ppm of Th using the three reagents, respectively.     

Stereochemistry of thorium in oxygen-containing compounds

Voronoi–Dirichlet (VD) polyhedra and the method of intersecting spheres have been used to perform analysis of coordination of 198 types of crystallographically different Th(IV) atoms in the crystal structures of oxygen-containing compounds characterized with R ≤ 0.05. The volumes of VD polyhedra have been determined for the thorium atoms forming ThO_n complexes in which the Th–O bond lengths (2.14–2.91 Å) are roughly independent of the CN (n), varying from 4 to 12. It has been found that the phase transition of thorianite ThO₂ at elevated pressure is accompanied by a considerable distortion of the thorium VD polyhedra because of the appearance of faces corresponding to Th–Th contacts in which the interatomic distances are shorter than in thorium metal. It has been demonstrated that the baric phase transitions in thorium metal and thorianite are accompanied by similar changes in characteristics of Th VD polyhedra, which are tentatively believed to be a result of appearance of bonding 5f interactions between thorium atoms.     

Preparation of high-purity thorium by solvent extraction with di-(2-ethylhexyl) 2-ethylhexyl phosphonate

The extraction behavior of thorium(IV) by di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) from nitric acid media has been investigated. The influence factors including the concentration of HNO₃, salting-out reagents, temperature, the concentration of metal ions and DEHEHP have been examined systematically. A possible extraction mechanism is proposed and the extracted species as Th(NO₃)₄·2B _(o) is confirmed by the slope analysis method. The extraction equilibrium constants (K _ex) and thermodynamic parameters (ΔG, ΔH and ΔS) were calculated under the present experimental conditions. DEHEHP shows a high selectivity of thorium(IV) over rare earths(III). Stripping study indicates that thorium can be completely stripped by distilled water from the Th-loaded DEHEHP. Furthermore, a solvent extraction process including six extraction stages, six scrubbing stages, and six stripping stages was designed for the preparation of highly pure thorium from thorium concentrate with DEHEHP as extractant in laboratory scale, and finally thorium product can be obtained with a purity of 99.999 % and a yield of 98 %.     

Threshold behavior of laser ionization spectra for small potassium clusters

One-photon ionization profiles in the threshold region have been obtained for potassium clusters K_x(3 ⩽ x ⩽ 8) in a crossed laser molecular beam coupled with a time-of-flight mass spectrometer. Different behavior in ionization potential profiles, between odd- and even-numbered clusters is shown. This gives evidence for a dimerization effect for K₄, K₆ and K₈.     

Direct determination of thorium in uranium oxide by X-ray fluorescence

Summary Thorium in uranium is determined directly at trace levels by an XRF method. Uranium oxide samples are put in the form of double layer pellets and analysed by using Philips PW-1220 X-ray spectrometer. The typical value of the precision of the method at 200 ppm level is ±10% and estimation range is 50–1000 ppm of thorium in uranium.

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Direkte Bestimmung von Thorium in Uranoxid durch Röntgenfluorescenz-Spektrometrie

Zusammenfassung Mit Hilfe der beschriebenen Methode kann Th in Spurenkonzentrationen direkt bestimmt werden. Die Uranoxidproben werden als Doppelschicht-Tabletten eingesetzt und mit Hilfe eines Philips PW-1220 Röntgenspektrometers analysiert. Die Genauigkeit im Bereich von 200 ppm beträgt ±10%. Der Anwendungsbereich liegt bei 50–1000 ppm.

     

Separation studies of uranium and thorium using tetra(2-ethylhexyl) diglycolamide (TEHDGA) as an extractant

The extraction behavior of uranium, thorium and nitric acid has been investigated for the TEHDGA/isodecyl alcohol/n-dodecane solvent system. Conditional acid uptake constant (K _H) of TEHDGA/n-dodecane and the ratio of TEHDGA to nitric acid were obtained as 1.72 and 1:0.96, respectively. The extracted species of uranium and thorium in the organic phase were found to be UO₂(NO₃)₂·2TEHDGA and Th(NO₃)₄·2TEHDGA. A workable separation factor (D _Th/D _U) of the order of 300 was observed between thorium and uranium in the nitric acid range of 0.5M to 1.5M. Similar separation factor was also achieved at higher acidity when thorium was present in large concentration compared to uranium. These results indicate that TEHDGA solvent system could be a potential candidate for separation of thorium from uranium.     

