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>     

Sorption and desorption of UO2 2+, Th4+ and Ru3+ on the synthetic analogue of muscovite</p> </p>

Summary Sorption and desorption of UO₂²⁺, Th⁴⁺ and Ru³⁺ on the synthetic analogue of the mica mineral muscovite has been studied by a batch technique. The synthesized gel was characterized by XRD, EDXRFS, FTIR, TGA and SEM and was found to have a composition K_1.4Al_4.2(Si₆Al₂O₂₀)(OH)₄ ^. 2H₂O. Different parameters like acid concentration, contact time, amount of gel, composition of gel: OPC admixture, effect of temperature, desorption of metal ions from loaded muscovite and effect on crystal morphology due to loading of metal ions were studied. The results has been expressed in terms of distribution coefficient (K_d).</p> </p>     

Cs and Sr removal from solution using potassium nickel hexacyanoferrate impregnated zeolites</p> </p>

Summary Potassium nickel hexacyanoferrate, KNiFC, was incorporated in the porous matrix of zeolites by successive impregnation with Ni(NO₃)₂ and</o:p></p> K₄Fe (CN)₆.¹ CFC and PFC exchangers were first prepared by impregnating the potassium nickel hexacyanoferrate into the clinoptilolite and the synthetic P zeolite, respectively. Ion-exchange isotherms and breakthrough curves were plotted. Results showed that the CFC sorbent is suitable for removal of Cs⁺ where PFC is more suitable for Sr²⁺. Negative effect of Na⁺ as a competing ion in these exchangers was less than in the parent zeolites. Isotherm plots fitted the Langmuir equation.</p> </p>     

Radiation effects on gaseous iodine at very low concentrations</p> </p>

Summary Exploratory experiments have been carried out to investigate the effects of gamma-radiation on iodine aerosols under various chemical conditions. The results indicate that iodide ions (I^-) in aerosol can be readily oxidized to I₂ and HIO, and some iodide ions may be converted to organic iodine when organic additives are present in the KI solution from which the aerosol is generated. The results also suggest that the chemical transformation of irradiated iodine aerosol depends on the chemical environment both carrier gas and iodide solution.</p> </p>     

Preconcentration of 198Au in a green alga, Rhizoclonium</p> </p>

Summary The bioaccumulation of ¹⁹⁸Au radionuclide, by Rhizoclonium riparium a member of Chlorophyceae has been studied. It has been observed that accumulation of gold on Rhizoclonium is almost pH independent and slightly higher at basic pH. Accumulation of gold was studied with ¹⁹⁸Au radiotracer, 0.1, 1 and 5 ppm concentrations of gold. It has been concluded from the biochemical analysis that the gold accumulation is due to adsorption in the cellulose and not in protein, fat and carbohydrate. Accumulated gold was recovered when washed with conc. HNO₃.</p> </p>     

Recovery of technetium adsorbed on charcoal</p> </p>

Two methods capable of near complete recovery of technetium adsorbed on charcoal are presented. The first involves liquid extraction of the technetium from the charcoal by hot 4M nitric acid. An average recovery of 98% (n=3) is obtained after three rounds of extraction. The second method involves dry ashing with air in a quartz combustion tube at 400-450 °C. This method yields an average recovery of 96% (n=5). Other thermal methods were attempted, but resulted in reduced recovery and incomplete material balance.</p> </p>     

Sorption of Co, Cs, Sr and I onto argillaceous rock as studied by radiotracers</p> </p>

Summary Sorption of⁶⁰Co,⁸⁵Sr, 137Cs and¹²⁵I have been studied on samples originated from Boda (siltstone-) claystone formation (BCF) (Hungary). The distribution of K_dvalues have been determined in static batch experiments using natural groundwater. The order of sorption of isotopes was Co>Cs>Sr>I, where iodine exhibits sorption properties in a modest extent. The sorption isotherm was determined for Cs from measurements carried out in 10^-5-10^-1M initial concentration range. The isotherm can be described with non-linear Freundlich approximation in the range of</o:p></p> 10^-7-10^-4M equilibrium concentration. At concentrations >10^-2M the isotherm achieves saturation. Hence, it is suggested that sorption of Cs on BCF is dominated by cation-exchange reactions on the illite mineral component. In the case of Co and Sr, precipitation reactions occurred during the experiments performed with carrier-containing solutions. This can be attributed to the low values of solubility product constants of SrCO₃, SrSO₄and Co(OH)₂, formed from anions present in the natural groundwater.</p> </p>     

