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1.
J Chromatogr A ; 1634: 461686, 2020 Dec 20.
Article in English | MEDLINE | ID: mdl-33220585

ABSTRACT

This work furthers the development of counter-current chromatography as an industrial separation process method. It was demonstrated that the industrial counter-current chromatography methods, in particular, for the separation groups of rare earth metals, can be implemented in a modified cascade of centrifugal mixer-settler extractors. The retention behavior of rare earth elements (samarium, europium, gadolinium, terbium, dysprosium and yttrium) on the pilot chromatographic unit consisting of 70 serially connected centrifugal mixer-settler extractors was experimentally studied under isocratic elution conditions using the mixture of 30 vol.% CyanexⓇ572 + 10 vol.% tributylphosphate in a hydrocarbon diluent as the stationary phase and aqueous nitric acid as the mobile phase. Theoretical analysis of experimental studies showed an acceptable agreement between the assumptions of the theory and experimental results.


Subject(s)
Countercurrent Distribution , Lanthanoid Series Elements/chemistry , Lanthanoid Series Elements/isolation & purification , Dysprosium/chemistry , Dysprosium/isolation & purification , Europium/chemistry , Europium/isolation & purification , Gadolinium/chemistry , Gadolinium/isolation & purification , Samarium/chemistry , Samarium/isolation & purification , Terbium/chemistry , Terbium/isolation & purification , Yttrium/chemistry , Yttrium/isolation & purification
2.
PLoS One ; 15(7): e0235711, 2020.
Article in English | MEDLINE | ID: mdl-32645091

ABSTRACT

The current knowledge of the half-lives (T1/2) of several radiolanthanides is either affected by a high uncertainty or is still awaiting confirmation. The scientific information deriving from this imprecise T1/2 data has a significant impact on a variety of research fields, e.g., astrophysics, fundamental nuclear sciences, and nuclear energy and safety. The main reason for these shortcomings in the nuclear databases is the limited availability of suitable sample material together with the difficulties in performing accurate activity measurements with low uncertainties. In reaction to the urgent need to improve the current nuclear databases, the long-term project "ERAWAST" (Exotic Radionuclides from Accelerator Waste for Science and Technology) was launched at Paul Scherrer Institute (PSI). In this context, we present a wet radiochemical separation procedure for the extraction and purification of dysprosium (Dy), terbium (Tb), gadolinium (Gd), and samarium (Sm) fractions from highly radioactive tantalum specimens, in order to obtain 154Dy, 157-158Tb, 148,150Gd, and 146Sm samples, needed for T1/2 determination studies. Ion-exchange chromatography was successfully applied for the separation of individual lanthanides. All separations were conducted in aqueous phase. The separation process was monitored via γ-spectrometry using suitable radioactive tracers. Both the purity and the quantification of the desired radiolanthanides were assessed by inductively coupled plasma mass spectrometry. Test experiments revealed that, prior to the Dy, Tb, Gd, and Sm separation, the removal of hafnium, lutetium, and barium from the irradiated tantalum material was necessary to minimize the overall dose rate exposure (in the mSv/h range), as well to obtain pure lanthanide fractions. With the herein proposed separation method, exotic 154Dy, 157-158Tb, 148,150Gd, and 146Sm radionuclides were obtained in sufficient amounts and purity for the preparation of samples for envisaged half-life measurements. During the separation process, fractions containing holmium, europium, and promethium radionuclides were collected and stored for further use.


Subject(s)
Lanthanoid Series Elements/isolation & purification , Radiochemistry/methods , Radioisotopes/chemistry , Chromatography, Ion Exchange , Europium/isolation & purification , Half-Life , Holmium/isolation & purification , Lanthanoid Series Elements/chemistry , Liquid-Liquid Extraction/methods , Mass Spectrometry , Promethium/isolation & purification , Spectrometry, Gamma , Tantalum/chemistry
3.
Environ Sci Pollut Res Int ; 25(19): 18813-18822, 2018 Jul.
Article in English | MEDLINE | ID: mdl-29713978