Analytical applications of the reaction of thorium with benzenephosphonic acid

Benzenephosphonic acid quantitatively precipitates thorium as Th(C₆H₅PO₃)₂·3H₂O at pH values as low as 0.5. The compound may be dried at 140° to 180° C and weighed, as a gravimetric means of determining thorium. On ignition, Th (C₂H₅PO₃)₂ 3 H₂O undergoes decomposition at 240° to 300° C to form Th(C₆H₅PO₃)₂·2H₂O, at 450° to 650° C to form Th(HPO₄)₂·2H₂O and finally at 800° to 1000° C to form Th(HPO₄)₂. The latter compound is stable to 1200° C.Potentiometrically (pK₁' = 0.91, pK₂' = 6.41) and spectrophotometrically (pK₁' = 0.96, pK₂' = 6.51) determined pK' values are reported. Absorption spectra of C₆H₅PO₃H₂, C₆H₅PO₃H^- and C₆H₅PO₃^-2 are reported. The solubility of Th (C₆H₅PO₃)₂·3H₂O was studied as a function of pH and the average value of the solubility product (K_sp = 4s³) was found to be 3.24·10^-31.     

Thermal decomposition of thorium(IV) complexes with benzenecarboxylic acids in air atmosphere

The conditions and products of thermal decomposition of thorium(IV) complexes with general formula Th(R-C₆H₄COO)₄ (whereR=2-CH₃, 3-CH₃, 4-CH₃), Th(OH)₂(4-CH₃C₆H₄COO)₂. H₂O and Th(OH)₂(R-C₆H₄COO)₂·nH₂O (whereR=2-COO, 3-COO,n=2;R=4-COO,n=1) were studied. Anhydrous thorium(IV) complexes decompose in two steps. On heating, tetra(2-methylbenzoato)-thorium(IV) decomposes to yield ThO₂ through the intermediate ThOCO₃ whereas tetra(3-methylbenzoato)thorium(IV) and tetra(4-methylbenzoato)thorium(IV) decompose to ThO₂ through oxocomplexes. Hydrated thorium(IV) complexes are dehydrated in one step and then anhydrous complexes decompose to ThO₂. Di [1,2-(benzene)dicarboxylato]dihydroxythorium(IV) decomposes directly to ThO₂, whereas the 1,3- and 1,4-isomers through the intermediate thorium(IV) oxocarbonates.     

NO x conversion on porous LSF15–CGO10 cell stacks with KNO3 or K2O impregnation

In the present work, it was investigated how addition of KNO₃ or K₂O affected the NO _x conversion on LSF15–CGO10 (La_0.85Sr₁₅FeO₃–Ce_0.9Gd_0.1O_1.95) composite electrodes during polarization. The LSF15–CGO10 electrodes were part of a porous 11-layer cell stack with alternating layers of LSF15–CGO10 electrodes and CGO10 electrolyte. The KNO₃ was added to the electrodes by impregnation and kept either as KNO₃ in the electrode or thermally decomposed into K₂O before testing. The cell stacks were tested in the temperature range 300–500?°C in 1,000?ppm NO, 10% O₂, and 1,000?ppm NO?+?10% O₂. During testing, the cells were characterized by electrochemical impedance spectroscopy, and the NO conversion was measured during polarization at ?3?V for 2?h. The concentration of NO and NO₂ was monitored by a chemiluminescence detector, while the concentration of O₂, N₂, and N₂O was detected on a mass spectrometer. A significant effect of impregnation with KNO₃ or K₂O on the NO _x conversion was observed. In 1,000?ppm NO, both impregnations caused an increased conversion of NO into N₂ in the temperature range of 300–400?°C with a current efficiency up to 73%. In 1,000?ppm NO?+?10% O₂, no formation of N₂ was observed during polarization, but the impregnations altered the conversion between NO and NO₂ on the electrodes. Both impregnations caused increased degradation of the cell stack, but the exact cause of the degradation has not been identified yet.     

Cation-exchange separation of uranium from thorium in nitric acid medium</p> </p>

Summary Sorption behavior of Th and U on cation-exchange resins was investigated from nitric acid medium by both batch and column methods. The cation-exchange studies involved the sorption of UO₂²⁺ and Th⁴⁺ and their cationic complexes onto Dowex 50Wx8 and Dowex 50Wx4 resins (50-100 mesh). The batch data yielded a separation factor (K_d,Th/K_d,U) value of >100 for the cation-exchanger, Dowex 50Wx4 at 1-2M HNO₃. Separation of uranium from thorium was also carried out by column method in nitric acid medium using cation-exchangers, Dowex 50Wx4 as well as Dowex 50Wx8. While uranium elution was possible at 1M HNO₃, Th could be eluted only at higher concentration of nitric acid (>6M). The stripped solution emanating from a mixer settler employing di-2-ethyl hexyl isobutyramide as extractant and feed solution similar to THOREX process comprising 350 mg/l U and 380 mg/l Th in 0.75M HNO₃ was loaded on the column and the decontamination factor value for U in the product was >1000.</p> </p>     

Determination of trace concentrations of thorium in uranium oxide matrix by epithermal instrumental neutron activation analysis

