Rare earth impurities in high purity lanthanum oxide determined by neutron activation analysis

Individual rare earth impurities in high purity La₂O₃ (99.9%) have been determined by NAA after pre-separation of the matrix (La). The separation is carried out on an anion exchanger (Dowex 1×8) using different mixtures of methanol/nitric acid as eluants. The rare earth elements from Dy to Lu are eluted quantitatively using a 10% 1M HNO₃-90% methanol mixture, while the light rare earths from Ce to Gd are eluted quantitatively using a 10% 0.05M HNO₃-90% methanol mixture. La, which is retained on the column, is eluted using 0.1M HNO₃. The recoveries of the various rare earth elements have been checked using radiotracers and also by spiking the sample with known amount of elements, and the recoveries are found to be quantitative. Results obtained on a typical high purity lanthanum oxide are reported here.     

Mutual Separation of Rare Earths in Monazite with Cation Exchange Elution Chromatography

Mutual separation of the individual rare earth elements (exception of cerium) in monazite from different districts was investigated by cation exchange elution method. Strong acid type cation exchange resin, Bio-Rad AG 50 Wx8 and eluting solution of a α-hydroxyisobutyric acid (α-HIBA) were used. Radioactivity tagged Eu-152, 154 or Tb-160 were used as radio active indicator for determination of the distribution coefficients by batch method or for the study of column elution conditions. By gradiently increase of the pH values from 3 to 5 in 0.3 M α-HIBA eluting solution, complete mutual separation of individual rare earth elements, exception of Dy and Y, were obtained. Dy and Y could not be separated by this scheme of separation and their elution zones were overlapped. Rare earth mixture samples of monazite from different districts were separated with this scheme and these results were compared. From this comparison followings were noticed; 1. Compositions of rare earth elements in monazite from different districts are evidently not alike. 2. Samples from Brazil and Southwestern Coast of Taiwan are much more alike in their compositions but not for those from Australia and Outskirt Island. 3. Sample from Outskirt Island has higher in contents of heavier rare earths and also Nd was higher than La.     

Synthesis and application of a macroporous silica-based polymeric octyl(phenyl)-N,N-diisobutylcarbamoylmethylphoshine oxide composite for the chromatographic separation of high level liquid waste

Summary The Minor Actinides Recovery from HLW by Extraction Chromatography (MAREC) process was used mainly for the separation of minor actinides (MAs) and some specific fission products (FPs) from highly active liquid waste (HLW) by the composite CMPO/SiO₂-P of the macroporous silica based polymeric octyl(phenyl)-N,N-diisobutylcarbamoylmethylphoshine oxide (CMPO) and others. In this study a cascade of chromatographic separation was performed on a 3.0M HNO₃ solution containing 5.0 ^. 10^-3M of 13 elements, at 323 K. The cascade consisted of three columns the first and second ones were packed with CMPO/SiO₂-P and the third with SiO₂-P particles. The first column was employed to prepare various eluents containing saturated CMPO. The second column was used for separation into groups. The CMPO of CMPO/SiO₂-P was recovered from the effluent by the third column and a CMPO-free effluent containing minor actinides was obtained. The elements contained in the simulated HLW of 3.0M HNO₃ were separated into (1) a non-adsorption group (Sr, Cs, and Ru etc.), (2) a MA-hRE (heavy rare earth)-Mo-Zr group, and (3) a lRE (light rare earth) group by eluting with 3.0M HNO₃, 0.05M DTPA (diethylenetriaminepentaacetic acid) (pH 2.0) and HNO₃ (pH 3.5), respectively. The resultant MA-hRE-Mo-Zr mixture containing minor actinides was then separated into the groups (1) Pd-Ru, (2) MA-hRE, and (3) Mo-Zr by utilizing 3.0M HNO₃, distilled water, and 0.05M DTPA (pH 2.0) as eluents. More than 92% of CMPO in the MA-hRE containing effluent was adsorbed by SiO₂-P particles. The effectivity and technical feasibility of MAREC process were demonstrated.     