ABSTRACT

Use of lime to mitigate acid mine drainage is, in general, accompanied by precipitation of iron (Fe) and aluminium (Al) (hydr)oxides which may increase the removal of trace elements from water. This work aimed to evaluate the precipitation of Fe/Al (hydr)oxides to remove rare earth elements (REE) from contaminated water and the stability of precipitates. Two sets of 60-day syntheses were carried out using different Fe/Al/REE molar ratios, for europium (Eu) and holmium (Ho). The pH was periodically adjusted to 9.0, and the stability of the resulting precipitates was evaluated by water-soluble and BCR extractable phases, namely (1) acid soluble, extracted by 0.11 mol L-1 acetic acid; (2) reducible, extracted with 0.5 mol L-1 hydroxylamine hydrochloride; and (3) oxidisable, extracted with 8.8 mol L-1 hydrogen peroxide efficiencies of the water treatments for both Eu and Ho that were higher than 99.9% irrespective to the Fe/Al/REE molar ratios. Water-soluble phases of Eu and Ho were lower than 0.01% of the total contents in the precipitates. Recoveries from precipitates by Bureau Communautaire de Référence (BCR) sequential extractions increased with increasing concentrations of Eu and Ho. Acetic acid extracted higher amounts of REE, but Eu recovery was superior to Ho. Lepidocrocite was formed as Eu concentration increased which decreased its stability in the precipitates.


Subject(s)
Aluminum Oxide/chemistry , Europium/isolation & purification , Ferric Compounds/chemistry , Holmium/isolation & purification , Mining , Water Pollutants, Chemical/isolation & purification , Acids , Calcium Compounds , Iron , Oxidation-Reduction , Oxides , Water Pollutants, Chemical/analysis , Water Purification
4.
Nucl Med Biol ; 58: 8-19, 2018 03.
Article in English | MEDLINE | ID: mdl-29309920

ABSTRACT

INTRODUCTION: Thermal neutron activation of 152Sm [152Sm(n,γ)153Sm] using natural or isotopically enriched (by 152Sm) samarium target is the established route for production of 153Sm used for preparation of 153Sm-EDTMP for pain palliation in cancer patients with disseminated bone metastases. However, some long-lived radionuclidic contaminants of Eu, such as, 154Eu (t½=8.6y) are also produced during the target activation process. This leads to detectable amount of Eu radionuclidic contaminants in patients' skeleton even years after administration with therapeutic doses of 153Sm-EDTMP. Further, the presence of such contaminants in 153Sm raises concerns related to radioactive waste management. The aim of the present study was to develop and demonstrate a viable method for large-scale purification of 153Sm from radionuclidic contaminants of Eu. METHODS: A radiochemical separation procedure adopting electroamalgamation approach has been critically evaluated. The influence of different experimental parameters for the quantitative removal radionuclidic contaminants of Eu from 153Sm was investigated and optimized. The effectiveness of the method was demonstrated by purification of ~37 GBq of 153Sm in several batches. As a proof of concept, 153Sm-EDTMP was administered in normal Wistar rats and ex vivo γ-spectrometry of bone samples were carried out. RESULTS: After carrying out the electrolysis under the optimized conditions, the radionuclidic contaminants of Eu could not be detected in purified 153Sm solution by γ-spectrometry. The overall yield of 153Sm obtained after the purification process was >85%. The reliability of this approach was amply demonstrated in several batches, wherein the performance remained consistent. Ex vivo γ-spectrometry of bone samples of Wistar rats administered with 153Sm-EDTMP (prepared using electrochemically purified 153Sm) did not show photo peaks corresponding to radionuclidic contaminants of Eu. CONCLUSIONS: A viable electrochemical strategy for the large-scale purification of 153Sm from radionuclidic contaminants of Eu has been successfully developed and demonstrated.


