Preconcentration of lanthanides from natural waters with a lipophilic crown ether carboxylic acid

Lipophilic crown ether carboxylic acids such as 2-(sym-dibenzo-16-crown-5-oxy)stearic acid with a cavity size comparable to the ionic radius of rare-earth elements are selective chelation agents for preconcentration and separation of lanthanides from natural waters for NAA. Interfering matrix elements such as sodium and bromine can be simultaneously eliminated during the extraction. The lanthanides can be back-extracted into a dilute acid solution for NAA, thus providing a large preconcentration factor. This two-step extraction method appears suitable for the determination of lanthanides in natural waters and in biological samples.     

Characterization of hot particles in surface soil around the Chernobyl NPP

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

Preconcentration neutron activation analysis of lanthanides by cloud point extraction using PAN

Summary Methods for the simultaneous preconcentration of lanthanides by cloud point extraction and their determination using neutron activation analysis have been developed. The preconcentration method involves the use of a nonionic surfactant and a chelating agent. A fairly small volume of surfactant-rich phase was obtained under optimized experimental conditions, leading to detection limits between 0.3 and 3.0 ng ^. g^-1. Critical parameters that influence extraction efficiency were solution pH and concentration of chelating agent, and to a lesser extent, ionic strength and temperature. Most of the chelates were quantitatively extracted (>90%) at high pH values. Selective separation can be achieved by varying some of the experimental conditions.     

Energy dispersive X-ray fluorescence (EDXRF) determination of lanthanides after preconcentration on 1-(2-pyridylazo)-2-naphthol modified naphthalene

A method is described for the simultaneous multielement determination of yttrium and lanthanides at microgram level. This is based on the preconcentration of these lanthanides on to 1-(2-pyridylazo)-2-naphthol (PAN) modified naphthalene. The optimal conditions for quantitative preconcentration viz., pH, amount of PAN modified naphthalene, time of stirring and aqueous phase volume were systematically evaluated. The quantitation of lanthanides was carried out by energy dispersive X-ray fluorescence analyzer, employing²⁴¹Am annular source, via their characteristic K X-rays. The developed procedure gave reliable results in the analysis of xenotime samples.     

Sorption of microamounts of Ce3+, Pm3+, Eu3+, Gd3+ and Yb3+ on aluminium hydroxide

The sorption of microamounts of trivalent lanthanides (Ln³⁺) on freshly precipitated Al(OH)₃ has been measured in dependence on pH and the time of sorption. Also, the influence of organic complexing ligands and inorganic electrolytes on the sorption process has been investigated. The mechanism of sorption is discussed. Freshly precipitated Al(OH)₃ can be used for the preconcentration of microamounts of trivalent lanthanides. However, the preconcentration is not quantitative in the presence of high concentrations of complexing ligands (citrate and similar) which form strong complexes with Ln³⁺ ions.     

Mixed-ligand chelate extraction of trivalent lanthanides with 4,4,4-trifluoro-1-phenyl-1,3-butanedione and neutral oxo-donors

Mixed-ligand chelate extraction of trivalent lanthanides such as Nd(III), Eu(III) and Lu(III) into benzene with mixtures of 4,4,4-trifluoro-1-phenyl-1,3-butanedione (HBFA) and bis-2-ethylhexyl sulphoxide (B2EHSO) or triphenylphosphine oxide (TPhPO) from thiocyanate solutions was investigated. The results demonstrate that these metal ions are extracted as Ln(BFA)(3) with HBFA alone and in the presence of a neutral oxo-donor, B2EHSO or TPhPO(S), as Ln(BFA)(3).S and Ln(BFA)(3).2S. The equilibrium constants of the above species increase monotonically with decreasing ionic radii of these metals ions. The addition of a neutral donor to the metal chelate system not only enhances the extraction efficiency but also improves the selectivity among these trivalent lanthanides. Hence this mixed-ligand system may be useful for the extraction and separation of individual lanthanides and also for the separation of lanthanides as a group from other metal ions.     

Extraction behavior and separation of lanthanides with a diglycol amic acid derivative and a nitrogen-donor ligand.