An epithermal instrumental neutron activation analysis (EINAA) method using cadmium filter was standardized to determine trace concentrations of thorium in four samples of uranium oxide (U₃O₈) samples. Samples and thorium standards, wrapped with cadmium foil, were irradiated at a reactor neutron flux of about 10¹² cm^?2 s^?1. Radioactive assay was carried out using a Compton suppressed anticoincidence gamma ray spectrometer consisting of HPGe-BGO detectors coupled to MCA. Concentrations of thorium in these samples were found to be in the range of 15–72 mg kg^?1. EINAA results were validated by determining thorium concentrations in uranium matrix by standard addition method. EINAA results were compared with those obtained by two wet chemical methods namely ion chromatography (IC) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The results obtained by the three methods were found to be in good agreement, indicating further validity of the proposed EINAA method.     

Adsorptive removal of thorium from aqueous solution using diglycolamide functionalized multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were functionalized with diglycolamide (DGA) through chemical covalent route. The adsorption behavior of the DGA-functionalized-MWCNTs (DGA-MWCNTs) towards thorium from aqueous solution was studied under varying operating conditions of pH, concentration of thorium, DGA-MWCNTs dosages, contact time, and temperature. The effective range of pH for the removal of Th(IV) is 3.0–4.0. Kinetic data followed a pseudo-second-order model. The equilibrium data were correlated with the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models. The equilibrium data are best fitted with Langmuir model. The equilibrium Th(IV) sorption capacity was estimated to be 10.58 mg g^?1 at 298 K. The standard enthalpy, entropy, and free energy of adsorption of the thorium with DGA-MWCNTs were calculated to be 8.952 kJ mol^?1, 0.093 kJ mol^?1 K^?1 and -18.521 kJ mol^?1 respectively at 298 K. The determined value of sticking probability (0.072) and observed kinetic and isotherm models reveal the chemical adsorption of thorium on DGA-MWCNTs.     

Boron in natural waters by atomic absorption spectrometry with electrothermal atomization

Rapid scanning of numerous rock samples when prospecting for uranium and thorium ores can be facilitated by using the shorter-lived nuclides. The samples are activated during short epithermal neutron irradiations and the 20-min activities of ²³⁹U and ²³³Th are observed instrumentally with a small Ge(Li) detector. The detection limits for uranium and thorium are less than 1 ppm and 20 ppm, respectively.     

Cation‐Mediated Conversion of the State of Charge in Uranium Arene Inverted‐Sandwich Complexes

Two new arene inverted‐sandwich complexes of uranium supported by siloxide ancillary ligands [K{U(OSi(OtBu)₃)₃}₂(μ‐η⁶:η⁶‐C₇H₈)] ( 3 ) and [K₂{U(OSi(OtBu)₃)₃}₂(μ‐η⁶:η⁶‐C₇H₈)] ( 4 ) were synthesized by the reduction of the parent arene‐bridged complex [{U(OSi(OtBu)₃)₃}₂(μ‐η⁶:η⁶‐C₇H₈)] ( 2 ) with stoichiometric amounts of KC₈ yielding a rare family of inverted‐sandwich complexes in three states of charge. The structural data and computational studies of the electronic structure are in agreement with the presence of high‐valent uranium centers bridged by a reduced tetra‐anionic toluene with the best formulation being U^V–(arene^4?)–U^V, KU^IV–(arene^4?)–U^V, and K₂U^IV–(arene^4?)–U^IV for complexes 2 , 3 , and 4 respectively. The potassium cations in complexes 3 and 4 are coordinated to the siloxide ligands both in the solid state and in solution. The addition of KOTf (OTf=triflate) to the neutral compound 2 promotes its disproportionation to yield complexes 3 and 4 (depending on the stoichiometry) and the U^IV mononuclear complex [U(OSi(OtBu)₃)₃(OTf)(thf)₂] ( 5 ). This unprecedented reactivity demonstrates the key role of potassium for the stability of these complexes.     

Use of ultra-filtration in organic-rich groundwater for the physical separation of thorium

During this work, size fractionation technique “ultra filtration” is used in physical speciation of thorium in organic rich groundwater. Laboratory simulated experiments were carried out to study the physical speciation of thorium in aquatic environment having elevated level of dissolved humus material classified as dissolved organic carbon (DOC). Samples were collected from organic rich environment having DOC in the range of 50–60 µg mL^?1. Th(IV) ions are extremely particle reactive having K _d value of the order of 10^5–6, hence to avoid adsorption on suspended particulate matter, spiking of the solution with Th(NO₃)₄ was carried out in ground water samples after filtering through 450 nm pore size using suction filtration. Particles in dissolved state (colloids) ranging between <450 and >220 nm were separated using suction filtration assembly having a membrane with a pore diameter of 220 nm. Thereafter, solution was sequentially passed through the ultra-filtration membranes having pore diameters of 14 nm [300 k NMWL (nominal molecular weight limit)], 3.1 nm (50 k NMWL), 2.2 nm (30 k NMWL), 1.6 nm (10 k NMWL) and 1.1 nm (0.5 k NMWL) by using “Stirred Ultra-filtration Cells”, operating in concentration mode. Thorium has only one stable oxidation state i.e. IV, under all redox conditions in natural waters and therefore, its speciation is dominated by its interaction with various fractions of DOC. Experimental results show 50–60 % of the spiked Th is in association with fraction enriched with particles of 10 k NMWL (1.6 nm) followed by fraction enriched with particle of 0.5 k NMWL and <220 nm.     