Subject(s)
Bone Neoplasms/secondary , Cancer Pain/radiotherapy , Europium/isolation & purification , Palliative Care , Radioisotopes/chemistry , Radioisotopes/isolation & purification , Radioisotopes/therapeutic use , Samarium/chemistry , Samarium/therapeutic use , Animals , Bone Neoplasms/complications , Cancer Pain/complications , Electrochemistry , Europium/chemistry , Feasibility Studies , Organophosphonates/chemistry , Radiochemistry , Radioisotopes/pharmacokinetics , Rats , Rats, Wistar , Samarium/pharmacokinetics
5.
Waste Manag ; 60: 765-774, 2017 Feb.
Article in English | MEDLINE | ID: mdl-27810122

ABSTRACT

Rare earth elements are key raw materials in high-technology industries. Mining activities and manufacturing processes of such industries have caused considerable environmental impacts, such as soil erosion, vegetation destruction, and various forms of pollution. Sustaining the long-term supply of rare earth elements is difficult because of the global shortage of rare earth resources. The diminishing supply of rare earth elements has attracted considerable concern because many industrialized countries regarded such elements as important strategic resources for economic growth. This study aims to explore the carbon footprints of yttrium and europium recovery techniques from phosphor. Two extraction recovery methods, namely, acid extraction and solvent extraction, were selected for the analysis and comparison of carbon footprints. The two following functional units were used: (1) the same phosphor amounts for specific Y and Eu recovery concentrations, and (2) the same phosphor amounts for extraction. For acid extraction method, two acidic solutions (H2SO4 and HCl) were used at two different temperatures (60 and 90°C). For solvent extraction method, acid leaching was performed followed by ionic liquid extraction. Carbon footprints from acid and solvent extraction methods were estimated to be 10.1 and 10.6kgCO2eq, respectively. Comparison of the carbon emissions of the two extraction methods shows that the solvent extraction method has significantly higher extraction efficiency, even though acid extraction method has a lower carbon footprint. These results may be used to develop strategies for life cycle management of rare earth resources to realize sustainable usage.


Subject(s)
Carbon Footprint , Europium/isolation & purification , Recycling/methods , Yttrium/isolation & purification , Chemical Fractionation/methods , Solvents/chemistry
6.
J Chromatogr A ; 1416: 57-63, 2015 Oct 16.
Article in English | MEDLINE | ID: mdl-26375205

ABSTRACT

The importance of rare earth elements in modern technological industry grows, and as a result the interest for developing separation processes increases. This work is a part of developing chromatography as a rare earth element processing method. Process optimization is an important step in process development, and there are several competing objectives that need to be considered in a chromatographic separation process. Most studies are limited to evaluating the two competing objectives productivity and yield, and studies of scenarios with tri-objective optimizations are scarce. Tri-objective optimizations are much needed when evaluating the chromatographic separation of rare earth elements due to the importance of product pool concentration along with productivity and yield as process objectives. In this work, a multi-objective optimization strategy considering productivity, yield and pool concentration is proposed. This was carried out in the frame of a model based optimization study on a batch chromatography separation of the rare earth elements samarium, europium and gadolinium. The findings from the multi-objective optimization were used to provide with a general strategy for achieving desirable operation points, resulting in a productivity ranging between 0.61 and 0.75 kgEu/mcolumn(3), h(-1) and a pool concentration between 0.52 and 0.79 kgEu/m(3), while maintaining a purity above 99% and never falling below an 80% yield for the main target component europium.


Subject(s)
Chromatography, High Pressure Liquid/standards , Europium/isolation & purification , Gadolinium/isolation & purification , Samarium/isolation & purification , Mass Spectrometry
7.
Environ Sci Technol ; 49(10): 6117-26, 2015 May 19.
Article in English | MEDLINE | ID: mdl-25895010

ABSTRACT

In this study, nanocomposite of graphene oxide and silane modified magnetic nanoparticles (silane@Fe3O4) were synthesized in a form of dendritic structure. For this, silane@Fe3O4 nanoparticle gets sandwiched between two layers of graphene oxide by chemical synthesis route. The synthesized dendritic structure was used as a monomer for synthesis of europium ion imprinted polymer. The synthesis of imprinted polymer was contemplated onto the surface of the vinyl group modified silica fiber by activated generated free radical atom-transfer radical polymerization, that is, AGET-ATRP technique. The synthesized dendritic monomer was characterized by XRD, FT-IR, VSM, FE-SEM, and TEM analyses. The imprinted polymer modified silica fiber was first validated in the aqueous and blood samples for successful extraction and detection of europium ion with limit of detection = 0.050 pg mL(-1) (signal/noise = 3). The imprinted polymer modified silica fiber was also used for preconcentration and separation of europium metal ion from various soil samples of coal mine areas. However, the same silica fiber was also used for wastewater treatment and shows 100% performance for europium removal. The findings herein suggested that dendritic nanocomposite could be potentially used as a highly effective material for the enrichment and preconcentration of europium or other trivalent lanthanides/actinides in nuclear waste management.


