Development of a method for recovery of 233U from thorium oxalate cake in reconversion step of reprocessing of irradiated thorium rods

A method is developed for the selective leaching of ²³³U from a thorium oxalate cake. The leaching capacity of ammonium carbonate and nitric acid have been investigated, showing that (NH₄)₂CO₃ leads to higher recovery. The maximum leaching efficiency is obtained using 0.5% ammonium carbonate, with a minimal thorium pick-up. A uranium recovery of 94% is obtained after three consecutive contact experiments in carbonate media, with minimal thorium uptake in the leachate. This process was applied to an actual plant stream, allowing the reduction of the ²³³U -activity from 5.64 to 0.3 Ci/g of thorium oxalate cake.     

Rapid spectrophotometric determination of thorium(IV) with 1-(2′-thiazolylazo)-2-naphthol

Thorium(IV) reacts with 1-(2-thiazolylazo)-2-naphthol (TAN) in the presence of antipyrine to form a sparingly soluble red-coloured chelate, soluble in 36% methanol (v/v). Complexation takes place instantaneously at pH 2.4–2.8, maintained by glycine buffer. Antipyrine is found to enhance sensitivity of the complex, which is stable for 19 hours. The 12 complex exhibits maximum absorbance at 555 nm, obyes Beer's law in the concentration range from 0.32 to 6.56 g of thorium(IV) per ml, has a molar absorptivity of 3.14·10⁴ dm³/mol^–1·cm^–1 and a Sandel sensitivity of 7.4 ng·cm^–2. The formation constant (log K) is found to be 8.62 and 8.45. Interference of 57 anions and cations in the determination of thorium(IV) has been studied. From ten repeated determinations, the coefficient of variation was found to be ±0.98%. The method was successfully applied for determination of thorium content in a sample of monazite.     

Selective adsorption of thorium on activated charcoal from electrolytic aqueous solution

The adsorption of thorium on activated charcoal has been studied as a function of shaking time, amount of adsorbent, pH, concentration of adsorbate and temperature. Adsorption of thorium obeys the Langmuir isotherm. H⁰ and S⁰ were calculated from the slope and intercept of ln K_D vs. 1/T plots. The influence of different anions and cations on thorium adsorption has been examined. The adsorption of other metal ions on activated charcoal has been studied under specified conditions to check its selectivity. Consequently, thorium was removed from Cs, Co, Ba, Cr, Sr, Cd, Cu, Mn and Zn. More than 98% adsorbed thorium on activated charcoal can be recovered with 55 ml 3M HNO₃ solution. Wavelength dispersive X-rays fluorescence spectrometer was used for measuring thorium concentration.     

Selective Extraction and Inductively Coupled Plasma Atomic Emission Spectrophotometric Determination of Thorium Using a Chromogenic Crown Ether

A method for the preconcentration and trace determination of thorium with crown hydroxamic acid (NHDTAHA) is described. The thorium is extracted from the chloroform solution of NHDTAHA at pH 4 which gives a colourless extract, _max = 365 nm; = 9.4·10^–3 l·mol^–1·cm^–1. The extract is directly inserted in the plasma for ICP-AES measurements of thorium. A linear calibration graph was obtained between 15–150 ng·ml^–:1 of thorium. The proposed method has been applied for the determination of thorium in the presence of several diverse ions in monazite sand, rare earth sand and in sea water.     

Determination of231Pa in coastal sediments and sea water and disequilibrium studies in231Pa/235U activity ratios

Coastal sediment samples are collected from the top surface layers of the sediments from Bombay to Kottilppad along the West coast of India in order to understand the geochemical behaviour of²³¹Pa and the activity ratios of²³¹Pa/²³⁵U in this region of the Indian sub-continent. These coastal regions offer a unique advantage for studying the geochemistry and transport of natural radioactivity due to the placer deposits of monazite in the southern part of India. The top layers of the surface sediments are leached with 1.0M oxalic acid for the extraction of protactinium activities without attacking the mineral core of the particles.²³³Pa tracer is added to the samples. The chemical recovery obtained by counting²³³Pa is found to vary from 40 to 90%. Total uranium leached from the sediment surface is determined by fluorimetric method and the concentrations of²³⁵U in the leachates are calculated. Using these data, the activity ratios of²³¹Pa/²³⁵U have been calculated. These ratios lie in the range of 11.0 to 21.0 for sediments from Bombay to Kottilppad. The data of²³¹Pa activity indicates that there is a deficiency of²³¹Pa in coastal waters of the ocean and that²³¹Pa is removed by precipitation as soon as it is formed by radioactive decay of²³⁵U.²³¹Pa is observed to be bound mostly to organic humous material on the surface of the sediment.     

