Comparative determination of uranium in rock phosphates and columbite by ICP-OES,alpha &; gamma spectrometry

During this work selective separation of uranium from rock phosphate and columbite mineral was done before its quantitative estimation by using Inductively Coupled Plasma Optical Emission Spectrometery (ICP-OES). Uranium from the rock phosphate and columubite was extracted by sodium peroxide fusion followed by leaching in 2 M HNO₃. To avoid spectral interference in the estimation of uranium by ICP-OES, the selective separation of uranium from the leachate was carried out by using two different extractants, 30% Tributyl Phophates (TBP) in CCl₄ and a equi-volume mixture of Di(2-ethylhexyl) phosphoric acid (D2EHPA) & TBP in petrofin. Uranium was stripped from the organic phase by using 1 M ammonium carbonate solution. Determination of uranium by ICP-OES was done after dissolving the residue left after evaporation of ammonium carbonate solution in 4% HNO₃. The concentration of the uranium observed in the rock phosphates samples was 40–200 μg g⁻¹ whereas in columbite samples the concentration range was 100–600 μg g⁻¹. Uranium concentration evaluated by ICP-OES was complimented by gamma & alpha spectrometry. Concentration of uranium evaluated by gamma spectrometry in case of rock phosphate and coulmbite was in close agreement with the uranium content obtained by ICP-OES. Uranium determination by alpha spectrometry showed only minor deviation (1–2%) from the results obtained by ICP-OES in case of rock phosphates whereas in case of coulmbites results are off by 20–30%.     

Isotopic uranium analysis in urine samples by alpha spectrometry

Urine assay is the preferred method for monitoring accidental or chronic internal intake of uranium into the human body. A new radiochemical separation procedure has been developed to provide isotopic uranium analysis in urine samples. In the procedure, uranium is co-precipitated with hydrous titanium oxide (HTiO) from urine matrix, and is then purified by anion exchange chromatographic column. Alpha spectrometry is used for isotopic uranium analysis after preparation of a thin-layer counting source by cerium fluoride micro-precipitation. Replicate spike and procedural blank samples were prepared and measured to validate the procedure. The ²³²U tracer was utilized for chemical recovery correction, and an average recovery of 76.2 ± 8.1% was found for 1400 mL urine samples. With 48 h of counting, the minimum detectable activity concentrations were determined to be 0.43, 0.21 and 0.42 mBq/L for ²³⁸U, ²³⁵U and ²³⁴U, respectively.     

Radiological measurement of phosphate rock and phosphogypsum from fertilizer industries in India

Phosphate deposits are generally characterized by high levels of natural radionuclide concentrations. Natural radionuclides from the uranium and thorium series were measured, using high-resolution gamma-spectrometry in phosphate rock and phosphogypsum samples from the phosphate fertilizer industry in India. Equilibrium was found to be disrupted during the chemical processing of phosphate rock with 83 % of the ²²⁶Ra and only 5 % of ²³⁸U fractionating to phosphogypsum. Activity concentrations of ²³⁸U and ²²⁶Ra in phosphogypsum produced from various fertilizer industries of India showed levels < 1,000 Bq kg^?1 and pose no restriction for use in building/construction material.     

Alpha spectroscopic analysis of actinides (Th,U and Pu) after separation from aqueous solutions by cation-exchange and liquid extraction

The radioactivity concentration of ²³⁶Pu, ²³²U and ²²⁸Th in aqueous samples has been determined by means of alpha spectroscopy after chemical separation and pre-concentration of the radionuclides by cation exchange and liquid–liquid extraction using the Chelex-100 resin and 30% TBP/dodecan, respectively. Method calibration using a ²³⁶Pu standard solution containing the daughter radionuclides results in a detector efficiency of 18% and in a chemical recovery for cation-exchange which is (30 ± 7)%, (90 ± 5)% and (20 ± 5)% for plutonium, uranium and thorium, respectively. The chemical recovery for liquid–liquid extraction is found to be (60 ± 7)%, (50 ± 5)% and (70 ± 5)%, for plutonium, uranium and thorium, respectively. The differences in the efficiencies can be ascribed to the oxidation states, the different actinides present in solution. Taking into account that the electrodeposition of the radionuclides under study is quantitative, the total method efficiency is calculated to be (18 ± 15)%, (46 ± 7)% and (15 ± 5)%, for plutonium, uranium and thorium, respectively, at the mBq concentration range. The detection limit of the alpha spectrometric system has been found to be 0.2 mBq/L, suggesting that the method could be successfully applied for the radiometric analysis of the studied radionuclides and particularly uranium in aqueous samples.     

