Studies on the recovery of Pu(IV) from hydrochloric acid-oxalic acid solutions using an anion exchange method

Sorption of Pu(IV) from hydrochloric acid-oxalic acid solutions has been investigated using different anion exchangers, viz., Dowex-1X4, Amberlite XE-270 (MP) and Amberlyst A-26 (MP) for the recovery of plutonium from plutonium oxalate solutions. Distribution ratios of Pu(IV) for its sorption on these anion exchangers have been determined. The sorption of Pu(IV) from hydrochloric acid solutions decreases drastically in the presence of oxalic acid. However, addition of aluminium chloride enhances the sorption of plutonium in the presence of oxalic acid, indicating the feasibility of recovery of plutonium. Pu(IV) breakthrough capacities have been determined with a 10 ml resin bed of each of these anion exchangers at a flow rate of 60 ml per hour using a solution of Pu(IV) with the composition: 6M HCl+0.05M HNO₃+0.1M H₂C₂O₄+0.5M AlCl₃+100 mg.l^–1 Pu(IV). The 10% Pu(IV) breakthrough capacities for Dowex-1X4, Amberlite XE-270 (MP) and Amberlyst A-26 (MP) are 15.0, 8.9 and 6.2 g of Pu(IV) l^–1 of resin respectively.     

Separation and Recovery of Uranium and Plutonium from Oxalate Supernatant

The separation of uranium and plutonium from oxalate supernatant, obtained after precipitating plutonium oxalate, containing ~10 g/l uranium and 30–100 mg/l plutonium in 3M HNO₃ and 0.10–0.18M oxalic acid solution has been carried out. In one extraction step with 30% TBP in dodecane: ~92% of uranium and ~7% of Pu is extracted. The raffinate containing the remaining U and Pu is extracted with 0.2M CMPO+1.2 M TBP in dodecane and near complete extraction of both the metal ions is achieved. The metal ions are back extracted from organic phases using suitable stripping agents. The recovery of both the metal ions separately is >99%. The uranium species extracted into the TBP phase from the HNO₃+oxalic acid medium was identified as UO₂(NO₃)₂·2TBP.     

One step U-Pu-Cs-Ln-steel separation using TRU preconditioned extraction resins from Eichrom for application on transmutation targets

A one step Cs, lanthanides (Ln), Pu and U separation using TRU resin (Eichrom), for subsequent isotopic analyses, is presented for samples of transmutation targets containing a predominant matrix of steel elements. Cs, Ln, Pu and U are successively eluted using minor volumes (<12 mL) of 2M HNO₃, 4M HCl, 0.075M oxalic acid in 1M HCl media and 0.1M ammonium hydrogen oxalate in 0.02M HNO₃ media, respectively. Accurate and precise isotopic compositions obtained for these elements by thermal ionization mass spectrometry or multiple collector inductively coupled mass spectrometry show neither significant fractionation nor contamination during the complete analytical process.     

Extraction of plutonium from acidic media using various phosphine oxides

Extraction, loading and stripping studies of Pu(IV) have been carried out using three phosphine oxides namely Cyanex^Ò-923 (cyn-923), Cyanex^Ò-925 (cyn-925) and TOPO in dodecane from nitric acid medium. All the three phosphine oxides have shown very high extraction of Pu. The order of extraction for Pu by these compounds is cyn-923 > TOPO - cyn-925. Loading of Pu (30.0 mg/l) in 3.0M HNO₃ was carried out using 5% solution of each of the phosphine oxides in dodecane. It was found that even at an organic to aqueous phase ratio of 1:10, the loading of Pu is >96%. From the loaded organic phase, Pu could be almost quantitatively stripped using 0.1 or 0.5M oxalic acid. The extraction of Pu(IV) with cyn-925 has also been carried out from HCl, HNO₃ or HClO₄ (0.5 to 9.1M). The species extracted into the cyn-925/dodecane phase from 3.0M HNO₃ or HCl media was found to be Pu(L)₄ ^.2 cyn-925 where L = NO₃ ^– or Cl^–. Similar species were observed to be formed when dodecane was replaced by xylene, chlorobenzene or o-dichlorobenzene.     