Separating Ag, B, Cd, Dy, Eu, and Sm in a Gd matrix using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction chromatography for ICP-AES analysis

The separation procedure for Ag, B, Cd, Dy, Eu and Sm as impurities in Gd matrix using ICP-AES technique with an extraction chromatographic column has been developed. The spectral interference of the Gd matrix on the elements was eliminated using a chromatography technique with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) as the mobile phase and XAD-16 resin as the stationary phase. Ag⁺, B₄O₇²⁻, and Cd²⁺ were eluted with 0.1 M HNO₃, while rare earth ions were not. The best eluent for separating Eu and Sm in the Gd matrix was 0.3 M HNO₃. The limit of quantitation for these elements was 0.6-3.0 ng mL⁻¹. The recovery of Ag, B, and Cd was 90-104% using 0.1 M HNO₃ as the eluent, while that of Eu, Gd, and Sm ranged from 100 to 102% with 0.3 M HNO₃. Dy was recovered quantitatively with 4 M HNO₃. The relative standard deviation of the methods for a set of three replicates was between 1.0 and 15.4% for the synthetic and standard Gd solutions. The proposed separation procedure was used to measure Ag, B, Cd, Dy, Eu, and Sm in a standard Gd solution.     

Determination of radioactive strontium in seawater

This paper describes the procedures of isolating strontium and yttrium from seawater that enable the determination of ^89,90Sr. In one procedure, strontium is directly isolated from seawater on the column filled with Sr resin by binding of strontium to the resin from 3 M HNO₃ in a seawater, and successive elution with HNO₃. In others, strontium is precipitated from seawater with (NH₄)₂CO₃, followed by isolation on a Sr column or an anion exchange column. It is shown that strontium precipitation is optimal with concentration of 0.3 M (NH₄)₂CO₃ at pH = 11. In these conditions, 100% Y, 78% Sr, 80% Ca and 50% Mg are precipitated. Strontium is bound on to Sr column from 5 to 8 M HNO₃, separated from other elements by elution with 3 M HNO₃ and 0.05 M HNO₃. Strontium and yttrium are bound on to anion exchange column from alcoholic solutions of nitric acid. The optimum mixture of alcohols for sample binding is a mixture of ethanol and methanol with the volume ratio 1:3. Strontium and yttrium are separated from Mg, Ca, K, and other elements by elution with 0.25 M HNO₃ in the mixture of ethanol and methanol. After the separation, yttrium and strontium are eluted from the column with water or methanol.In the procedure of direct isolation from 1 l of the sample, the average recovery of 50% was obtained. In the remaining two procedures, the strontium recovery was about 60% for the Sr column and 65% for anion exchange column. Recovery of yttrium is about 70% for the anion exchange column. It turned out that the procedure with the Sr resin (direct isolation and isolation after precipitation) is simpler and faster in the phase of the isolation on the column in comparison with the procedure with the anion exchanger. The procedure with the anion exchanger, however, enables the simultaneous isolation of yttrium and strontium and rapid determination of ^89,90Sr. These procedures were tested by determination of ^89,90Sr on liquid scintillation counter and Cherenkov counting in 5 M HNO₃. Obtained results showed that activity of 50 mBq l⁻¹ of ^89,90Sr and higher can be simultaneously determined.     

Separation of Sr in combination of ion exchange and Sr resin with alcohol-nitric acid solution and rapid determination of <Superscript>90</Superscript>Sr in wine and soil samples

This paper describes the procedures of isolating strontium from wine and soil samples which enable creating of procedure for rapid determination of ⁹⁰Sr. The method of determination of ⁹⁰Sr includes binding of Sr on the cationic exchanger IR-120 from the sample and simultaneous elution from the cation column and binding on the Sr column, separation of Sr on Sr resin with HNO₃ even in presence of alcohols and subsequent Cherenkov counting. Sr can be efficiently bind on Sr resin and separated from the other elements with lower acid concentrations in the presence of a low portion of alcohol, or even from a wine sample without the loss of Sr resin capacity. The binding strength of Sr on Sr resin decreases with the rising of HNO₃ concentration (1–5 M) in the presence of 13% of ethanol or methanol, and with the rising of the alcohol portion in constant concentration of HNO₃. Application of cation exchanger for Sr binding in phase of sample preparation decreases Sr column loading and improve Sr recovery. The method allows the determination of ⁹⁰Sr activities in wine and soil sample lower than 10 mBq in reasonable time.     