Determination of the radon emanation fraction from phosphogypsum using LSC

A simple method for the determination of the radon emanation fraction was studied using a liquid scintillation counter. The radon activity of the gaseous phase in a closed container was measured 1 day and 35 days after sealing and used to calculate the radon emanation fraction. Radon leakage from the container was investigated using a ²²⁶Ra radioactive standard solution (SRM4967, NIST) to plot a radon growth curve. The method was applied to materials that typically contain a high level of radium, such as phosphogypsum, phosphate fertilizer and a rock sample. The effect of temperature on the radon emanation fraction from the materials was investigated at 0, 10, 20, 30 and 40 °C. It was found that there is a linear correlation (R ² = 0.746 − 0.946) between temperature and the emanation fraction. Within the temperature range, the radon emanation fractions were 0.241–0.466 for phosphogypsum, 0.225–0.351 for phosphate fertilizer and 0.154–0.351 for the rock sample.     

Determination of uranium and thorium in phosphate rocks by a combined ion-exchange — Spectrophotometric method

Summary Determination of Uranium and Thorium in Phosphate Rocks by a Combined Ion-Exchange — Spectrophotometric Method A selective anion-exchange separation and Spectrophotometric method has been developed for the determination of uranium and thorium in phosphate rocks. About 0.2 g of rock sample is decomposed with nitric acid. Uranium and thorium are adsorbed by anion-exchange on an Amberlite CG 400 (NO₃ ^–) column from the sample solution adjusted to 2.5M in magnesium nitrate and 0.1M in nitric acid. Uranium and thorium are eluted consecutively with 6.6M nitric acid and 0.1M nitric acid, respectively. Uranium and thorium in the respective effluents are determined spectrophotometrically with Arsenazo III. Results are quoted on uranium and thorium in NBS standard phosphate rock and others.     

Liquid–liquid extraction of uranium(VI) using cyanex 272 in toluene from sodium salicylate medium

Liquid–liquid extraction and separation studies of uranium have been carried out from sodium salicylate media using cyanex 272 in toluene. Uranium was quantitatively extracted by 1 × 10⁻³ M sodium salicylate with 5 × 10⁻⁴ M cyanex 272 in toluene. The extracted uranium(VI) was stripped out quantitatively from the organic phase with 1.0 M hydrochloric acid and determined spectrophotometrically with arsenazo(III) at 660 nm. The effect of concentration of sodium salicylate, extractant, diluents, metal ion and strippants has been studied. Separation of uranium(VI) from other elements was achieved from binary as well as from multicomponent mixtures. The method was extended for the separation and determination of uranium(VI) in geological samples. The method is simple, rapid and selective with good reproducibility (approximately ± 2%).     

Separation of tantalum from niobium in rock phosphates and its determination through neutron activation analysis

A simple solvent extraction procedure for an effective separation of traces of tantalum from rock phosphate samples has been developed and used in its determination through neutron activation analysis. The tantalum contents in the samples were found to be about 3.10⁻⁷%.     

Thorium determination in water samples by liquid scintillation counting after its separation by cloud point extraction

The aim of this study is the separation and pre-concentration of thorium from aqueous solutions by cloud point extraction (CPE) and its the radiometric determination by liquid scintillation counting (LSC). For CPE, tributyl phosphate (TBP) was used as the complexing agent and (1,1,3,3-Tetramethylbutyl)phenyl-polyethylene glycol (Triton X-114) as the surfactant. The radiometric measurements were performed after phase separation by mixing of the surfactant phase with the liquid scintillation cocktail. The effect of experimental conditions such as pH, ionic strength (e.g. [NaCl]) and the presence of other chemical species (e.g. Ca²⁺ and Fe³⁺ ions, and humic acid colloids) on the CPE separation recovery have been investigated at constant reactant ratio (m(TBP)/m(Triton) = 0.1). According to the experimental results the maximum chemical recovery is (60 ± 5)% at pH 3. Regarding the other parameters, generally Ca²⁺ and Fe³⁺ ions as well as the presence of colloidal species in solution (even at low concentrations) results in significant decrease of the chemical recovery of uranium. On the other hand increasing NaCl concentration leads to enhancement of chemical recovery. Generally, the method could be applied successfully for the radiometric determination of thorium in water solutions with relatively increased thorium content.     

