Separation of trace rare earths and other metals from uranium by liquid-liquid extraction with quantitation by inductively-coupled plasma/mass spectrometry

N,N-Dihexylacetamide in toluene was used to extract uranium selectively from an aqueous phase containing 30 elements at 10 or 100 μg l^?1 concentrations. After three extractions, the uranium level fell from 119 000 mg l^?1 (0.5 M) to less than 3 mg l^?1. An inductively-coupled plasma/mass spectrometer (i.c.p./m.s.) was used to determine recoveries of the trace elements in the aqueous phase, which, in most cases, were in the range 90–110%. This combination of liquid-liquid extraction with i.c.p./m.s. offers determinations at the 10 ng g^?1 level in uranium for most of the elements studied.     

Solvent extraction separations with bpha. applications to the microanalysis of niobium and zirconium in uranium

A detailed study of the benzoylphenylhydroxylamine (BPHA)-chloroform-hydrochloric acid solvent extraction system with 52 elements is described with emphasis placed on extraction of the easily hydrolyzed transition metals from strong hydrochloric acid. From this study, a separation procedure for hafnium, niobium, tantalum, titanium, vanadium, and zirconium from uranium was developed, and procedures are given for the microanalysis of niobium and zirconium in uranium. Niobium and zirconium are separated from uranium by extraction into BPHA-chloroform from 10-N HCl.The separated elements are then measured colorimetrically as the niobium-4-(2-pyridylazo)resorcinol and zirconium-arsenazo III complexes. The limit of detection is 1 μg/g U.     

The atomic absorption determination of zinc with a graphite furnace

The use of a heated graphite furnace has been evaluated for the atomic absorption determination of zinc. Interferences were found to occur with most elements when present in large amounts; solvent extraction procedures have been investigated to avoid such effects. Results are reported for the solvent extraction and determination of zinc in the range 0.002–1 p.p.m.     

Determination of impurities in uranium compounds by atomic absorption

A method is described for the determination of 14 elements (Al, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, Mn, Ni, K, Na, Zn) in uranium and uranium compounds by atomic absorption spectroscopy. A sample is dissolved in 6–8 N nitric acid, from which the uranium is selectively removed by a single extraction with tributyl phos phate. The aqueous layer is evaporated to dryness and the residue is re-dissolved in 0.2 N hydrochloric acid. Any or all of the elements can then be determined in the solution by atomic absorption spectroscopy. The limits of error in the analyses are less than 10%. Thus, the method gives about the same precision as colorimetric procedures, and it is much more precise than emission spectroscopy.     

Separation and spectrophotometric determination of thorium contained in uranium concentrate

A method for the determination of thorium in uranium concentrate by spectrophotometry with Arsenazo III has been developed. Preliminary solvent extraction procedures were used to eliminate interfering species. Samples were dissolved in nitric, perchloric and sulfuric acid and the uranium extracted from the solution using tri-octylamine. The aqueous layer was evaporated to dryness and the residue re-dissolved with hydrochloric acid, thorium was extracted by tri-n-octyl phosphine oxide and stripped with oxalic acid. For a typical uranium concentrate produced from the phosphate rock of Itataia, Brazil, concentrations of thorium as low as 5 g·g^-1 can be determined.     

Spectrophotometric determination of microgram quantities of indium in uranium and thorium metals and their salts

A method based on dithizone extraction and determination of indium in the range of 0 1 to l0 p p,m in reactor gracde uranium and thorium samples is described Sodium thiosulphatc is uscd as a, complexing agent for removing interference by lead and bismuth     

Solid phase extraction and preconcentration of uranium(VI) and thorium(IV) on Duolite XAD761 prior to their inductively coupled plasma mass spectrometric determination