Novel Thorium Membrane Sensors with Anionic Response Based on Trioctylphosphine Oxide and Toluate Ionophores

Two novel potentiometric polymeric membrane sensors for rapid and accurate determination of thorium are described. These are based on the use of trioctylphosphine oxide (TOPO) and thorium toluate (Th‐TA) as ionophores dispersed in poly(vinyl chloride) matrix membranes plasticized with nitrophenyloctyl ether. In strong nitric acid medium, Th(IV) nitrate is converted into [Th(NO₃)₆]^2? complex and sensed as anionic divalent ion which exclude most cationic effect. Validation of the assay methods using the quality assurance standards (linearity range, accuracy, precision, within‐day variability, between‐day‐repeatability, lower detection limit and sensitivity) reveals excellent performance characteristics of both sensors. The sensors exhibit near‐Nernstian response for 1.0×10^?6–1.0×10^?1 M Th over the pH range 2.5–4.5. Calibration slopes of ?32.3±0.3 and ?27.2±0.2 mV/decade, precision of ±0.5 and ±0.8% and accuracy of 98.8±0.9 and 97.9±0.7% are obtained with TOPO and Th‐TA based sensors, respectively. Negligible interferences are caused by most interfering mono‐, di‐, tri‐, tetra‐, penta‐, and hexa‐valent elements commonly associated with thorium in naturally occurring minerals and ores. High concentrations of Cl^?, F^?, SO₄^2?, and NO₃^? ions have no diverse effect. Complete removal of the effect of the interferents in complex matrices is achieved by retention of [Th(NO₃)₆]^2? complex from 5 M nitric acid/methanol mixture (1 : 9 v/v) on a strong anion exchanger, washing out the cationic interferents followed by stripping off thorium anion complex and measurements. Both sensors are used for determining thorium in certified thorium ore samples (20–120 mg Th/kg) and some naturally occurring ores (200–600 mg Th/kg). The results obtained agree fairly well with the certified labeled values or the data obtained using X‐ray fluorescence spectrometry     

Adsorption and kinetic behavior of uranium and thorium in seawater-sediment system

The adsorption and kinetic mechanism of uranium (U) and thorium (Th) in seawater-sediments system of Mumbai Harbour Bay (MHB) has been studied by K _d values of two sets of experimental determinations using a batch experiment. After equilibrium time (7 days), under static conditions, K _d for U and Th ranged from 25,030 to 55,662 mL/g (mean: 42,140 mL/g) and 24,926 to 38,561 mL/g (mean: 34,256 L/kg), respectively. Extraction studies showed that both U and Th were strongly bound to sediment components due to insignificant difference in their mean concentration in equilibrium solution. Rate constants (k) for transfer between seawater and the exchangeable fraction were found to be similar for the sediments as 1.02 ± 0.03 day^?1 for uptake of U and Th. The resulting adsorption data were fitted to Freundlich, linear and Langmuir isotherm models. All the three models showed a significant correlation (R ² >0.9), indicating that there is more complex relationships with adsorption behavior of U and Th on sediment surface. Since, the Freundlich constant (n) for U and Th was found to be closer to unity. Therefore linear model was observed to be highly suitable. Based on the linear model, the distribution coefficient (k _d) of Th was about 1.5 times higher than U. According to Freundlich model, sorption of U in sediments observed to be higher than Th. However, Langmuir model considered in opposite to Freundlich and showed a higher value of K _L constant for Th than U. The pH (water) of the sediments ranged from 7.8 to 8.2 and the estimated total carbon (determined by C H N S–O elemental analyser) ranged from 1.7 to 3.4 %.     

Massenspektrometrische Bestimmung von ppm-Mengen Thorium in Uranerzen durch Isotopenverdünnungsanalyse

Thorium is chemically separated from uranium ores in a non-quantitative way. In one sample the isotopic ratio ²³⁰Th/²³²Th is determined in a mass spectrometer. In another sample ionium is added as indicator for the isotopic dilution; the thorium of this particular sample is also analysed in a mass spectrometer. The content of ²³⁰Th and ²³²Th is calculated from the measurements of the isotopic ratios and the amount of the ionium indicator. The results are compared with the results obtained by other methods.