Separation and determination of rare earth elements by Dowex 2-X8 resin using sodium trimetaphosphate as elution agent

The distribution coefficients of rare earth elements and thorium with Dowex 2-X8, 200-400 mesh, a strongly basic anion-exchange resin, have been determined regarding four different concentrations of sodium trimetaphosphate (3 x 10(-3), 5 x 10(-3), 7 x 10(-3) and 0.01 M). The separation of the rare earths and thorium obtained from an Australian monazite has been investigated by anion-exchange chromatography with sodium trimetaphosphate concentration gradient on a Dowex 2-X8 ion-exchange columns. The order of elution of the elements was the reverse of the order of elution of the same elements on Dowex 1 resin. The elution was investigated using 5 mg and 250 mg samples. In the separation of 5 mg samples, all elements were separated in 29 min. It has been seen that the elution peaks are narrow, tailing effects are very small, Dy and Y are well separated. Qualitative and quantitative determinations were realized by spectrofluorometry.     

Cation-exchange isolation and ICP-AES determination of rare earth elements in geological silicate materials

An ion-exchange ICP-AES method for the determination of 14 rare earth elements (REEs) and Y in geological materials is described. The separation of REEs from Ba using a Dowex 50W-X8 cation resin is especially considered since Ba is an excellent internal standard for REE determination by this technique. Although total recovery with either HCl or HNO₃ may be achieved, it is advantageous to use both acids sequentially. Volume and concentration of the acids are optimized attaining a quantitative separation of REEs from Ba by the introduction of the sample solution in a 1.75 mol/l HCl medium, followed by elution with 2 mol/l HNO₃ to remove matrix elements and with 7 mol/l HNO₃ to elute the analytes. The total elution volume is significantly reduced without decreasing the efficiency. The behaviour of the matrix constituents under the selected conditions is also studied, evaluating their elution percentages in each step. The final solution obtained contains only the REEs and Y, with the bulk of Sc and minor amounts of Cr, Fe, Hf and Ta. Experimental data for 5 geological reference standards (NIM-G, GSP-1, AGV-1, NIM-L and NIM-S) are reported. Good agreement between the present results and previously accepted values by various analytical techniques is observed.     

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>     

Preconcentration and determination of rare-earth elements in iron-rich water samples by extraction chromatography and plasma source mass spectrometry (ICP-MS)

A 100-fold preconcentration procedure based on rare-earth elements (REEs) separation from water samples with an extraction chromatographic column has been developed. The separation of REEs from matrix elements (mainly Fe, alkaline and alkaline-earth elements) in water samples was performed loading the samples, previously acidified to pH 2.0 with HNO₃, in a 2 ml column preconditioned with 20 ml 0.01 M HNO₃. Subsequently, REEs were quantitatively eluted with 20 ml 7 M HNO₃. This solution was evaporated to dryness and the final residue was dissolved in 10 ml 2% HNO₃ containing 1 μg l⁻¹ of cesium used as internal standard. The solution was directly analysed by inductively coupled plasma mass spectrometry (ICP-MS), using ultrasonic nebulization, obtaining quantification limits ranging from 0.05 to 0.10 ng l⁻¹. The proposed method has been applied to granitic waters running through fracture fillings coated by iron and manganese oxy-hydroxides in the area of the Ratones (Cáceres, Spain) old uranium mine.     

Extraction of rare earth elements with 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene with the use of 1,1,7-trihydrododecafluoroheptanol as a solvent

Extraction of rare earth elements from nitric acid solutions in a 1,1,7-trihydrododecafluoroheptanol-water system with the use of phosphoryl-containing podand 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene (L) was studied. The content of metals in organic phase was shown to be negligible at nitric acid concentration lower 1 mol/L. Distribution ratio sharply increases with nitric acid concentration from 1 mol/L and reaches 5.5 for the yttrium subgroup elements at HNO₃ concentration of 6 mol/L. The rare earth elements of the yttrium subgroup were found to be extracted much better than the rare earth elements of the cerium subgroup under the same conditions, the distribution ratios in both subgroups smoothly rise with atomic number of element. It was shown using the shift of extraction equilibrium that the M: L ratio in extracted complexes is 1: 2 irrespective of the nature of rare earth element. The structure of complex {Yb[η²-(O,O′)-L]₂(η²-O₂NO)₂}(O₂NOHNO₃), whose single crystals were isolated from extraction solution, was established by X-ray diffraction study. The system can be used for the isolation and separation of rare earth elements.     