A simple and effective method is presented for the separation and preconcentration of thorium(IV) and uranium(VI) by solid phase extraction on Duolite XAD761 adsorption resin. Thorium(IV) and uranium(VI) 9-phenyl-3-fluorone chelates are formed and adsorbed onto the Duolite XAD761. Thorium(IV) and uranium(VI) are quantitatively eluted with 2 mol L⁻¹ HCl and determined by inductively coupled plasma-mass spectrometry (ICP-MS). The influences of analytical parameters including pH, amount of reagents, amount of Duolite XAD761 and sample volume, etc. were investigated on the recovery of analyte ions. The interference of a large number of anions and cations has been studied and the optimized conditions developed have been utilized for the trace determination of uranium and thorium. A preconcentration factor of 30 for uranium and thorium was achieved. The relative standard deviation (N = 10) was 2.3% for uranium and 4.5% for thorium ions for 10 replicate determinations in the solution containing 0.5 μg of uranium and thorium. The three sigma detection limits (N = 15) for thorium(IV) and uranium(VI) ions were found to be 4.5 and 6.3 ng L⁻¹, respectively. The developed solid phase extraction method was successively utilized for the determination of traces thorium(IV) and uranium(VI) in environmental samples by ICP-MS.     

Determination of uranium in plutonium by differential linear sweep oscillographic polarography

The polarographic behavior of uranium in hydroxylamine hydrochloride was investigated by differential oscillographic polarography. A procedure is presented for the determination of uranium in plutonium for concentrations of uranium greater than 10 p.p.m. Analyses of solutions containing 22 common impurities found in plutonium metal revealed that antimony, copper, and titanium cause significant interference. A reversible peak corresponding to a one-electron reduction was obtained with a peak potential of -0.167 V vs. Hg pool electrode. The diffusion coefficient is 0.51·10^-5 cm²/sec and the diffusion current constant is 1.59 with an average relative standard deviation of 2.28%. The peak current of uranium can be affected by hydrochloric, nitric, perchloric, and sulfuric acids, depending on the acid concentration.     

Properties of PAN-TBP extraction chromatographic material

Three production routes of the preparation of a solid extractant based on tributylphosphate (TBP) embedded in the polyacrylonitrile matrix (PAN) have been studied. The method of direct PAN coagulation with TBP was found to be not viable due to the significant TBP solubility in the coagulation bath. The most suitable PAN-TBP solid extractant was prepared by the well-known impregnation method of ready-made neat PAN beads. The kinetics of uranium extraction from 3 mol L^?1 HNO₃, the effect of nitrate and nitric acids concentrations on the value of weight distribution coefficients D _g as well as the uranium “extraction isotherm” were determined for this material. Uranium extraction was rather fast, approximately 1 h was sufficient for the equilibrium achievement. Capacity for the uranium uptake, measured in batch experiments on PAN-TBP for 0.048 mol L^?1 of uranium in 3 mol L^?1 nitric acid, was found to be q = 0.363 mmol g^?1 (58 % of the theoretical capacity). It was concluded that PAN-TBP material behaves like TBP in liquid–liquid extraction. Extraction capacity determined in column experiments was lower (by about 23 %) than expected from the “extraction isotherm” due to the TBP leaching out of the column. The thus prepared material is therefore not very suitable for multicycle extraction and stripping and can be used once, particularly for the analytical purposes.     

Determination of manganese in uranium by ion exchange and square-wave polarography

Traces of manganese in uranium and its compounds can be determined by ion-exchange separation and square-wave polarography. When a 9 M hydrochloric acid solution of the sample is introduced into a column of strongly basic anion-exchange resin, manganese can be quantitatively separated from uranium by cluting with 9 M hydrochloric acid. The determination of the separated manganese by square-wave polarography is performed in 1 M potassium hydroxide-0.4 M triethanolamine solution with an excellent sensitivity. The lower limit of the method is 0.5 p.p.m. of manganese.     