The extraction and separation of lanthanides have been investigated using CHON-type extractants, which are composed of only C, H, O, and N atoms. N,N-Dioctyldiglycol amic acid (DODGAA) showed high extraction and separation performances for heavier lanthanides compared with typical CHON-type extractants. On the other hand, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) provided an unprecedentedly high selectivity for lighter lanthanides. Furthermore, it was found that the combination of DODGAA and TPEN under suitable conditions enabled the mutual separation of light, middle, and heavy lanthanides.     

Determination of lanthanides by source excited energy dispersive X-ray fluorescence (EDXRF) method after preconcentration with ammonium pyrrolidine dithiocarbamate (APDC)

A new analytical procedure for determination of lanthanides in environmental samples after chemical separation from major matrix elements on DOWEX 50W-X8 resin followed by preconcentration with chelating agent ammonium pyrrolidine dithiocarbamate (APDC) and analyses of thin targets by energy dispersive X-ray fluorescence (EDXRF) method using ¹⁰⁹Cd as the source of excitation was presented. Characteristic L X-ray lines of the lanthanides were used for calculations of the net peak area and mass concentrations. The influence of pH value of the solution and addition of organic matter on the complexation was investigated. Percentage of recovery of each lanthanide after separation on DOWEX 50W-X8 resin was also determined. Accuracy of the method was tested on standard reference materials and real environmental samples (red mud material). For that purpose samples of standard reference materials and red mud were prepared as thick targets and directly analyzed (without the separation step) by EDXRF method using ²⁴¹Am as the excitation source. In that case lanthanides concentrations were determined over their characteristic K X-ray lines and results were compared with those obtained after separation/preconcentration step described above. Results showed that selected lanthanides made stable complexes with APDC in the alkaline medium with the maximum recovery at pH = 8. The presence of organic matter slightly modified the complexation by means of somewhat higher recovery percentage at pH lower than 7 and approx. 20% lower recovery at pH higher than 7.

Recovery of the elements after separation on DOWEX 50W-X8 resin and preconcentration with APDC at pH = 8 varied from 91.4% (Pr) to only 24.9% in the case of Dy.

Concentrations of lanthanides measured in standard reference material and environmental samples of red mud after microwave digestion, separation on DOWEX 50W-X8 resin, preconcentration with APDC at pH = 8 and recalculation on the percentage of recovery were in good agreement with certified values in the case of SRM as well as with the concentrations obtained by direct determination over K lines using ²⁴¹Am excitation source in the case of red mud leading to the conclusion that presented method was applicable for the determination of lanthanides in real environmental samples.     

Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers

Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.     

Microviscosity of ions and salting-out in the extraction of rare-earth and transplutonium elements

A chemical procedure has been developed for the separation of U, Th, Fe, Sc, Na, Ta and Mo, which interfere in neutron activation analysis of the lanthanide elements in rocks. This methods in based on the extraction of interferents, before irradiation of the samples, using a solution of tetracycline in benzyl alcohol. The lanthanide elements remain in the aqueous phase and are coprecipitated with calcium oxlate or ferric hydroxide for irradiation and subsequent determination by gamma-ray spectrometry. Conditions for the separation of these interferences are examined determining the extraction curves. The chemical separation procedure was applied in the analysis of lanthanides in geological materials and the results showing the accuracy and the reproducibility of the method are presented. The sensitivity for all the lanthanides was determined.     

Extraction of Am(III) in the presence of lanthanides and yttrium by benzyldimethyldodecylammonium nitrate from acidic nitrate solutions

We have investigated the effect of coextraction of lanthanides and yttrium on the distribution coefficients D_Am in the extraction of americium by benzyldimethyldodecylammonium nitrate (BDMLNNO₃) from nitrate solutions. In the coextraction of lanthanides, the extraction of Am(NO₃)₃ is suppressed, which is markedly manifested in the extraction of light lanthanides (La, Ce, Pr); of the series of lanthanides their extraction is the highest. The effect of nitric acid and the possibility of separation of lanthanides and americium by the application of three-stage multiple extraction is discussed.     