Mathematical modeling of separation of microamounts of strontium from yttrium in water - HCl -nitrobenzene - 15-crown-5 - hydrogen a dicarbollylcobaltate extraction system</p> </p>

Summary A rapid separation of microamounts of Sr²⁺ from Y³⁺ using HCl, 15-crown-5 (15C5) and hydrogen dicarbollylcobaltate (H⁺B^-) in the two-phase water - nitrobenzene extraction system was developed. The reached separation factor a(Sr/Y) was approximately 10. ^5.4</p> __</p>     

Preparation and characterization of uranyl complexes with phosphonate ligands

The preparation, spectroscopic characterization and thermal stability of neutral complexes of uranyl ion, UO₂ ²⁺, with phosphonate ligands, such as diphenylphosphonic acid (DPhP), diphenyl phosphate (DPhPO) and phenylphosphonic acid (PhP) are described. The complexes were prepared by a reaction of hydrated uranyl nitrate with appropriate ligands in methanolic solution. The ligands studied and their uranyl complexes were characterized using thermogravimetric and elemental analyses, ESI-MS, IR and UV–Vis absorption and luminescence spectroscopy as well as luminescence lifetime measurements. Compositions of the products obtained dependent on the ligands used: DPhP and DPhPO form UO₂L₂ type of complexes, whereas PhP forms UO₂L complex. Based on TG and DTG curves a thermal stability of the complexes was determined. The complexes UO₂PhP·2H₂O and UO₂(DPhPO)₂ undergo one-step decomposition, while UO₂PhP · 2H₂O is decomposed in a two-step process. The thermal stability of anhydrous uranyl complexes increases in the series: DPhPO < PhP < DPhP. Obtained IR spectra indicate bonding of P–OH groups with uranyl ion. The main fluorescence emission bands and the lifetimes of these complexes were determined. The complex of DPhP shows a green uranyl luminescence, while the uranyl emission of the UO₂PhP and UO₂(DPhPO)₂ complexes is considerably weaker.     

Selective separation of uranium using trimethylammonium acetosalycoylhydrazone modified Duolite C20 resin</p> </p>

Summary Duolite C20 resin modified with trimethylammonium acetosalycoylhydrazone has been developed, for the selective separation and/or preconcentration of uranium. The modified resin was characterized by elemental analysis and infrared spectra. Batch and column modes were applied. The newly designed resin quantitatively sorbs uranium ion at pH 3 when the flow rate equals to 2 ml ^. min ^-1 . The sorption capacity was 0.750 mmol ^. g^-1 for uranium ion, whereas its preconcentration factor was 200. The lower limit of detection was 5 ng ^. ml^-1 and its desorption was effective with 5 ml of 3 mol ^. l^-1 HCl or HNO₃ prior to detection spectrophotometry. The modified resin was highly ion-selective in nature even in the presence of large concentrations of electrolyte or organic media, with a preconcentrating ability for uranium ion. The modified resin was tested on its utility with synthetic, real and certified ore samples, showed RSD values of <2% reflecting the accuracy and reproducibility of the newly modified resin.</p> </p>     

Thermodynamic modeling for the removal of Cs+, Sr2+, Ca2+and Mg2+ions from aqueous waste solutions using zeolite A</p> </p>

Summary The batch removal ofCs⁺, Sr²⁺, Ca²⁺and Mg²⁺ions from aqueous solutions using synthetic zeolite A was investigated. The influence of the initial ion concentration, pH and temperature was studied. The obtained isotherm data have been correlated with Langumir, Freundlich, and Dubinin-Radushkevich(D-R) isotherm models. The effect of the temperature on the equilibrium distribution values has been utilized to evaluate the standard thermodynamic parameters such as free energy (DG), enthalpy (DH) and entropy (DS). Based on the D-R isotherm expression, the maximum ion-exchange capacity and the mean free energy of each studied ion has been determined. The selectivity sequence, deduced from the equilibrium isotherm data is: Sr²⁺>Ca²⁺>Mg²⁺>Cs⁺>Na⁺.</p> </p>     

UO<Subscript>2</Subscript>(VI), Sn(IV), Th(IV) and Li(I) complexes of 4-azomalononitrile antipyrine

UO₂(VI), Sn(IV), Th(IV) and Li(I) complexes of 4-azomalononitrile antipyrine (L) have been isolated and characterized based on IR spectra, ¹H NMR, elemental analyses, molar conductance and thermal analysis (DTA/TG). The study revealed that the ligand behaves as a neutral bidentate one and coordination takes place via the carbonyl atom of pyrazolone ring >C=O and the azomethine nitrogen >C=N. The thermal stability of the metal complexes were investigated by thermogravimetry (TG), differential thermal analysis (DTA) techniques and infrared spectra, and correlated to their structure. The thermal study revealed that Th(IV) complexes show lower thermal stability than both UO₂(VI) and Sn(IV) complexes.     