Sequential radioanalytical method for the determination of U and Th isotopes, <Superscript>226</Superscript>Ra and <Superscript>210</Superscript>Po using alpha spectrometry in samples of the Brazilian phosphate industry

The phosphate rocks used for the production of phosphate fertilizers present in their composition radionuclides of the U and Th series. During the chemical attack, the radionuclides are distributed to final products and phosphogypsum. A sequential radiochemical procedure was implemented to determine the content of radionuclides alpha emitters in samples of fertilizers and phosphogypsum produced in Brazil. The results obtained show that the levels of radioactivity present in the fertilizers are of the same order of magnitude on those found in the phosphogypsum, reaching values up to 1158 and 457 Bq kg⁻¹, for the U and Th series, respectively.     

Separation of gram quantities of uranium from fission products by extraction chromatography

The separation of gram quantities of uranium from fission products has been investigated by extraction chromatography. The separation which is based on the difference in distribution coefficients between uranium and the fission products on a tributyl phosphate (TBP) resin in nitric acid medium, was carried out by means of high acidity feed and stepwise elution on a TBP chromatography column. The results show that this technique is capable to separate 5 g of uranium from a large quantity of fission products. The recovery of uranium is more than 99%. The decontamination factors of g- and b-activities were 2.1^.10³ and 2.3^.10³, respectively.     

Solid phase extractive preconcentration of uranium(VI) onto diarylazobisphenol modified activated carbon

Diarylazobisphenol (DAB) 1 and diarylazobisphenol modified carbon 2 were synthesized and characterised. The latter has been used for solid phase extractive preconcentration and separation of trace amounts of uranium(VI) from other inorganics. In this, a column mode preconcentration of uranium(VI) was carried out in the pH range 4.0-5.0, eluted with 1.0 mol l⁻¹ HCl and determined by an Arsenazo III spectrophotometric procedure. Calibration graphs were rectilinear over the uranium(VI) concentrations in the range 5-200 μg l⁻¹. Five replicate determinations of 25 μg of uranium(VI) present in 1 l solution gave a mean absorbance of 0.032 with a relative standard deviation of 2.52%. The detection limit corresponding to three times the standard deviation of the blank was found to be 5 μg l⁻¹. The accuracy of the developed preconcentration method in conjunction with the Arsenazo III procedure was tested by analysing MESS-3, a marine sediment certified reference material. Further, the above procedure has been successfully employed for analysis of uranium(VI) in soil and sediment samples.     

Development of reliable analytical method for extraction and separation of thorium(IV) by Cyanex 272 in kerosene

A simple and selective spectrophotometric method has been developed for the extraction and separation of thorium(IV) from sodium salicylate media using Cyanex 272 in kerosene. Thorium(IV) was quantitatively extracted by 5 × 10⁻⁴ M Cyanex 272 in kerosene from 1 × 10⁻⁵M sodium salicylate medium. The extracted thorium(IV) was stripped out quantitatively from the organic phase with 4.0 M hydrochloric acid and determined spectrophotometrically with arsenazo(III) at 620 nm. The effect of concentrations of sodium salicylate, extractant, diluents, metal ion and strippants has been studied. Separation of thorium(IV) from other elements was achieved from binary as well as multicomponent mixtures such as uranium(VI), strontium(II), rubidium(I), cesium(I), potassium(I), Sodium(I), lithium(I), lead(II), barium(II), beryllium(II) etc. Using this method separation and determination of thorium(IV) in geological and real samples has been carried out. The method is simple, rapid and selective with good reproducibility (approximately ±2%).     