Subject(s)
Europium/isolation & purification , Magnetite Nanoparticles/chemistry , Soil/chemistry , Wastewater/chemistry , Coal/analysis , Europium/chemistry , Limit of Detection , Nanocomposites/chemistry , Silanes
8.
Dalton Trans ; 44(13): 6193-201, 2015 Apr 07.
Article in English | MEDLINE | ID: mdl-25736729

ABSTRACT

Mutual separation of trivalent actinide (An(3+)) and lanthanide (Ln(3+)) using several soft (N) donor ligands (bis(5,6-dialkyl-1,2,4-triazinyl)pyridine (R-BTP)) is attempted for the first time in room temperature ionic liquid (RTIL) medium. The results indicate a spectacular enhancement in the selectivity as compared to that in molecular diluents with a separation factor (S.F.) of >3000 for Am(3+) over Eu(3+) using the methyl derivative (Me-BTP) in RTIL medium using [C(n)mim]·[NTf2] as the diluents (where n = 2, 3, 4, 6 or 8). Such a high S.F. value has never been reported before with any of the R-BTP derivatives in molecular diluents. An opposite trend in the distribution ratio values of both Am(3+) and Eu(3+) with the increasing size of the alkyl (R) group is observed in RTIL medium when compared with that in molecular diluents. The differences in the extraction behaviour of R-BTPs in RTILs vis-à-vis molecular diluents are explained on the basis of the difference in the nature of complexes extracted in these two distinctly different media as supported by the time resolved fluorescence (TRFS) study. An unusually high extractability and selectivity for Am(3+) over Eu(3+) with Me-BTP was attributed to the formation of a 1 : 4 complex for Am(3+), which was never reported earlier with any of the R-BTP derivatives in molecular diluents. DFT studies indicated higher metal 'd' and 'f' orbital participation (covalence) in the bonding with R-BTP in the case of Am(3+) complexes as compared to that in the case of Eu(3+) complexes, which resulted in the selectivity of these classes of ligands. The observed results may have a great significance in the radioactive waste management involving the partitioning and transmutation strategy.


Subject(s)
Americium/isolation & purification , Coordination Complexes/chemistry , Europium/isolation & purification , Ionic Liquids/chemistry , Pyridines/chemistry , Solvents/chemistry , Triazines/chemistry , Americium/chemistry , Chemical Fractionation , Europium/chemistry , Ligands , Models, Molecular , Models, Theoretical , Molecular Structure
9.
J Chromatogr A ; 1348: 47-51, 2014 Jun 27.
Article in English | MEDLINE | ID: mdl-24835593

ABSTRACT

Separating individual rare earth elements from a complex mixture with several elements is difficult and this is emphasized for the middle elements: Samarium, Europium and Gadolinium. In this study we have accomplished an overloaded one-step separation of these rare earth elements through preparative ion-exchange high-performance liquid chromatography with an bis (2-ethylhexyl) phosphoric acid impregnated column and nitric acid as eluent. An inductively coupled plasma mass spectrometry unit was used for post column element detection. The main focus was to optimize the productivity rate, subject to a yield requirement of 80% and a purity requirement of 99% for each element, by varying the flow rate and batch load size. The optimal productivity rate in this study was 1.32kgSamarium/(hmcolumn(3)), 0.38kgEuropium/(hmcolumn(3)) and 0.81kgGadolinium/(hmcolumn(3)).


Subject(s)
Chromatography, High Pressure Liquid , Metals, Rare Earth/isolation & purification , Solid Phase Extraction , Europium/isolation & purification , Gadolinium/isolation & purification , Samarium/isolation & purification
10.
Environ Sci Technol ; 48(12): 6874-81, 2014 Jun 17.
Article in English | MEDLINE | ID: mdl-24842652