Extraction chromatography of thorium ion by solid phase impregnated resins containing bi-functional organic extractants</p> </p>

Summary Macroporous methyl methacrylate polymeric resin (XAD-7) was investigated incorporating both acidic organophosphorous extractant (cyanex-301) and one neutral extractant from the followings: dibenzo 18 crown 6 (DB18C6), 18 crown 6 (18C6) and 15 crown 5 (15C5). The sorption behavior of the solvent impregnated resin (SIR) towards thorium ion, including batch equilibrium, and kinetic operation are described. Different factors affecting the uptake of metal ions and hence, the separation efficiency of the impregnated resins were investigated. The maximum uptakes of Th⁴⁺ were found to be 62.9, 66.7 and 92.6% for DB18C6, 18C6 and 15C5, respectively. Synergistic extraction of various CE towards thorium ion was tested with cyanex-301 to enhance the sorption capacity as well as the selective separation efficiency. A relatively high capacity of the chelating resin towards tetravalent thorium was found. The capacities of the co-impregnated resins were found to be 2.11, 2.42 and 3.85 mmol/g for DB18C6, 18C6 and 15C5, respectively. The impregnated resin containing cyanex-301 and 15C5 can be utilized for selective separation and pre-concentration of thorium ion from nitrate medium in the presence of several interfering metal ions.</p> </p>     

Synthesis and structure of [UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>){CONH<Subscript>2</Subscript>N(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

The single crystals of [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 7.461(2) Å, b = 8.828(2) Å, c = 11.756(2) Å, β = 107.21(3)°, space group Pc, Z = 2, R = 2.94%. The structure comprises infinite chains [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] extended along [001] and corresponding to the AT¹¹M ₂ ¹ crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = C₂O ₄ ^2? , M¹ = N,N-CONH₂N(CH₃)₂) of uranyl complexes. The chains are connected into a three-dimensional framework by hydrogen bonds involving the oxygen atoms of oxalate and uranyl ions and the N,N-dimethylcarbamide methyl groups.     

Inorganic ion-exchangers in radioactive waste management</p> </p>

Summary The uptake of indigenously synthesized amorphous stannic and zirconium phosphate was assessed for, one of the important fission fragment, cesium from aqueous solutions using a radiotracer technique. A virtual increase in sorptive concentration (from 1.0 ^. 10^-8 to 1.0 ^. 10^-2 mol ^. dm^-3) and pH (from 2.4 to 10.2) and temperature (from 303 to 333 K) enhanced the uptake of cesium on stannic phosphate. However, the extremely high degree of uptake of cesium on zirconium phosphate was almost unaffected with the dilution beyond 10^-5 mol ^. dm^-3 and pH (i.e., from 2.4 to 10.2) and temperature (from 303 to 323 K). Irreversible uptake occurring for these solids follow the Freundlich adsorption isotherm and the presence of several complexing agents viz., sulphate, phosphate, glycine and EDTA did not affect appreciably the uptake of cesium on zirconium phosphate but it did affect for stannic phosphate system. Both these solids showed good radiation stability towards a 11.1 GBq Ra-Be neutron source having neutron flux ca. 3.2 ^. 10⁶ n ^. cm^{-2 .} s^-1 and associated with a nominalg-dose of ca. 1.72 Gy/h, at least for the uptake of cesium.</p> </p>     

Synthesis and crystal structure of (NH<Subscript>4</Subscript>)(CN<Subscript>3</Subscript>H<Subscript>6</Subscript>)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of (NH₄)(CN₃H₆)[UO₂(SeO₃)₂] (I) are synthesized and studied by X-ray diffraction analysis. The compound crystallizes in the triclinic crystal system with the unit cell parameters: a = 7.0051(2) Å, b = 9.4234(3) Å, c = 9.5408(3) Å, α = 88.727(1)°, β = 70.565(1)°, γ= 77.034(1)°, space group P ₁, Z = 2, R = 0.0224. The main structural units of crystals I are the [UO₂(SeO₃)₂]^2? chains of the crystal-chemical group AB²B₁₁ (A = UO ₂ ²⁺ , B₂= SeO₃ ^2?, B₁₁= SeO₃ ^2?) of the uranyl complexes. The uranium-containing complexes are joined into a three-dimensional framework by the ammonium and guanidinium ions and a system of hydrogen bonds.     