Precipitation of plutonium oxalate from homogeneous solutions

A method for the precipitation of plutonium(IV) oxalate from homogeneous solutions using diethyl oxalate is reported. The precipitate obtained is crystalline and easily filterable with yields in the range of 92–98% for precipitations involving a few mg to g quantities of plutonium. Decontamination factors for common impurities such as U(VI), Am(III) and Fe(III) were determined. TGA and chemical analysis of the compound indicate its composition as Pu(C₂O₄)₂·6H₂O. Data are obtained on the solubility of the oxalate in nitric acid and in mixtures of nitric acid and oxalic acid of varying concentrations. Green PuO₂ obtained by calcination of the oxalate has specifications within the recommended values for trace foreign substances such as chlorine, fluorine, carbon and nitrogen.     

An improved actinide separation method for environmental samples

This paper presents a rapid method of separation of five actinide elements (Th, U, Np, Pu, and Am) for aqueous media samples. This separation method utilizes the unique chemistries of the actinides at low concentrations^1,2 and the properties of the EIChroM TRU-Resin^TM extraction resin. In order to cleanly recover the five actinides from aqueous samples or solubilized soil samples, the sample is passed through the column twice. The sample is first loaded in an HCl solution with hydrogen peroxide. This allows the Am and most matrix ions to pass through the column. Then the Th is eluted using dilute HCl followed by the Np and Pu which are eluted together with oxalic acid in dilute HCl solution. Finally, the U is eluted with ammonium oxalate solution. A calcium-oxalate coprecipitation is performed on the original load solution containing the Am ions and the dissolved precipitate is then reloaded onto the TRU-Resin^TM column in HNO₃ with ascorbic acid. The procedure requires approximately 1.5 working days for experienced technicians, greatly reduces waste, and generally results in actinide recoveries of 80–100%.     

Extraction of Am(III) from different acid media by di-2-ethyl hexyl phosphoric acid containing phosphorous pentoxide

The extraction of Am(III) from nitric, hydrochloric, oxalic, phosphoric and hydrofluoric acids was studied using 0.4F di-2-ethyl hexyl phosphoric acid (HDEHP) containing 0.1M phosphorous pentoxide (P₂O₅) in dodecane/xylene. The extraction with pure 0.4F HDEHP was found to be negligible from all the media studied. However, the presence of a small amount of P₂O₅ in it increased the extraction substantially. The distribution ratios of Am(III) obtained for HDEHP - P₂O₅ mixture 3M nitric acid containing different concentrations of oxalic acid/phosphoric acid/hydrofluoric acid are in the order of 200-250. The same for 3M hydrochloric acid is very high (800). These distribution ratios are sufficiently high for the quantitative extraction of Am(III) from all the acid media studied. Different reagents such as ammonium oxalate, sodium oxalate, oxalic acid, hydrofluoric acid, sodium carbonate and potassium sulphate were explored for the back extraction of Am(III) from 0.4F HDEHP + 0.1M P₂O₅ in dodecane/xylene. Of these, 0.35M ammonium oxalate and 1M sodium carbonate were found to be most suitable. The back extraction of Am(III) was also attempted with water and 1M H₂SO₄, HNO₃, HClO₄ and HCl solutions after allowing the extracted organics to degrade on its own. It was found that more than 90% of Am could be back extracted with these acids. Using this method more than 90% of Am(III) was recovered from nitric acid solutions containing calcium and fluoride ions.     

Extraction studies of Pu(IV) with octylphenyl acid phosphate

Octylphenyl acid phosphate, the commercially available mixture of monooctylphenylphosphoric acid (MOPPA) and dioctylphenylphosphoric acid (DOPPA) in xylene medium has been employed as an extractant for distribution studies on Pu(IV) in different mineral acids including phosphoric acid. It was found possible to extract Pu quantitatively from an acid mixture comprising 2.5M H₃PO₄, 0.75M H₂SO₄ and 0.5M HNO₃. Quantitative stripping was observed with a mixture of 0.25M oxalic acid and 0.2M ammonium oxalate.Parts of this work have been reported at symposie (Refs^1,2)     

Determination of 210Pb, 210Bi and 210Po in natural drinking water

A new method for the radioanalytical determination of the ²²²Rn progenies ²¹⁰Pb, ²¹⁰Bi and ²¹⁰Powill be presented, which has been improved for analyses of water samples fromdifferent regions in Austria. 1–2 liter samples were taken in polyethylenebottles prefilled with conc. HNO₃ to obtain 0.2M acidic solutions,thus avoiding adsorption effects. After adding 1.6 mg of inactive lead carrier,the water sample was evaporated to dryness, converted to the chloride formand dissolved in 1M HCl.     