Extraction and spectrophotometric determination of uranium in phosphate fertilizers

An extraction and spectrophotometric method for determination of trace amounts of uranium in phosphate fertilizers is described. It is based on the extraction of uranium with trioctylphosphine oxide in benzene and the spectrophotometric determination of uranium with Arsenazo III in buffer-alcoholic medium. The maximum absorbance occurs at 655 nm with a molar absorptivity of 1.2·10⁴ l·mol^–1·cm^–1. Beer's law is obeyed over the range 0.6–15.0 g·ml^–1 of uranium(VI). The proposed method has been applied successfully to the analysis of phosphate fertilizers with phosphate concentrations of 45% P₂O₅.     

Characterization of hot particles in surface soil around the Chernobyl NPP

An ICP-AES method for the analysis of trace amounts of lanthanides and yttrium in sodium or magnesium diuranate samples (yellow cake) and other beneficiation product generated during the uranium extraction process (hydrometallurgy) from its ores is described. Most of the matrix elements are removed by an initial oxalate precipitation of lanthanides using calcium as carrier. A solvent extraction procedure using a mixture of mono 2-ethylhexyl dihydrogen phosphate (H₂MEHP) and bis (2-ethylhexyl) hydrogen phosphate (HDEHP) is used for the removal of calcium, iron and the occluded uranium. A combination of oxalate precipitation and solvent extraction procedure is applied for the selective separation and preconcentration of traces of lanthanides from yellow cake and iron cake samples. The solvent extraction procedure is directly applied for the separation of lanthanides from the uranium leach liquor and lime cake. The accuracy of the method is checked by analyzing synthetic mixture containing known amounts of traces of lanthanides and also by comparing with another standard separation procedure like ion exchange method, and the recovery was better than 95%. The method is rapid, simple, accurate and suitable for the separation of lanthanides from uranium, iron and calcium rich materials. The precision of the method is characterized by an RSD of 2 to 4%.     

Method development and validation for melamine and its derivatives in rice concentrates by liquid chromatography. Application to animal feed samples

An isocratic LC method for the determination of melamine and its degradation products (ammelide, ammeline, and cyanuric acid), used to increase the apparent protein content of rice protein concentrate, has been developed. Method development involved optimization of different RP columns, aqueous mobile phases, pH, phosphate concentration, and temperature. The optimum separation of these compounds was achieved using a Luna CN column (30 °C), 5 mmol L⁻¹ sodium phosphate (pH 5.0) as mobile phase, 1 mL min⁻¹ flow-rate, UV absorbance-DAD detection at 220 nm, and resorcine as internal standard; this enabled separation of these compounds with baseline resolution (values in the 2.1–10.1 range) in about 8 min. Prior to HPLC, the developed sample preparation procedure consisted in a leaching process using the above mentioned mobile phase. Method validation was carried out in rice protein concentrates in accordance with the European Commission decision 2002/657/EC criteria. For this purpose, eight mandatory performance characteristics for the conventional validation approach were determined: calibration graphs, extraction efficiencies, decision limits, detection capabilities, precision (repeatability and within-laboratory reproducibility), accuracy, selectivity, and robustness. The extraction efficiencies for these compounds were in the range 99–100% and the within-laboratory reproducibility at 1.0, 1.5, and 2.0 detection capabilities concentration levels were smaller than 5, 4, and 3%, respectively. Finally, the proposed method was successfully applied to the analysis of other rice protein concentrates and several animal feed samples.     

Extraction of uranium with 2,3-dihydroxynaphthalene and cetyltrimethylammonium bromide, and its fluorimetric determination in silicate rocks

A novel procedure for the extraction of uranium has been described. UO₂ ²⁺ forms a 1:3 anionic complex with 2,3-dihydroxynaphthalene in the pH range, 4–12. This anionic complex is best extracted into ethyl acetate at pH 11–12 under the influence of a counter cation, cetyltrimethylammonium bromide. This extraction technique has been extended to the separation of uranium from silicate rock matrices for its determination by fluorimetry. Except Co, Cr, and Fe, most elements present in silicate rocks do not interfere. While the interferences of Co and Cr are suppressed by the addition of EDTA, iron is removed by prior extraction at pH 4–5 as its neutral complex with 2,3-dihydroxynaphthalene. The results compare favourably with those obtained from the conventional technique, i.e., extraction of uranium in ethyl acetate from NHO₃ medium under the influence of Al(NO₃)₃ ^.9H₂O as salting out agent. The extraction system under study is capable of separating even ultra-trace amounts of uranium quantitatively from complex matrices of rock samples. Besides, the method is simple, rapid, cost effective and precludes the use of reagents like nitric acid and aluminum nitrate (salting out agent) required in bulk quantities in the conventional system.     