Cloud-point preconcentration and HPLC determination of polycyclic aromatic hydrocarbons in marine sediments

Cloud-point methodology has been used to develop a new procedure for preconcentration of polycyclic aromatic hydrocarbons previously extracted from marine sediment with a micellar polyoxyethylene-10-lauryl ether medium by microwave- or ultrasound-assisted extraction. The optimum conditions for preconcentration and determination of PAH by HPLC with UV detection were established. The optimized procedure was applied to determination of these analytes in fortified marine sediment. The mean recoveries obtained after extraction and preconcentration by use of microwave- or ultrasound-assisted extraction were 105.8 and 99.5%, respectively. Precision, however, is considerably higher when extraction is performed ultrasonically.     

The determination of rare earths in yttrium oxide by means of a preconcentration technique and Ge(Li) gamma-spectrometry

Before preconcentration the yttrium matrix is separated from the lanthanides by means of cation- and/or anion-exchange. The rare earth elements are then concentrated by coprecipitation with 5.0 mg of iron as Fe(OH) in quartz centrifuge tubes. The dehydrated Fe-REE mixture is then irradiated and counted, without any further major manipulations, by means of Ge(Li) gamma-spectrometry, the⁵⁹Fe activity acting as a f' x monitor and as an internal standard.     

Extraction behavior of lanthanides using a diglycolamide derivative TODGA in ionic liquids

Liquid-liquid extraction of lanthanides from aqueous solutions into ionic liquids (ILs) has been investigated using N,N,N',N'-tetra(n-octyl)diglycolamide (TODGA) as an extractant, and compared with that in the isooctane system. Application of ILs as the extracting phase provided unprecedented enhancement of the extraction performance of TODGA for lanthanides compared with that of the isooctane system. Slope analysis confirmed that TODGA in ILs formed a 1 : 3 complex with La(3+), Eu(3+), or Lu(3+). On the other hand, the molar ratios of species extracted into isooctane were 1 : 3 for La(3+) or 1 : 4 for Eu(3+) and Lu(3+), depending on the atomic number of the lanthanide. The transfer of lanthanides with TODGA into ILs proceeded via a cation-exchange mechanism, in contrast to ion pair extraction in the isooctane system. Furthermore, we clarified that TODGA provided selectivity for the middle lanthanides in the ILs systems, but heavier lanthanides in the isooctane system.     

Synergic solvent extraction of lanthanides with mixtures of aliphatic fluorinated beta-diketones and organophosphorus donors

The extraction of lanthanides from an aqueous acetatechloride medium into cyclohexane solutions of trifluoroacetylacetone, hexafluoroacetylacctone, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and tri-n-butyl phosphate was studied. The extraction properties of other fluorinated aliphatic beta-diketones and fluoroorganophosphates were also investigated. The efficiency of the extraction of the lanthanides, the composition of the complexes transferred to the organic phase and the extraction and stability constants for the synergic reactions were determined. Synergic extraction, as a technique for the preparation of lanthanide species, was evaluated for compatibility with subsequent gas chromatography. The lanthanides were found to be rapidly and quantitatively transferred into organic phases containing mixtures of fluorinated aliphatic beta-diketones and TBP. The resulting mixed complexes that contained fully fluorinated beta-diketones had a distinct stoichiometry and were thermodynamically more stable dan similar mixed complexes of partially fluorinated beta-diketones. These properties of the synergic systems allow precise control of the formation of anhydrous complexes in the organic phase and are compatible with the use of these systems for gas chromatography.     

Extraction of complexes of lanthanides and actinides with Arsenazo III in an ammonium sulfate-poly(ethylene glycol)-water two-phase system

The distribution of lanthanides and actinides in a two-phase liquid system obtained by mixing an aqueous solution of poly(ethylene glycol) and ammonium sulfate has been studied as a function of pH. Conditions are reported which provide the heterogeneity of the system suggested. It is shown that thorium and plutonium can be separated from transplutonium elements and lanthanides. Conditions have been chosen for quantitative group extraction of actinides and lanthanides.     