Removal of uranium from sulfate leach liquor of salcrete deposits using tri-n-octyl amine

A uranyl sulfate leach liquor obtained by uranium leaching of a technological sample of salcrete deposits of Gabal Qatrani ore was subjected to uranium extraction using the liquid–liquid technique. Uranium was effectively extracted from sulfate leach liquor by [(10 %) tri-n-octylamine (TOA)] dissolved in xylene as a diluent. The extraction efficiency was markedly enhanced as the concentration of TOA increases from 1 to 10 %. The relevant factors controlling the extraction process of uranium using tri-n-octylamine were studied. These factors include the effect of diluents used, TOA concentration, contact time, settling time and phase ratio (O/A) v/v. The optimum extraction conditions were chosen. Stripping of uranium from the loaded TOA has been carried out using 5 % Na₂CO₃ as an effective stripping agent. More than 97 % of uranium was extracted by 10 % TOA, at contact time 10 min, settling time 5 min, phase ratio (V_O/V_A) 1/1 and at room temperature. The feasibility of using the TOA for preconcentration-separation of uranium was assessed by stripping studies. The loaded uranium onto TOA has been stripped by 100 % when using 5 % Na₂CO₃ as an efficient eluting agent at 15 min contact time, 5 min settling time and phase ratio (O/A) 2/1.     

Studies of leaching of copper ores and flotation wastes

In Poland, there are significant deposits of copper ores. During the copper extraction, large amounts of flotation wastes are produced. In the ores and flotation wastes many other important elements are present. The main goal of this work was analysis of uranium content and to elaborate procedures for recovery of U from these materials. Two types of ores and four types of waste were examined. It has been found that uranium content varies from 4.5 to 25 ppm. The other elements have also been determined in these materials: Cu (4–5 % in ores and 0.3–1.7 % in waste), Ag, Re, Mo, La, Ni, V, etc. For leaching, sulfuric acid and sodium carbonates of various concentrations (temperature, time) were used. The optimum conditions for leaching have been found. The concentration of uranium in the final solution was generally less than 25 μg/mL. The other elements are also present in the leaching solutions. Simultaneous liquid–liquid extraction of uranium with these elements from leaching solution is under study. In our opinion, only such combined procedure for the recovery of uranium together with the accompanying elements could be cost-effective.     

An improved method for the determination of uranium isotopes in environmental samples by alpha-spectrometry

In order to improve the selectivity of the uranium isotopes determination in environmental samples, further studies have been carried out, including (1) interference of ²¹⁰Po with uranium isotope determination, (2) distribution coefficients of polonium between 5% TOPO in toluene and aqueous hydrochloric and nitric acids, (3) decontamination factor of uranium from polonium of the recommended procedure, and (4) leaching effect comparison of two different leaching procedures in a lichen sample. Based on the new findings, a more accurate extraction chromatographic/ a-spectroscopy method has been developed. For the method's validation, four kinds of reference materials supplied by the IAEA have been tested. It is observed that nearly all the ²³⁸U, ²³⁴U and ²³⁵U concentrations obtained are in good agreement with the recommended or information values, showing that the method can give reliable results. A comparison with existing uranium determination methods has also been made. It is concluded that due to involving preconcentration and chemical separation, the extraction chromatographic/a-spectroscopy method is a more selective, very sensitive and accurate, and low cost method. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polarographic behavior of uranium(VI) in malonic acid media determination of uranium in plutonium

The polarographic behavior of the uranium-malonate complex was investigated over the pH range 1.1–6.5. A reversible, one-electron wave was obtained. Below pH 4.9, the rate of disproportionation is nearly instantaneous and gives rise to a pseudo uranium(VI)-uranium(IV) reduction. Above pH 4.8 the concentration of uranium(V) is stable with respect to disproportionation. The half-wave potential is pH-dependent below pH 4.9, but it is independent of the malonate concentration above O.1 M. The diffusion current constant is 2.78 for the conditions described. A procedure for the determination of uranium in plutonium was developed for uranium concentrations greater than 225 p.p.m. Of 21 common impurities found in plutonium metal, only Cu, Fe, Pb, Sb and Ti cause significant interference ; titanium can be removed by ion exchange, and the other interferences by mercury cathode electrolysis.     