Absorption spectroscopic properties for Pu(III,IV and VI) in nitric and hydrochloric acid media

Absorption spectroscopic properties for various Pu oxidation states in nitric and hydrochloric acid solutions were investigated with UV-Visible spectrophotometry. As a result, it was confirmed that the intensities of the major absorption peaks had a tendency to decrease for Pu(III), Pu(IV) and Pu(VI) in HCl and HNO₃ media, and the major peak positions were shifted to longer or shorter wavelengths depending on the complexforming abilities of Pu(III), Pu(IV) and Pu(VI) with the chloride or nitrate ion with increasing acid concentrations. The values of the wavelength and the molar absorptivity for the principal peaks of Pu(III), Pu(IV) and Pu(VI) in NHO₃ and HCl solutions were similar to those reported in other works. The values of the molar absorptivity for the principal peaks of Pu(III), Pu(IV) and Pu(VI) in the HNO₃ solution were a little higher than those in the HCl solution.     

Recovery of plutonium from oxalate supernatant using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

Summary Extraction of Pu(IV) from oxalate supernatant was carried out employing 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) in xylene as extractant. The conditions for quantitative extraction were determined by the variation of ligand, oxalic acid and nitric acid concentration. Quantitative stripping was achieved using a mixture of 0.4M oxalic acid and 0.4M ammonium oxalate. Extraction of Pu(IV) from synthetic oxalate supernatant solution containing 3M nitric acid and 0.2M oxalic acid was investigated under various loading conditions employing 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone in xylene as extractant. Under uranium loading conditions the Pu extraction decreased significantly while with increased Pu loading whereas the D_Pu value was influenced marginally. The effect of a redox reagent on Pu extraction was also investigated.     

Studies on the sorption of Pu(IV) on alumina microspheres from nitric acid-oxalic acid solutions

Sorption of Pu(IV) on alumina microspheres prepared by the sol-gel procedure has been investigated for the recovery of plutonium from nitric acid-oxalic acid solutions. Distribution ratio for Pu(IV) between alumina microspheres and nitric acid-oxalic acid have been determined. The influence of the mode of preparation and heat treatment of these microspheres, on the sorption of Pu(IV) have been investigated. Pu(IV) breakthrough capacities have been determined using a 5 ml bed of alumina with solutions of Pu(IV) in 1M HNO₃+0.05M H₂C₂O₄ and 0.5M HNO₃+0.05M H₂C₂O₄. The elution behavior of Pu(IV) loaded on these microspheres were studied using nitric acid solutions containing different oxidising and reducing agents. Investigations were also carried out to fix the activity in the alumina matrix by heat treatment.     

Interference study of the Pu(III) spectrophotometric assay

The study was undertaken to determine the immunity of the Pu(III) spectrophotometric assay to diverse species. We acquired spectra of a set of solutions containing 10 mM Pu(III), reduced with ascorbic acid-aminoguanidine in 2M HCl, and of a similar set of solutions containing a spike of test species. The initial molar ratio of plutonium to species was 101, and after interference it was increased to 100.1, etc., until no interference occurred. The species examined were element numbers 1, 9, 11–13, 17, 19, 22–31, 35, 42, 44–46, 48, 50, 53, 57, 58, 60, 62, 73, 74, 76, 77, 79, 83, 90, 92, 93, 95 and nitrate, phosphate, sulfate, and oxalic acid.     

Extraction of U(VI), Pu(IV), Am(III) and some fission products by 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester immobilized polyvinyl alcohol hydrogels