Determination of rare-earth elements in uranium-bearing materials by inductively coupled plasma mass spectrometry

A novel and simple analytical procedure has been developed for the trace-level determination of lanthanides (rare-earth elements) in uranium-bearing materials by inductively coupled plasma sector-field mass spectrometry (ICP-SFMS). The method involves a selective extraction chromatographic separation of lanthanides using TRU™ resin followed by ICP-SFMS analysis. The limits of detection of the method proposed is in the low pg g⁻¹ range, which are approximately two orders of magnitude better than that of without chemical separation. The method was validated by the measurement of reference material and applied for the analysis of uranium ore concentrates (yellow cakes) for nuclear forensic purposes, as a potential application of the methodology.     

Amberlite XAD-4 functionalized with succinic acid for the solid phase extractive preconcentration and separation of uranium(VI)

Amberlite XAD-4 resin has been functionalized with succinic acid by coupling it with dibromosuccinic acid after acetylation. The resulting resin has been characterized by FT-IR, elemental analysis and TGA and has been used for preconcentrative separation of uranium(VI) from host of other inorganic species prior to its determination by spectrophotometry. The optimum pH value for quantitative sorption of uranium(VI) in both batch and column modes is 4.5-8.0 and desorption can be achieved by using 5.0 ml of 1.0 mol l⁻¹ HCl. The sorption capacity of functionalized resin is 12.3 mg g⁻¹. Calibration graphs were rectilinear over the uranium(VI) concentrations in the range 5-200 μg l⁻¹. Five replicate determinations of 50 μg of uranium(VI) present in 1000 ml of solution gave a mean absorbance of 0.10 with a relative standard deviation of 2.56%. The detection limit corresponding to three times the standard deviation of the blank was found to be 2 μg l⁻¹. Various cationic and anionic species at 200-fold amounts do not interfere during the preconcentration of 5.0 μg of uranium(VI) present in 1000 ml (batch) or 100 ml (column) of sample solution. Further, adsorption kinetic and isotherm studies were also carried out by a batch method to understand the nature of sorption of uranium(VI) with the succinic acid functionalized resin. The accuracy of the developed solid phase extractive preconcentration method in conjunction with Arsenazo III procedure was tested by analyzing marine sediment (MESS-3) and soil (IAEA soil-7) reference material. Further, the above procedure has been successfully employed for the analysis of soil and sediment samples.     

Lichen specie Canoparmelia texana as bioindicator of environmental impact from the phosphate fertilizer industry of São Paulo,Brazil

The Brazilian phosphate industry is the sixth worldwide producer of phosphate rock concentrate generating phosphoric acid, fertilizers, intermediates for fertilizers and other products. Two of the most important of these industries are both located in the city of Cubatão—São Paulo, Brazil, and they are responsible for the production of P₂O₅, generating a residue known as phosphogypsum. The raw material, phosphate rock and products are commonly transported to the industrial complex by a railroad line and present in their composition natural radionuclides from the U and Th series and rare earth elements. Lichens have been used for monitoring atmospheric pollution and radiological contamination for a long time and have proven to be an important tool. This paper aims to highlight the use of the lichen specie Canoparmelia texana (family Parmeliacea) as a bioindicator of atmospheric pollution by the natural radionuclides from the U and Th series and RREs due to the operation of these industries and the storage of their residue in the open air. Samples of these lichen specie were collected in the vicinity of the industries and the railroad. The radionuclides ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb were measured by alpha and beta counting, after radiochemical separation, and ²³⁸U, ²³²Th as well as REEs were determined by instrumental neutron activation analysis. The results showed that the lichens present the same fingerprint as the phosphate rock and phosphogypsum, furthermore the cluster analysis of the results showed that the lichen samples collected near to the railroad line presented the highest values for all the elements studied.