On-line sample preconcentration in capillary electrophoresis, focused on the determination of proteins and peptides

This overview highlights the possibilities of on- or in-line preconcentration procedures in combination with a CZE separation, focused on the determination of peptides and proteins. The discussed methods, including sample stacking, field-amplified injection, isotachophoresis, solid phase extraction, membrane preconcentration, electroextraction, supported liquid membranes, hollow fibers, immunoaffinity, and molecularly imprinted polymers technology preconcentration are categorized in electrophoresis-based and chromatography-based preconcentration. The chromatography-based preconcentration is subdivided in low-specificity and high-specificity methods. A number of preconcentration methods are available, however, this paper demonstrates that various compounds in different media (aqueous solutions, urine, and plasma) require different preconcentration systems. The preconcentration techniques of first choice in general seem to be solid-phase extraction and membrane preconcentration, because of their high concentration ability, multiapplicability, relative simplicity and clean-up capability. For the future, hollow fibers seem to hold a great potential as preconcentration technique, yielding high concentration factors, using simple designs. New techniques, such as hollow fibers, molecularly imprinted polymers technology and supported liquid membranes may have the potential to supersede the conventional preconcentration techniques in some cases. The larger the arsenal of preconcentration techniques becomes, the more efficiently peptides and proteins may be analyzed in the future. These techniques, in some cases, require pre-cleanup procedures, to ensure the purity of the samples to concentrate.     

Molecular octopus: octa functionalized calix[4]resorcinarene-hydroxamic acid [C4RAHA] for selective extraction, separation and preconcentration of U(VI)

A solvent extraction separation of uranium, in the presence of thorium, cerium and lanthanides with a new calix[4]resorcinarene bearing eight hydroxamic acid groups (C4RAHA) is described. Quantitative extraction of uranium is possible in ethyl acetate solution of C4RAHA at pH 8.0. The lambda(max) and molar absorptivity (varepsilon) for uranium is 356nm and 8352Lmol(-1)cm(-1). The Binding ratio of uranium with C4RAHA as evaluated by Job's method is 4:1. The system obeys Beer's law over the range 0.075-6.0mugml(-1) of uranium with Sandell sensitivity 0.0284mugcm(-2). A preconcentration factor of 142 was achieved by directly aspirating the extract for GF-AAS measurements. The two-phase stability constant evaluated at 25 degrees C for uranium is 15.91. The complexation is characterized by favorable enthalpy and entropy changes. A liquid membrane transport study of uranium was carried out from source to the receiving phase under controlled conditions and a mechanism of transport is proposed. Uranium has been determined in standard and environmental samples.     

Separation of Am from lanthanides by a synergistic mixture of purified Cyanex 301 and TBP

The dependence of the distribution ratios of ²⁴¹Am and lanthanides between purified Cyanex 301 (HBTMPDTP)–TBP–kerosene/nitrate solution on pH, lanthanide concentration in aqueous phase and degree of saponification of HBTMPDTP was investigated. The distribution ratios of ²⁴¹Am and lanthanides increase with pH and degree of saponification of HBTMPDTP and decrease with lanthanides concentration. Countercurrent multistage extraction consisting of 7 extraction, 3 washing and 2 stripping stages showed that more than 99.99% of ²⁴¹Am and less than 0.04% of lanthanides were extracted. The pH_1/2 value of Am was 2.45 compared to 3.16 in case of HBTMPDTP–kerosene extraction.     

Micelle-mediated extraction and preconcentration of ginsenosides from Chinese herbal medicine

The feasibility of employing micelle-mediated extraction as an alternative and effective method for the solubilization, purification and/or preconcentration of active ingredients from herbal products is demonstrated for the first time using the root of American ginseng as a model. When compared to methanol and water, an aqueous surfactant solution containing 10% Triton X-100 yielded faster kinetics and higher recovery for the extraction of various ginsenosides. An experimental design approach (uniform design) was demonstrated as a novel and useful method for the optimization of experimental factors involved in the micelle-mediated extraction process. For the preconcentration of ginsenosides prior to chromatographic determination, a salting-out agent (sodium sulfate) was employed to make the efficient cloud point extraction of both hydrophobic and hydrophilic ginsenosides into the surfactant-rich phase possible, as well as to increase the preconcentration factor by reducing the volume of the surfactant-rich phase.