Cross-linked hydrogel matrices immobilized with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HA), were prepared to investigate their application in the recovery of radionuclide from acidic waste solutions. Gamma-radiation was used to produce HA immobilized polyvinyl alcohol (PVA) hydrogels (HA-gel). The hydrogels with different characteristics such as: degree of cross-linking (by varying radiation dose) and quantity of extractant immobilized (by starting with aqueous PVA solution containing different amounts of HA), were synthesised. These HA-gels were investigated for solid-liquid phase extraction of U(VI), Pu(IV), Am(III) and some fission products, under various experimental conditions. The concentration of HNO₃ in the aqueous phase was found to play an important role in the extraction of these radionuclei. Extraction of U(VI) was more favourable at lower concentration of HNO₃ (∼0.001 to 0.5M), while at higher concentrations (∼0.5 to 3M HNO₃), more than 90% of Pu(IV) present in the aqueous phase, could be extracted by the HA-gel. The extraction of Am(III) was also found predominant only at lower acidities (at pH∼2 and above). Under optimized conditions, maximum metal loading capacities obtained were 19±0.8 mg, 8±0.4 mg and 11±0.5 mg per gram of swollen HA-gel, for U(VI), Pu(IV) and Am(III), respectively. Under the experimental conditions, extractions of Cs(I) and Sr(II) were observed to be negligible. No leaching out of HA from the HA-gel particles was noted even after its repetitive use for the studied ten cycles of extraction and stripping experiments, as evident from its unchanged extraction efficiency.     

Rapid Separation of Plutonium in Environmental Samples Using an Anion Exchange Resin Disk

A rapid analytical method of Pu in environmental samples by alpha-ray spectrometry and high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) using a 3M Empore anion exchange resin disk for solid phase extraction has been developed. A trace amount of Pu was quantitatively adsorbed with an Empore anion exchange resin disk (47 mm diam.) at a flow rate of 150–200 ml/min from 8M HNO₃ sample solution. The disk was washed with 10 ml of 8M HNO₃ and 12 ml of 9M HCl and then the Pu was quantitatively eluted with 15 ml of 1M HNO₃/0.03M ascorbic acid solution. The time needed to separate Pu from the sample solution with the present method was about 20 minutes. The separated Pu was determined with alpha-ray spectrometry and HR-ICP-MS. The present method was applied to the determination of Pu in the certified reference material (IAEA-135) and the environmental soil sample. The analytical results were almost in good agreement with the literature values.     

Determination of plutonium in environmental samples by controlled valence in aniion exchange

The title method was successfully used for collecting^239,249Pu from 200 litres of seawater by coprecipitation with 16 g FeSO₄·7H₂O under redcing conditions witout filtering. The plutonium is leached by concentrate HNO₃+HCl from the coprecipitate and the solid particles. The precipitate is heated at 400°C and digested in aqua regia. Na₂SO₃ and NaNO₂ have been applied to obtain the Pu⁴⁺ valence state in 0.5–1N HNO₃ for different samples. Plutonium and thorium are coadsorbed on anionic resin from 8N HNO₃. The column is eluted with 8N HNO₃ containing fresh NaNO₂ to keep the Pu⁴⁺ state for uranium decontaination. The system of the column is changed from 8N HNO₃ to concentrated HCl with 50 ml concentrated HCl containing a few milligrams of NaNO₂. Furtheer decontaimination of torium was achieved by elution with concentrated HCl instead of 9N HCl. The plutonium is successfully stripped by H₂O, NaOH, 2N HNO₃ and 0.5N HNO₃ containign 0.01M NaNO₃. The chemica yield of plutonium for a 2001 seawate sample is 60–80%. The resolution of the electroplated thin source is very good.     

Analysis of Th, U, Pu, and Am in radioactive metal waste using extraction chromatography

In order to analyze actinide elements in radioactive metal waste, the dissolution and chemical separation conditions were optimized. The surfaces of a type 304 stainless steel plate and of pipe waste sampled from the prototype advanced thermal reactor (Fugen) were dissolved in mixed acid solution (HNO₃:HCl:H₂O = 1:1:4). The resulting solution was evaporated to dryness and dissolved with 2 mol/dm³ of HNO₃ to prepare sample solutions. In order to analyze trivalent actinide elements in the sample solution containing a large amount of Fe(III) (>0.1 g) using TRU resin, the effect of Fe(III) concentration on the recovery of Am(III) and reduction effect of Fe(III) to Fe(II) with ascorbic acid were studied. On the basis of results of this study, chemical separation scheme was constructed and Pu and Am in the sample solutions were separated. Thorium and U in the sample solutions were separated with UTEVA resin. High recoveries for all experimented elements were obtained from the analysis of spiked sample solutions, the effectiveness of the method was confirmed.     