Removal of radium from sand filters by inorganic acids</p> </p>

Summary Sand filters are used in water treatment stations to remove particulate matter from underground water, where iron and manganese are collected forming thin oxide films. These oxides of iron and manganese adsorb radium from underground water. Radium concentration increases in time on the filters, and consequently the level of radioactivity increases in the station. The removal of adsorbed radium on sand using inorganic acids was studied. Good efficiency of radium removal was obtained by controlling different parameters like temperature, time, pH, addition of competitive cations and anions. It was found that hydrochloric acid is the best for radium removal from sand filters. Maximum removal obtained was about 60% at 5M BaCl₂ and 2M HCl at 50 °C for 180-minute contact time. Kinetic parameters of the removal process were studied and compared with literature data.</p> </p>     

Structure and some properties of [UO<Subscript>2</Subscript>CrO<Subscript>4</Subscript>{CH<Subscript>3</Subscript>CON(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

A new complex [UO₂CrO₄{CH₃CON(CH₃)₂}₂] (I) was studied by thermal analysis, IR spectroscopy, and X-ray crystallography. The crystals are monoclinic: a = 13.8108(11) Å, b = 8.6804(7) Å, c = 13.0989(10) Å, β = 104.777(1)°, V = 1518.4(2) ų, space group P2₁/c, Z = 4, R = 2.39%. The structure of I contains infinite chains of the [UO₂CrO₄{CH₃CON(CH₃)₂}₂] composition running along [001]; the complex belongs to the AT¹¹M¹ ₂ crystal-chemical group (A = UO ₂ ²⁺ , T¹¹ = CrO ₄ ^2? , M¹ = CH₃CON(CH₃)₂) of uranyl complexes. The chains are linked into a three-dimensional framework due to hydrogen bonds between oxygen atoms of chromate ions and hydrogen atoms of methyl groups of the dimethylacetamide.     

Factors affecting the sorption of Eu(III) on modified silica gel</p> </p>

Summary 8-Hydroxyquinoline in benzene, xylene, chloroform and toluene diluents was used to modify silica gel as a solid phase extractant (SPE) for the sorption of Eu(III) in batch extraction techniques. Influences of solid/liquid ratio, pH, metal ion concentration, particle size and temperature were studied. The optimum initial pH is 4.2, while the maximum sorption capacities for the prepared impregnated resins in benzene, xylene, chloroform and toluene diluents are 18.52, 14.98, 14.79 and 5.94 mg ^. g^-1, respectively. The sorption process is found to be affected by both metal ion concentration and particle size of the impregnated resin. Thermodynamic parameters for the sorption of Eu(III) were determined and the reaction is found to be exothermic and spontaneous with enthalpy-14.23 and-23.71 kJ ^. mol^-1 for benzene and xylene as diluents. Release of the element from the loaded solid particles into 0.01M HNO₃ is@85% and@53% from 8-HQ/benzene/silica gel and 8-HQ/xylene/silica gel.</p> </p>     

Structural and spectroscopy studies of complexes of the uranyl ion with 2,2′-bipyridine-N,N′-dioxide

2,2′-Bipyridine-N,N′-dioxide (bypO₂ = L) complexes of the composition [UO₂(bypO₂)₂(NO₃)₂]·2H₂O (UO₂–L₂–NO₃), [UO₂(bypO₂)₂H₂O](ClO₄)₂ (UO₂–L₂–ClO₄) and [UO₂bypO₂(H₂O)₂SO₄] (UO₂–L–SO₄) have been prepared by the reactions of the respective hydrated uranyl salts with the bypO₂ ligand in water. The structures of the complexes were elucidated using elemental and thermal analyses, IR and luminescence spectroscopy as well as luminescence lifetime measurements. The IR spectra show that the bonding between uranium and bypO₂, as well as uranium and water or a counter ion (NO₃⁻ and SO₄²⁻) is formed. The nitrate or sulfate groups coordinate to the central metal ions in a monodentate manner. From TG–DTA curves, the nature of the water molecules present in the complexes and the decomposition temperature of the dehydrated uranyl complexes were determined. The thermal stability of the anhydrous uranyl complexes increases in the series: (UO₂–L₂–NO₃) < (UO₂–L₂–ClO₄) < (UO₂–L–SO₄). All the compounds show green-yellow intense luminescence. The main fluorescence bands and the emission lifetimes in these complexes were determined. The luminescence spectra of all the prepared complexes differ from each other with respect to their peak maxima positions. The luminescence lifetimes also vary. The structure of the (UO₂–L–SO₄) complex was determined by X-ray single-crystal analysis.