Simultaneous determination of trace uranium and thorium by radiochemical neutron activation analysis

A method for the simultaneous, radiochemical neutron activation analysis of uranium and thorium at trace levels in biological materials is described, based on a technique known as LICSIR, in which a double neutron irradiation is employed. In the first, long irradiation²³³Pa (27.0 d) is induced by neutron capture on²³²Th and then the sample is cooled for several weeks. A second short irradiation to induce²³⁹U (23.5 m) is followed by a rapid sequential radiochemical separation by solvent extraction of²³⁹U with TBP and²³³Pa with TOPO. Chemical yields of²³⁹U and²³³Pa were measured for each sample aliquot using added²³⁵U and²³¹Pa tracers from the -spectra of the separated fractions. The technique was validated by quality control analyses.     

A study on the hydrolytic behavior of thorium (IV) and dioxo-uranium(VI) in the absence and presence of fluoride ions

The hydrolytic behavior of thorium(IV) and dioxo-uranium(VI) was studied in the absence as well as in the presence of small concentration of fluoride in the pH range of 2.0 to 4.0 and 2.0 to 5.5, respectively. Effects of metal ion concentration and time dependence of the hydrolytic process were also investigated. The log values of ₁₁ ^* and ₁₃ ^* computed from the best model of species distribution were found to be -3.51±0.03, and -10.75±0.14 for thorium(IV). Similarly, the best model for dioxo-uranium consisted of ₂₂ ^*, ₄₆ ^* and ₄₇ ^* species having values -6.15±0.05-18.43±0.09 and -23.36±0.07, respectively. Recently developed HYPERQUAD computer program was used for analyzing the various aspects of solution equilibrium species. Different models of chemically possible species distribution were invoked to identify the best model for which HYPERQUAD yields the best fitting of experimental data with least errors. The best model was also decided on the basis of chemical feasibility of the reaction. The species distribution of hydrolytic product remained unaffected in the presence of small quantity of fluoride ions (~1% of thorium and uranium concentration). Moreover, fluoride was found to be helpful in suppressing the early polymerization and colloid formation at the metal ion concentrations investigated. The small amounts of fluoride did not seem to affect the response of glass electrode significantly. The formations of fluoride containing ternary complexes were also not observed at 1% fluoride concentration.     

Thorium in man and environment uptake and clearance

The intake and tissue distribution of thorium (^{2 3 2}Th) was studied in an urban (Bombay) population in India. From the analysis of 16 whole diet samples, the average daily intake through food was found to be 2 g (range 0.8–4.3 g·d^–1). The estimated intake through drinking water and inhalation comes out to be 0.03 and 0.02 g per day. From the analysis of human autopsy tissue samples it is observed that the concentration ranges in lungs and bone are 1.5–16 g/kg and 0.2–9.0 g/kg fresh weight respectively. The average urinary concentration is 12 ng/1 (range 7–22 ng/l for 10 samples). Among the different body tissues, pulmonary lymph nodes were found to contain the highest concentration (geometric mean 53.4 g/kg, range 31.4–85.5 g/kg for 6 samples). Analysis of the samples was done by the neutron activation technique. 311.8 keV gamma photons of^{2 3 3}Pa which is the activation product of^{2 3 2}Th, were counted after chemical separation. A 54 cm³ intrinsic Ge detector coupled to 1024-channel analyser was used. Using the average lung content and the daily average intake values of thorium through inhalation, the clearance half-time from lung was estimated.     

The dependence of build-up233U,232U,233Pa and fission products from ThO2 irradiated in HFETR on integral thermal neutron fluxes and neutron spectra

In this paper the dependence of build-up²³³U,²³²U,²³³Pa and fission products from ThO₂ irradiated in HFETR on integral thermal neutron fluxes and neutron spectra have been investigated. The yields of all above nuclides in ThO₂ increase with the increase of integral thermal neutron fluxes at different neutron spectra. The values of²³³U/²³²Th increase with the increases of _th and decreases with the increase of fast/thermal neutron ratios (_f/_th). The values of²³²U/²³³U increase with the increase of both _th and _f/_th ratio. The amount of fission products relative to original irradiated thorium decreases with the increase of _f/_th ratios. These results could be used to evaluate the behaviour of thorium-based nuclear fuel in reactor.     