ABSTRACT

Efficient capture of highly toxic radionuclides with long half-lives such as Americium-241 is crucial to prevent radionuclides from diffusing into the biosphere. To reach this purpose, three different types of mesoporous silicas functionalized with phosphonic acid ligands (SBA-POH, MCM-POH, and BPMO-POH) were synthesized via a facile procedure. The structure, surface chemistry, and micromorphology of the materials were fully characterized by (31)P/(13)C/(29)Si MAS NMR, XPS, and XRD analysis. Efficient adsorption of Am(III) was realized with a fast rate to reach equilibrium (within 10 min). Influences including structural parameters and functionalization degree on the adsorption behavior were investigated. Slope analysis of the equilibrium data suggested that the coordination with Am(III) involved the exchange of three protons. Moreover, extended X-ray absorption fine structure (EXAFS) analysis, in combination with XPS survey, was employed for an in-depth probe into the binding mechanism by using Eu(III) as a simulant due to its similar coordination behavior and benign property. The results showed three phosphonic acid ligands were coordinated to Eu(III) in bidentate fashion, and Eu(P(O)O)3(H2O) species were formed with the Eu-O coordination number of 7. These phosphonic acid-functionalized mesoporous silicas should be promising for the treatment of Am-containing radioactive liquid waste.


Subject(s)
Americium/isolation & purification , Phosphorous Acids/chemistry , Photoelectron Spectroscopy , Silicon Dioxide/chemistry , X-Ray Absorption Spectroscopy , Adsorption , Environment , Europium/isolation & purification , Hydrogen-Ion Concentration , Kinetics , Magnetic Resonance Spectroscopy , Microscopy, Electron, Transmission , Porosity , X-Ray Diffraction
11.
Acta Chim Slov ; 60(3): 695-700, 2013.
Article in English | MEDLINE | ID: mdl-24169726

ABSTRACT

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B-) in the presence of dodecaethylene glycol (DDEG, L) has been investigated. The equilibrium data have been explained assuming that the species HL+, H2L2+, ML3+ and MH-1L2+ (M3+ = Eu3+, Am3+; L = DDEG) are extracted into the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene saturated with water have been determined. It was found that in this nitrobenzene medium, the stability constant of the EuL3+ complex is comparable with that of AmL3+.


Subject(s)
Allyl Compounds/chemistry , Americium/isolation & purification , Cobalt/chemistry , Europium/isolation & purification , Hydrogen/chemistry , Nitrobenzenes/chemistry , Polyethylene Glycols/chemistry
12.
Appl Radiat Isot ; 82: 158-65, 2013 Dec.
Article in English | MEDLINE | ID: mdl-24001618

ABSTRACT

Gadolinium-153 is a low-energy gamma-emitter used in nuclear medicine imaging quality assurance. Produced in nuclear reactors using natural Eu2O3 targets, ¹5³Gd is radiochemically separated from europium isotopes by europium reduction. However, conventional aqueous europium reduction produces hydrogen gas, a flammability hazard in radiological hot cells. We altered the traditional reduction method, using methanol as the process solvent to nearly eliminate hydrogen gas production. This new, non-aqueous reduction process demonstrates greater than 98% europium removal and gadolinium yields of 90%.


Subject(s)
Europium/isolation & purification , Gadolinium/isolation & purification , Radioisotopes/isolation & purification , Equipment Design , Gadolinium/standards , Humans , Methanol , Nuclear Medicine/instrumentation , Nuclear Medicine/methods , Nuclear Medicine/standards , Radioisotopes/standards , Radiopharmaceuticals/isolation & purification , Solvents , Tomography, Emission-Computed, Single-Photon/standards
13.
Talanta ; 115: 342-8, 2013 Oct 15.
Article in English | MEDLINE | ID: mdl-24054601