Anion Exchange Separation of Rare Earths in Methanol-Nitric Acid Mixed Solutions I. Study on the Distribution Coefficients and Column Elution Method

Anion exchange method for the mutual separation of rare earth was studied in methanol-nitric acid mixed solutions. For each of rare earth element, the distribution coefficients in different concentrations of nitric acid and also in various compositions of methanol solution were studied with the batch equilibrium method. From these distribution coefficients, elution of rare earth by gradient variation in the compositions of methonal was devised. That is, by keeping constant nitric acid at 2 N acidity and gradiently diluting methanol from its original 80% by volume. Results were satisfactory for the mutual separation of the lighter rare earths, but only fairly for the heavier earths. The secondary metal effect for this anion exchange was also studied in 80% by volume of methanol solution by keeping total concentration of nitrate at 0.8 N. Distribution coefficients were larger than nitric acid with LiNO₃ but smaller in the case of NH₄NO₃ and NaNO₃. Despite of these difference in distribution coefficients, no remarkable differences were observed for the separation factors of adjacent pairs.     

Use of alcoholic solutions for the isolation and purification of americium and curium with anion-exchangers

The sorption of transplutonium (TPE), rare-earth (RE) and other elements by anion-exchangers (Dowex 1 type) from aqueous alcoholic solutions of nitric acid and ammonium thiocyanate was investigated. This investigation allowed the development of simple and effective methods of americium—curium separation from frradiated plutonium. Plutonium, TPE (in a +3 oxidation state) and RE are firmly sorbed by the anion-exchanger from 1 M HNO₃ in 90% alcohol, Fe, Al and fission products Cs, Sr, Nb, Zr, and Ru pass through the column under these conditions. The RE separation from TPE is achieved by washing the column with 0.5M NH₄SCN in 80% alcohol. The column is then washed with 0.5 M HNO₃ in 85% alcohol, and americium—curium separation proceeds. Use of this method for recovery of an irradiated plutonium target containing 100 mg Pu, Am and Cm is described.     

Chromatographic separation of trivalent actinides and rare earth elements by using pyridine type resin

Summary In order to develop the partitioning-transmutation system for the reduction of high-level radioactive wastes, the group and mutual separation of actinides and rare earth elements in spent fuels is required. In the present work, a chromatographic separation of trivalent actinides (Am and Cm) and rare earth elements was examined in hydrochloric acid/methanol mixed solvents by using a pyridine resin embedded in high-porous silica beads. In a 70 vol% hydrochloric acid (11.7 mol HCl/dm³)/30 vol% methanol mixed solvent, the elution curves of the trivalent actinides were separated completely from those of rare earth elements at room temperature. The present paper discusses the separation behavior of trivalent actinides and rare earth elements as a function of flow rate, temperature and solvent compositions.     

Radiochemical separation of 88Y from a SrCl2 target using chelating resin Chelex 100

Summary Yttrium-88 was produced from irradiation of a SrCl₂ target (4.8 g, pressed into a 19 mm disc) by 33 MeV proton beam at a current of up to 90 mA. Chelating resin Chelex 100 (H⁺ form, 100-200 mesh) was used for the separation of yttrium radionuclides (including ⁸⁸Y) from strontium. 0.01M nitric acid was used for the dissolution of target (100 ml), retention of Y and elution of Sr (200 ml). For the elution of yttrium, 25 ml 1M HNO₃ was employed. The column was 4 cm long with internal diameter of 1.6 cm. The flow rate was 1 ml/min throughout the separation procedure. The ⁸⁸Y recovery yield was 94% average and the stable Sr content in the final product (5 ml 0.1M HCl) was estimated to be less than 3 ppm.     