First chemical on-line separation and detection of a subsecond α-decaying nuclide, 224Pa

Subsecond ²²⁴ Pa (T _1/2 = 0.85 s) was produced via the ²⁰⁹ Bi(¹⁸ O,3n)²²⁴ Pa reaction at the 88 inch cyclotron at the Lawrence Berkeley National Laboratory. After production it was transported via a gas-jet system to the centrifuge system SISAK 3. Following on-line extraction with trioctylamine/scintillation solutions from 1M lactic acid, ²²⁴ Pa was detected applying on-line -liquid scintillation counting. Unambiguous identification was achieved using time-correlated --decay chain analysis. This constitutes the first chemical on-line separation and detection of a subsecond -decaying nuclide, 0.85-s ²²⁴ Pa with the fast extraction system SISAK 3.     

Estimation of natural thorium in low level effluents from processing plants

This is a report of simple estimations of natural thorium in low level effluents generated during the reprocessing of irradiated Th/ThO₂ rods for the recovery of²³³U. The method involved co-precipitation of thorium with ceric iodate at pH 1.29±0.01 and subsequent photometric determination. Conditions were optimised to eliminate the interferences of other ions present in the effluent. Approximately 15 mg each of phosphate, fluoride, and sulphate, 10 mg of iron, and 300 g zirconium did not interfere in the estimation of 2–5 g Th/100 ml of the effluent. Average thorium recovery was around 101.9%±2.6% when nearly 10 g of thorium were spiked.     

Selective Extraction and Separation of Thorium from Monazite Using N-Phenylbenzo-18-crown-6-hydroxamic Acid

A method for the liquid–liquid extraction, separation, preconcentration and trace determination of thorium with N-phenylbenzo-18-crown-6-hydroxamic acid (PBCHA) is described. Thorium is extracted from the dichloromethane solution of PBCHA at pH 4.5 which gives a colourless extract (_max 375nm, =1.5×10⁴Lmol^–1 cm^–1, linear range following Beers law 0.77–18.48µgmL^–1). The extract is directly inserted into the plasma for ICP-AES measurements of thorium. A linear calibration graph was obtained between 10 and 130ngmL^–1 of thorium. The proposed method has been applied for the separation and determination of thorium in the presence of several ions in monazite sand, rare earths, sand and sea water samples. The thorium-PBCHA complexes are very stable, having the formation constant (log ₂) 13.45 compared to lanthanum (log ₂) 2.95, cerium (log₂) 2.95 and uranium (log ₂) 3.80. Hence, thorium can easily be separated and determined in monazite sand.Received October 31, 2002; accepted April 13, 2003 Published online July 16, 2003     

Variation of <Superscript>231</Superscript>Pa, <Superscript>230</Superscript>Th and <Superscript>231</Superscript>Pa<Subscript>ex</Subscript>/<Superscript>230</Superscript>Th<Subscript>ex</Subscript> in surface sediments of the Sabah–Sarawak coastal waters

Protactinium and thorium activities were measured in eight surface sediment taken in 2004 to determine effectiveness scavenging of ²³¹Pa at Sabah–Sarawak coastal waters. The result found that activity ratios of ²³¹Pa_ex/²³⁰Th_ex were ranged from 0.07 to 0.13 at all sampling stations. The high ²³¹Pa_ex/²³⁰Th_ex activity ratio than the production ratio of 0.093 in seawater at station SR 01, SR 02, SR 04, SB 02 and SB 05, revealed that ²³¹Pa is effectively removed from the water column into the sediment in comparison with ²³⁰Th at those stations. Low percentage of ²³⁰Th_ex (90–95%) in comparison with ²³¹Pa_ex at all stations can be attributed to less efficiently scavenged of ²³⁰Th onto particles prior deposited at the marine sediment bed.     

Studies on the Complexation Behavior of Thorium(IV). 1. Hydrolysis Equilibria

The stability constants of thorium(IV) hydrolysis species have been measured at15, 25, and 35°C (in 1.0 mol dm^–3 NaClO₄) using both potentiometry and solventextraction. The results indicate the presence of the monomeric speciesTh(OH)³⁺, Th(OH)²⁺ ₂, Th(OH)⁺ ₃, and Th(OH)₄, in addition to the polymericspecies Th₄(OH)^{8+ 8} and Th₆(OH)⁹⁺ ₁₅. The polymeric species were found to beimportant, although the total thorium concentration was limited to 0.01–0.1mmol-dm^–3. The solvent extraction measurements required the use of acetylacetone.As such, the stability constants of thorium(IV) with acetylacetone were alsomeasured using both potentiometry and solvent extraction. All logarithms of thestability constants were found to be linear functions of the reciprocal absolutetemperature indicating that H ^o and S^o of reaction are both independent oftemperature (over the temperature range examined in the study).     