ABSTRACT

In this work, a congo red modified single wall carbon nanotubes (CR-SWCNTs) coated fused-silica capillary was prepared and used for capillary microextraction (CME) of trace amounts of lanthanum (La), europium (Eu), dysprosium (Dy) and yttrium (Y) in human hair followed by fluorinating assisted electrothermal vaporization-inductively coupled plasma-optical emission spectrometry (FETV-ICP-OES) determination. The adsorption properties and stability of the prepared CR-SWCNTs coated capillary along with the various factors affecting the separation/preconcentration of La, Eu, Dy and Y by CME were investigated in detail. Under the optimized conditions, with a consumption of 2 mL sample solution, a theoretical enrichment factor of 50 and a detection limit (3σ) of 0.12 ng mL(-1) for La, 0.03 ng mL(-1) for Eu, 0.11 ng mL(-1) for Dy and 0.03 ng mL(-1) for Y were obtained, respectively. The preparation reproducibility of the CR-SWCNTs coated capillary was investigated and the relative standard deviations (RSDs) were ranging from 4.1% (Eu) to 4.4% (La) (CLa, Dy=1.4 ng mL(-1); CY, Eu=0.25 ng mL(-1), n=7) in one batch, and from 5.7% (Eu) to 6.1% (Y) (CLa, Dy=1.4 ng mL(-1); CY, Eu=0.25 ng mL(-1), n=5) among different batches. The proposed method was applied to the analysis of real-world human hair sample and the recoveries for the spiked sample were in the range of 93-105%. The method was also applied to the determination of La, Eu, Dy and Y in Certified Reference Material of GBW07601 human hair, and the determined values were in good agreement with the certified values.


Subject(s)
Dysprosium/isolation & purification , Europium/isolation & purification , Hair/chemistry , Lanthanum/isolation & purification , Liquid Phase Microextraction/methods , Spectrophotometry, Atomic/methods , Yttrium/isolation & purification , Capillary Action , Congo Red , Electricity , Halogenation , Hot Temperature , Humans , Nanotubes, Carbon , Silicon Dioxide , Volatilization
14.
Appl Radiat Isot ; 82: 139-44, 2013 Dec.
Article in English | MEDLINE | ID: mdl-23994739

ABSTRACT

For the safety assessment of geological disposal of high-level radioactive waste (HLW), the migration of Eu(III) through compacted bentonite-sand mixtures was measured under expected repository conditions. Under the evaluated conditions, advection and dispersion is the dominant migration mechanism. The role of sorption on the retardation of migration was also evaluated. The hydraulic conductivities of compacted bentonite-sand mixtures were K=2.07×10(-10)-5.23×10(-10)cm/s, The sorption and diffusion of Eu(III) were examined using a flexible wall permeameter for a solute concentration of 2.0×10(-5)mol/l. The effective diffusion coefficients and apparent diffusion coefficients of Eu(III) in compacted bentonite-sand mixtures were in the range of 1.62×10(-12)-4.87×10(-12)m(2)/s, 1.44×10(-14)-9.41×10(-14)m(2)/s, respectively, which has a very important significance to forecast the relationship between migration length of Eu(III) in buffer/backfill material and time and provide a reference for the design of buffer/backfill material for HLW disposal in China.


Subject(s)
Europium/isolation & purification , Hazardous Waste Sites , Radioactive Waste , Waste Management/methods , Bentonite , China , Diffusion , Hydrodynamics , Silicon Dioxide , Waste Management/instrumentation
15.
Dalton Trans ; 41(47): 14416-24, 2012 Dec 21.
Article in English | MEDLINE | ID: mdl-23104258

ABSTRACT

Theoretical studies were carried out on two pairs of americium and europium complexes formed by tetra-N-dentate lipophilic BTBP ligands, neutral [ML(NO(3))(3)] and cationic [ML(2)](3+) where M = Am(III) or Eu(III), and L = 6,6'-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine (C2-BTBP). Molecular structures of the complexes have been optimized at the B3LYP/6-31G(d) level and total energies of the complexes in various media were estimated using single point calculations performed at the B3LYP/6-311G(d,p) and MP2/6-311G(d,p) levels of theory. In the calculations americium and europium ions were treated using pseudo-relativistic Stuttgart-Dresden effective core potentials and the accompanying basis sets. Selectivity in solvent extraction separation of two metal ions is a co-operative function of contributions from all extractable metal complexes, which depend on physico-chemical properties of each individual complex and on its relative amount in the system. Semi-quantitative analysis of BTBP selectivity in the Am/Eu separation process, based on the contributions from the two pairs of Am(III) and Eu(III) complexes, has been carried out. To calculate the energy of Am/Eu separation, a model of the extraction process was used, consisting of complex formation in water and transfer of the formed complex to the organic phase. Under the assumptions discussed in the paper, this simple two-step model results in reliable values of the calculated differences in the energy changes for each pair of the Am/Eu complexes in both steps of the process. The greater thermodynamic stability (in water) of the Am-BTBP complexes, as compared with the analogous Eu species, caused by greater covalency of the Am-N than Eu-N bonds, is most likely the main reason for BTBP selectivity in the separation of the two metal ions. The other potential reason, i.e. differences in lipophilic properties of the analogous complexes of Am and Eu, is less important with regard to this selectivity.