Extraction of molybdenum(VI) by 4-(5-nonyl)pyridine in benzene from aqueous mineral acid solutions containing thiocyanate ions

Extraction of Mo(VI) by 4-(5-nonyl)pyridine (NPy) in benzene from mineral acid solutions containing thiocyanate ions has been investigated at room temperature (23±2°C). From mineral acid (HCl, HNO₃, and H₂SO₄) solutions alone Mo(VI) is not extracted quantitatively while the presence of small amounts of KSCN in the system augments the extraction by a large factor. Stoichiometric studies indicate that ion-pair type complexes (NPyH)₂·[MoO₂(SCN)₄] are responsible for the extraction. Separation factors determined at fixed extraction conditions (0.1M Npy/C₆H₆–0.1M acid +0.2M KSCN) reveal that Ag(I), Cu(II), Co(II), Zn(II), Hg(II) and U(VI) are co-extracted while a clean separation from alkali metals, alkaline earths and some transition metals like Ln(III), Zr(IV), Hf(IV), Cr(III), Cr(VI) and Ir(III) is possible. Some of the complexing anions like oxalate, citrate, acetate, thiosulfate or ascorbate do not affect the degree of extraction of Mo(VI) allowing it to be recovered from diverse matrices.     

Preparation, characterization and application of thorium oxalate for sorption of plutonium and americium from aqueous solution

Synthetic inorganic exchangers exhibit good thermal and radiation stability. Thorium oxalate precipitate shows potential for co-precipitation of plutonium and americium from oxalate supernatant generated during plutonium oxalate precipitation. In the present study, efforts were made to prepare thorium oxalate precipitate to be used for column operation. Distribution ratios were determined to optimize conditions for sorption of plutonium and americium on thorium oxalate from nitric acid + oxalic acid solutions with composition similar to that of oxalate supernatant. Column experiments were also performed to evaluate the sorption capacity of thorium oxalate for plutonium and americium from the same medium. The result showed that, thorium oxalate prepared in 1.75M HNO₃ at 70 °C is suitable for column operations. These studies showed that plutonium and americium could be simultaneously removed from aqueous solutions with composition similar to plutonium oxalate waste using glass column packed with thorium oxalate and these nuclides could be recovered by eluting with 3M HNO₃.     

Use of organophosphorus extractants impregnated on silica gel for the extraction chromatographic separation of minor actinides from high level waste solutions

Silica-gel has been used as an inert support for the extraction chromatographic separation of actinides and lanthanides from HNO₃ and synthetic high level waste (HLW) solutions. Silica-gel was impregnated with tri-butyl phosphate (TBP), to yield STBP; 2-ethylhexyl phosphonic acid, mono 2-ethylhexyl ester (KSM-17, equivalent to PC-88A), SKSM; octyl(phenyl)-N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO), SCMPO; and trialkylphosphine oxide (Cyanex-923), SCYN and sorption of Pu(IV), Am(III) and Eu(III) from HNO₃ solutions was studied batchwise. Several parameters, like time of equilibration, HNO₃ and Pu(IV) concentrations were varied. The uptake of Pu(IV) from 3.0M HNO₃ followed the order SCMPO>SCYN>SKSM>STBP. With increasing HNO₃ concentration, D _Pu increased up to 3.0M of HNO₃ for STBP, SKSM and SCMPO and then decreased. In the case of Am and Eu with SCMPO, the D values initially increased between 0.5 to 1.0M of HNO₃, remained constant up to 5.0M and then slightly decreased at 7.5M. Also, the effects of NaNO₃, Nd(III) and U(VI) concentrations on the uptake of Am(III) from HNO₃ solutions were evaluated. With increasing NaNO₃ concentration up to 3.0M, D _Am remained almost constant while it was observed that it decreases drastically by adding Nd(III) or U(VI). The uptake of Pu and Am from synthetic pressurized heavy water reactor high level waste (PHWR-HLW) in presence of high concentrations of uranium and after depleting the uranium content, and finally extraction chromatographic column separation of Pu and Am from U-depleted synthetic PHWR-HLW have been carried out. Using SCMPO, high sorption of Pu, Am and U was obtained from the U-depleted HLW solution. These metal ions were subsequently eluted using various reagents. The sorption results of the metal ions on silica-gel impregnated with several phosphorus based extractants have been compared. The uptake of Am, Pu and rare earths by SCMPO has been compared with those where CMPO was sorbed on Chromosorb-102, Amberchrom CG-71 and styrene divinylbenzene copolymer immobilized in porous silica particles.