Determination of rare earth elements in Taiwan monazite by chemical neutron activation analysis

Taiwan monazite is a unique mineral obtained from the heavy sand found in the river floor of Tzuo-suei river and En-suei river. Both rivers are flowing parallel with separated narrow area into the sea at southwestern coast of Taiwan. The characteristic of monazite is that it contains considerable rare earth elements (REEs). REEs are considered very useful elements in the local industries and scientific researches such as ceramic, semiconductors, and glass optics. In this study, chemical neutron activation analysis (CNAA) was used to determine the contents of REEs in Taiwan monazite. A few milligram of monazite was digested in the microwave oven for 25 minutes with mixed acid (conc. HNO₃ and HClO₄). REEs were preconcentrated by hydrated magnesium oxide and CNAA was performed.     

Separation of thorium by anion-exchange chromatography in malic acid media

Summary Systematic studies on the anion-exchange behaviour of thorium in malic acid solution on Amberlite IRA-401 have been carried out. Acids such as HNO₃, HCl, H₂SO₄, HClO₄ and salts such as NH₄Cl, (NH₄)₂SO₄, NaClO₄, NaCl and NaNO₃ have been tested as eluants for thorium, their efficiency being evaluated in terms of their distribution coefficients. HNO₃ is the best eluent for thorium. Methods have been developed for the separation of thorium from several elements in malic acid media using selective adsorption or selective elution. The proposed method is applied to the analysis of thorium in monazite where HClO₄ is a better eluant than HNO₃. The method is simple and the accuracy about ±3%.     

Anion exchange separation of the light lanthanoids with nitric acid-methyl alcohol mixed media at elevated temperature

Anion exchange chromatography with nitric acid-methyl alcohol mixed media at elevated temperature has been applied to mutual separation of the light lanthanoids, La, Ce, Pr, Nd and Pm. The individual elements could be effectively separated from each other, main fission products and actinoids with 0.01M HNO₃-90% CH₃OH or 0.5M HNO₃-80% CH₃OH eluent at 90 °C.     

Preparation and characterization of an extraction chromatography column for technetium separation based on Aliquat-336 and silica gel support

An extraction chromatographic material based on Aliquat-336 anchored on hydrophobized silica gel support was prepared as an ion exchanger. The prepared material appeared to be suitable for the separation of ⁹⁹Tc from environmental matrices in column application. The properties of the material, sorption characteristic and distribution coefficient of ^99mTcO₄ ^-in various media were studied. The prepared sorbent was conditioned by washing with nitric acid. The solution containing ^99mTcO₄ ^- in 0.1M HNO₃ was passed through the column. Tc was eluted from the column by 8M HNO₃. The flow rate was 0.4 ml/min. The chemical yield of technetium during the separation process was determined using ^99mTc tracer and gamma measurement. The sorption recovery of Tc from the prepared sorbent with 0.1M HNO₃ solution was more than 98%, and the desorption recovery from the column using 8M HNO₃ varied between 92-96%. It was found that the prepared sorbent is suitable for the separation of technetium from environmental matrices and radioactive wastes. This revised version was published online in July 2006 with corrections to the Cover Date.     

Simultaneous production and separation of no-carrier-added 111In, 109Cd from alpha particle induced silver target

A natural silver foil was bombarded by 30 MeV α-particles which produced ¹¹¹In, ¹⁰⁹Cd and ^106mAg in the target matrix. ¹¹¹In and ¹⁰⁹Cd were separated from the Ag target matrix employing ion-exchange chromatography and liquid–liquid extraction (LLX). In the chromatographic separation, the active solution containing the NCA products were adsorbed in the column containing Dowex 50 and were eluted with HNO₃. Bulk silver and ¹⁰⁹Cd were sequentially eluted with 1 M HNO₃. After complete elution of ¹⁰⁹Cd and the bulk, ¹¹¹In was eluted with 1.5 M HNO₃. In the LLX, the NCA ¹¹¹In was extracted to 1 % HDEHP (di-2(ethylhexyl)phosphoric acid) from 10^?2 M HNO₃ solution, leaving cadmium and bulk silver quantitatively in the aqueous phase. The NCA ¹⁰⁹Cd was separated from the bulk Ag by precipitating Ag as AgCl. NCA ¹¹¹In was stripped back quantitatively from HDEHP phase using 8 M HNO₃.