Subject(s)
2,2'-Dipyridyl/chemistry , Americium/isolation & purification , Coordination Complexes/chemistry , Europium/isolation & purification , Americium/chemistry , Chemical Fractionation , Europium/chemistry , Ligands , Models, Molecular , Solvents , Thermodynamics
16.
Environ Sci Technol ; 46(17): 9378-87, 2012 Sep 04.
Article in English | MEDLINE | ID: mdl-22861645

ABSTRACT

The spatial deposition of polystyrene latex colloids (d = 1 µm) at rough mineral and rock surfaces was investigated quantitatively as a function of Eu(III) concentration. Granodiorite samples from Grimsel test site (GTS), Switzerland, were used as collector surfaces for sorption experiments. At a scan area of 300 × 300 µm(2), the surface roughness (rms roughness, Rq) range was 100-2000 nm, including roughness contribution from asperities of several tens of nanometers in height to the sample topography. Although, an increase in both roughness and [Eu(III)] resulted in enhanced colloid deposition on granodiorite surfaces, surface roughness governs colloid deposition mainly at low Eu(III) concentrations (≤5 × 10(-7) M). Highest deposition efficiency on granodiorite has been found at walls of intergranular pores at surface sections with roughness Rq = 500-2000 nm. An about 2 orders of magnitude lower colloid deposition has been observed at granodiorite sections with low surface roughness (Rq < 500 nm), such as large and smooth feldspar or quartz crystal surface sections as well as intragranular pores. The site-specific deposition of colloids at intergranular pores is induced by small scale protrusions (mean height = 0.5 ± 0.3 µm). These protrusions diminish locally the overall DLVO interaction energy at the interface. The protrusions prevent further rolling over the surface by increasing the hydrodynamic drag required for detachment. Moreover, colloid sorption is favored at surface sections with high density of small protrusions (density (D) = 2.6 ± 0.55 µm(-1), asperity diameter (φ) = 0.6 ± 0.2 µm, height (h) = 0.4 ± 0.1 µm) in contrast to surface sections with larger asperities and lower asperity density (D = 1.2 ± 0.6 µm(-1), φ = 1.4 ± 0.4 µm, h = 0.6 ± 0.2 µm). The study elucidates the importance to include surface roughness parameters into predictive colloid-borne contaminant migration calculations.


Subject(s)
Colloids/isolation & purification , Europium/isolation & purification , Geologic Sediments/chemistry , Microspheres , Silicon Dioxide/chemistry , Adsorption , Particle Size , Polystyrenes/isolation & purification , Porosity , Radioisotopes/isolation & purification , Surface Properties , Switzerland
17.
J Chromatogr A ; 1220: 21-5, 2012 Jan 13.
Article in English | MEDLINE | ID: mdl-22189296

ABSTRACT

A model commonly used to describe the separation of biomolecules was used to simulate the harsh environment when eluting neodymium, samarium, europium and gadolinium with a hot acid. After calibration, the model was used to optimise the preparative separation of europium, as this is the most valuable of the four elements. A kinetic dispersive model with a Langmuir mobile phase modulator isotherm was used to describe the process. The equilibration constant, the stoichiometric coefficient and the column capacity for the components were calibrated. The model fitted the experimental observations well. Optimisation was achieved using a differential evolution method. As the two objective functions used in optimising the process, productivity and yield, are competing objectives, the result was not a single set point but a Pareto front.