Comparison of two ultra-sensitive methods for the determination of 232Thby recovery corrected pre-concentration radiochemicalneutron activation analysis

The determination of isotopic thorium by alpha spectrometric methods is a routine practice for bioassay and environmental measurement programs. Alpha-spectrometry has excellent detection limits (by mass) for all isotopes of thorium except ²³²Th due to its extremely long half-life. This paper discusses improvements in the detection limit and sensitivity over previously reported methods of pre-concentration neutron activation analysis (PCNAA) for the recovery corrected, isotopic determination of thorium in various matrices. Following irradiation, the samples weredissolved, ²³¹Pa added as a tracer, and Pa isolated by two different methods and compared (extraction chromatography and anion exchange chromatography) followed by alpha spectrometry for recovery correction. Ion exchange chromatography was found to be superior for this application at this time, principally for reliability. The detection limit for ²³²Th of 3.5 · 10^-7 Bq is almost three orders of magnitude lower than foralpha spectrometry using the PCRNAA method and one order of magnitude below previously reported PCNAA methods.     

Non-destructive determination of uranium and thorium in geological materials by resonance-neutron activation analysis

A simple method is described for the determination of uranium and thorium in gological materials. The samples are irradiated in a reactor with resonance and fast neutrons behind a cadmium filter. Compared with an irradiation with the whole reactor neutron spectrum, the matrix activities are reduced to about 1%, those of uranium (²³⁹Np) and thorium (²³³Pa) to about only 50 and 25%, respectively. This relative diminution of matrix activities allows the γ-measurement of²³⁹Np and²³³Pa as early as after two days' cooling time; in samples with high uranium contents the determination of²³³Pa requires one month's cooling time. This non-destructive procedure yields a detection limit of 0.1 ppm for uranium and thorium in samples of 200 mg, with an error of ±5%. Dedicated to ProfessorW. Borchert on the occasion of his 60th birthday.     

Thorium equilibria with the sodium form of clinoptilolite and mordenite

A study has been performed in order to examine the iron exchange behavior of tetravalent thorium ions using natural sodium clinoptilolite and mordenite. The free energy values, G ⁰, were calculated and found to be 3.33 kJ/g eq for the Th/Na-CLI system, and for Th/Na-MOR 3.94 kJ/g eq. Despite the fact that the overall preference of the zeolites is for the sodium ions, thorium uptake was quite significant for mordenite, covering 30% of its theoretical exchange capacity at the equilibrium point, while for clinoptilolite only 10% was occupied.     

Uptake of thorium ions from aqueous solutions by a molecular sieve (13X type) powder

The adsorption of thorium(IV) ions on molecular sieve (13X type) powder from aqueous solutions has been studied as a function of shaking time pH, thorium ion concentration and temperature. The conditions of maximum adsorption of thorium ions obeys Langmuir and D-R isotherms over the entire concentration range studied. Thermodynamic quantities such as H, G and S have been calculated fromK _D values determined at various temperatures. The results show endothermic heat of adsorption, but negative free energy value indicates that the process of thorium adsorption on molecular sieve powder is favored at high temperature. The influence of various cations and anions on thorium(IV) ion adsorption was examined. A wavelength dispersive X-ray fluorescence spectrometer was used for measuring the thorium ion concentration in solutions.     

Spectrofluorimetric determination of trace amounts of thorium

A spectrofluorimetric method, based on the formation of a fluorescent complex with salicyladehyde carbohydrazone, is optimized for the determination of thorium (20–800 μg l^?1) at “pH” 1.3–1.7. The relative standard deviation is 2.7% for 100 μg Th l^?1. The method is applied to synthetic mixtures containing various amounts of thorium and to the determination of thorium in monazite samples.     

Uranium and thorium determination in Brazilian coals by epithermal neutron activation analysis

An experimental technique has been developed to determine impurities in coal. Uranium was determined by counting the²³⁹Np 106.1 keV -ray with a LEPS detector and thorium by counting the²³³Pa 311.8 keV -ray with a Ge(Li) detector. Seventeen coal samples were analyzed with an average precision of 3% and a quantitative determination limit of 0.153 g/g for uranium and 0.078 g/g for thorium. The technique allows determinations of up to twenty elements besides U and Th and can be applied in routine analysis.