Investigation of U(VI) extraction with calixarene: Application to analysis of urine sample

A macrocyclic molecule, the calix[6]arene 4₆, functionalized with carboxy groups, has been studied and its extraction efficiency towards uranium determined in a two phases solvent-extraction system. Two solvents, dichloromethane and benzene were used to follow uranium extraction from media containing sodium ions. The study of the extraction parameters allowed proposing an extraction scheme with each solvent. The extraction efficiency was found to increase with pH, with an optimal efficiency of nearly 100%. No decrease of uranium extraction was observed in synthetic solutions containing sodium ions (spiked with²²Na) and/or²³⁹Pu. Under specific conditions, almost 100% of uranium have been extracted by the calixarene from real urine samples.     

Extraction of uranium(VI) through reversed micelle by primary amine N1923

A study on extraction of uranium(VI) from sulfuric acid media by the primary amine N₁₉₂₃ in chloroform is described. Extraction coefficients of uranium(VI) as a function of aqueous H₂SO₄ concentration, extractant concentration and temperature have been studied. From the data, the compositions of extracted species, equilibrium constants and enthalpies of extraction reaction have been evaluated. A new extraction mechanism of amine has been suggested, that is the formation of reversed micelle as a result of the aggregation of ammonium salt in the organic phase of the extraction. This assumption may be used for interpreting extraction data satisfactorily, which can not be explained by the slope analysis method.     

Comparative studies on co-extraction of uranium(VI) and different mineral acid from aqueous feed solutions using TBP,TOPO and TOA

Equilibrium and kinetics of co-extraction of hexavalent uranium and mineral acids from aqueous solutions into a hydrocarbon phase (paraffin) using tri n-butyl phosphate (TBP), tri-n-octyl phosphine oxide (TOPO) and tri-n-octyl amine (TOA) has been studied. Relative rates of extraction of uranium(VI) and mineral acid by different complexing ligands were measured simultaneously using bulk-liquid membrane system. Acid extraction by complexing ligands was found to be significant. Wherever there was a possibility of the formation of the third phase, isodecanol was used as an organic phase modifier. Study revealed that isodecanol promotes acid extraction and substantially reduces distribution coefficient of U(VI) into the hydrocarbon phase. The rate of acid extraction by different ligand was in the order of TOPO > TOA > TBP–isodecanol > TBP, whereas the rate of extraction of uranium(VI) was in the order TOPO > TOA > TBP > TBP–isodecanol. A kinetic model was developed to predict concentration of acid and U(VI) in the feed, organic and the strip phase during extraction. The mass transfer coefficients for acid and metal were determined by fitting the model to the observed concentration–time data.     

Dosage de l'oxygene dans l'uranium et ses composes par la methode au monochlorure de soufre

A sulfur monochloride method is proposed for the determination of oxygen in uranium compounds. Sulfur monochloride reacts with oxygenated compounds at temperatures depending upon their nature; the sulfur dioxide produced is titrated by iodometry, after the excess reagent has been eliminated by a selective adsorption-desorption process using activated charcoal. This method has been successfully applied to uranium oxides (UO₂, U₃O₈), to mixtures of uranium dioxide with uranium, uranium nitride, and uranium carbide, and to substituted carbides (UC_1-xO_x). The results are generally satisfactory for oxygen contents higher than 500 p.p.m. However, in the presence of free or combined carbon, this limit is considerably higher. A loss of oxygen as carbon monoxide is also possible, and a simultaneous determination of carbon monoxide must be carried out. The relative error is of the order of a few per cent.     

Individual determination of uranium and plutonium in a single aliquot

Studies on the individual potentiometric determination of uranium and plutonium in a single aliquot have been initiated recently in our laboratory. It was required to adapt the reported procedures (for the precise determination of uranium and plutonium individually when present together in a sample) at various stages to make them suitable for the successive application of the procedures to the same aliquot. Two alternative schemes are proposed in the present work. In the first, plutonium is determined by HClO₄ oxidation followed by the determination of total uranium and plutonium by Zn(Hg) reduction. In the second, plutonium is determined by AgO oxidation following the determination of total uranium and plutonium by Zn(Hg) reduction. Amount of uranium is computed in both cases from the difference of two determinations. Precision for the assay of plutonium and uranium was found to be ±0.25% and ±0.35%, respectively, at milligram levels.