Subject(s)
Chromatography, Ion Exchange/methods , Europium/isolation & purification , Calibration , Europium/chemistry , Kinetics , Models, Chemical , Reproducibility of Results
18.
J Hazard Mater ; 195: 238-44, 2011 Nov 15.
Article in English | MEDLINE | ID: mdl-21889846

ABSTRACT

Solvent extraction and supported liquid membrane transport studies for the preferential removal of Am(3+) from feeds containing a mixture of Am(3+) and Eu(3+) was carried out using 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (n-Pr-BTP) as the extractant. Diluent plays an important role in these studies. It was observed that the distribution coefficients deteriorate significantly for both Am(3+) and Eu(3+) though the separation factors were affected only marginally. The transport studies were carried out at pH 2.0 in the presence of NaNO(3) to result in the preferential Am(3+) transport with high separation factors. Effect of different experimental parameters, viz. feed composition, stripping agents, diluents of the organic liquid membrane and membrane pore size was studied on the transport and separation behaviour of Am(3+) and Eu(3+). The supported liquid membrane studies indicated about 85% Am(3+) and 6% Eu(3+) transport in 6h using 0.03 M n-Pr-BTP in n-dodecane/1-octanol (7:3) diluent mixture for a feed containing 1M NaNO(3) at pH 2 and a receiver phase containing pH 2 solution as the strippant. Consequently, a permeability coefficient of (1.75 ± 0.21) × 10(-4)cms(-1) was determined for the Am(3+) transport. Stability of the n-Pr-BTP and its SLM was also studied by carrying out the distribution and transport experiment after different time intervals.


Subject(s)
Americium/isolation & purification , Europium/isolation & purification , Liquid-Liquid Extraction , Pyridines/chemistry , Triazines/chemistry , Magnetic Resonance Spectroscopy
19.
J Hazard Mater ; 178(1-3): 771-6, 2010 Jun 15.
Article in English | MEDLINE | ID: mdl-20236759

ABSTRACT

Sodium aluminosilicate has been synthesized by solution route for use as a sorbent for various radionuclides. It was characterized by XRD, zeta potential, BET surface area, FTIR spectroscopy and site density measurement. Sorption studies of (137)Cs, (133)Ba and (154)Eu on synthesized sodium aluminosilicate have been carried out at varying pH (3-10). Sorption of all the metal ions was found to increase with pH of suspension with the saturation value increasing with the oxidation state of metal ion. Effect of Aldrich humic acid (2mg/l) on sorption was also investigated. In case of (137)Cs, the sorption was not affected by the presence of humic acid, while in case of (133)Ba and (154)Eu, sorption was enhanced at lower pH and decreased at higher pH in presence of HA. A series of experiments were carried out for (154)Eu sorption on sodium aluminosilicate at various conditions. Sorption of europium was analyzed by different sorption isotherms, viz., Freundlich and D-R isotherm. Thermodynamic data reveal sorption phenomena as endothermic and spontaneous. Studies were further extended to find out effect of diverse ions (Ca(2+) and CO(3)(2-)) on sorption of europium.


Subject(s)
Aluminum Silicates/chemistry , Barium Radioisotopes/isolation & purification , Cesium Radioisotopes/isolation & purification , Europium/isolation & purification , Adsorption , Humic Substances , Hydrogen-Ion Concentration , Indicators and Reagents , Kinetics , Radioisotopes/isolation & purification , Spectroscopy, Fourier Transform Infrared , Temperature , X-Ray Diffraction
20.
Appl Radiat Isot ; 68(7-8): 1240-6; discussion 1246, 2010.
Article in English | MEDLINE | ID: mdl-20138529

ABSTRACT

A set of 60 spiked simulated air filter sources was developed for the 2004-2005 proficiency test of the Italian radioactivity surveillance network. Each simulated filter source was prepared by reproducible volumetric dispensing of 19 drops of a mixed radioactive solution containing Co-57, Cs-134, Cs-137, Co-60 and Eu-152. The spiking pattern was investigated and optimized by numerical simulations. The filter sources were checked by double counting on HPGe and NaI(Tl) detectors. The standard deviation (SD) of activity values was 1.5%.


Subject(s)
Air Pollutants, Radioactive/isolation & purification , Radiation Monitoring/methods , Spectrometry, Gamma/methods , Air Pollutants, Radioactive/analysis , Cesium/analysis , Cesium/isolation & purification , Cobalt Radioisotopes/analysis , Cobalt Radioisotopes/isolation & purification , Europium/analysis , Europium/isolation & purification , Filtration , Italy , Materials Testing/methods , Membranes, Artificial , Radiation Monitoring/standards , Reproducibility of Results
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