Extraction Of Cations Research Articles

The production and separation of 161Tb with high specific activity at the University of Utah

Targeted radiotherapy (TRT) is an increasingly prominent area of research in nuclear medicine, particularly in the context of treating cancerous tumors. One radionuclide of considerable interest for TRT is terbium-161 (t1/2 = 6.95 days), which undergoes beta emission and shares similar decay properties as 177Lu (FDA-approved as LUTATHERA® and PLUVICTO®). Besides beta emission, 161Tb also emits a significant number of conversion and Auger electrons further enhancing its therapeutic potential. Terbium-161 can be produced using nuclear reactors through an indirect neutron capture reaction, G64160dn,γG64161d→3.66min,β−T65161b, from 160Gd targets. However, a key challenge in utilizing 161Tb for TRT lies in effectively separating target and product materials to attain high specific activity for radiolabeling. Here, we detail the production of no-carrier added 161Tb using low flux research reactors (mean thermal (<0.625 eV) neutron flux: 1.356×1012n∙cm−2∙s−1) like the University of Utah TRIGA Reactor, using enriched 160Gd2O3 targets (1.5 ± 0.3 μCi of 161Tb per mg of 160Gd target per hour of irradiation). We also developed a separation technique based on cation exchange and extraction chromatography, suitable for mCi level irradiations with targets exceeding 200 mg. In a simulated full-scale irradiation, 161Tb was successfully isolated from large mass targets using cation exchange (AG 50W-X8, with 2-hydroxyisobutyric acid at 70 mM, pH 4.75) and extraction chromatography (LN Resin, 0.5–0.75 M HNO3) methods. This resulted in high apparent molar activities of [161Tb]Tb-DOTA (113 ± 3 MBq/nmol), demonstrating high purity 161Tb relevant for potential future preclinical applications.

Synergistic extraction of some divalent cations into nitrobenzene by using dicarbollylcobaltate and substituted calix[5]arenes

Abstract From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibriums Sr2+ (aq) + 2 picrate (aq) + L (nb) ⇔ SrL2+ (nb) + 2 picrate (nb) and M2+ (aq) + SrL2+ (nb) ⇔ ML2+ (nb) + Sr2+ (aq) taking place in the two–phase water–nitrobenzene system (M2+ = Ca2+, Ba2+, Pb2+, Cu2+, Zn2+, Cd2+, Mn2+, Co2+, Ni2+, UO 2 2 + ${\text{UO}}_{2}^{2+}$ ; L = substituted calix[5]arenes; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the ML2+ complexes in nitrobenzene saturated with water were calculated. Very high stability constants of pentaethyl p-tert-butylcalix[5]arene pentaacetate ligand with Ba2+ cation has been found.

Concentration of heavy metal ions from aqueous media under dynamic conditions using a composite sorbent based on chitosan and silica

Objectives. The study set out to investigate the sorption, toxicological, and regeneration properties of a composite sorbent based on chitosan hydrogel and unsuspended silicon dioxide (chitosan–colloidal silica), which manifest themselves under dynamic conditions of purification of aqueous solutions, as a means of removing heavy metal ions.Methods. The total dynamic exchange capacity of a chitosan–colloidal silica composite sorbent was evaluated under dynamic sorption conditions by passing solutions containing Zn(II), Cd(II), Cu(II), and Cr(III) ions having a concentration of 240–251 mg/L through a fixed sorption bed. The method for determining acute toxicity using daphnia (Daphnia magna Straus) is based on the direct calculation of the mortality of daphnia exposed to toxic substances contained in the test aqueous extract in comparison with a reference culture in samples that do not contain toxic substances. The regeneration ability of the sorbent was assessed by counting the number of sorption–desorption cycles using 0.1 M NaOH and 0.1 M NaHCO3 eluents, as well as aqueous solutions of H2O2 (1 and 3%).Results. The effectiveness of the chitosan–colloidal silica composite sorbent in the process of dynamic purification of aqueous media to remove Cu(II), Zn(II), Cd(II), and Cr(III) ions was established. After determining the times of ion breakthrough and saturation of the developed sorbent, its dynamic exchange capacity was calculated by processing the kinetic curves of sorption of heavy metal ions under dynamic conditions. The results of regeneration of the sorbent were presented in the context of the possibility of its reuse. It is shown that the sorbent can withstand up to five sorption–desorption cycles while maintaining a level copper cation extraction above 90%.Conclusions. Analysis of the kinetic curves demonstrated that the driving force behind the removal of heavy metals from aqueous media by means of the obtained sorbent is the external diffusion mass transfer of ions from the mobile phase of the solution. Biotesting of samples showed that the developed chitosan-based sorbent does not have acute toxicity.

Assessment of Ammoniacal Leaching Agents for Metal Cation Extraction from Construction Wastes in Mineral Carbonation.

The use of carbon mineralization to produce carbonates from alkaline industrial wastes is gaining traction as a method to decarbonize the built environment. One of the environmental concerns during this process is the use of acids, which are required to extract Ca2+ or Mg2+ from the alkaline waste to produce carbonates. Conventionally, acids such as hydrochloric, nitric, or sulfuric are used which allow for the highest material recovery but are corrosive and difficult to regenerate as they are utilized in a linear fashion and generate additional process waste. An alternative is to use regenerable protonatable salts of ammonia, such as ammonium chloride (AC) or ammonium sulfate, the former of which is used globally during the Solvay process as a reversible proton shuttle. In this study, we show that regenerable ammonium salts, such as AC (NH4Cl) and ammonium bisulfate (NH4HSO4), can be effectively used for material recovery and the production of calcium carbonate during the leaching of waste cement paste as an alternative to conventional acids such as HCl. Leaching kinetics, postreaction residue, and carbonate characterization were performed to assess the productivity of this system and potential uses of these materials downstream. The stabilization of vaterite was observed in the case of AC leaching, suggesting its importance in the kinetic stability of vaterite and suppression of calcite nucleation. Overall, this study motivates the use of alternative leaching agents, such as salts of ammonia, to facilitate material recovery and carbon capture from alkaline industrial wastes.

EXTRACTION OF CHROME FROM FERROCHROME PRODUCTION SLAG USING THE SULFURIC ACID METHOD

Currently, the development of industrial waste recycling processes that reduce the anthropogenic load on the biosphere and ensure the rational use of natural resources is an urgent task. Technogenic waste from ferrochrome production contains chromium, which is one of the most toxic components of industrial waste. To extract chromium from them, the most acceptable method is acid leaching. The purpose of the work is to study the influence of temperature, process duration and H2SO4 concentration on the extraction of chromium from high-carbon ferrochrome slag into a sulfuric acid solution. Using mathematical planning of a 3-factor experiment, experiments were carried out to extract chromium from the slags of high-carbon ferrochrome production. The H2SO4 concentration was varied from 5 to 95% by diluting the concentrated acid. The duration of the process ranged from 10 to 180 minutes at S:L = 1:30, the temperature varied from 22 to 90 °C. Results and discussion. The maximum transition of chromium into acid occurs at a temperature of 76-90 °C and a process duration of 145-180 minutes. The degree of extraction reaches 97.9%. The smallest amount of chromium, about 20 mg/L, passes into the weakly concentrated H2SO4 solution, the degree of leaching is low and equal to 20.6%. When using 50% H2SO4, the highest degree of transition of Cr (94.8%) from ferrochrome slag to sulfuric acid occurs at a high temperature of 90 °C in 150-180 minutes. Deeper extraction of chromium cations into acid occurs at 80-90 °C. The maximum content of Cr3+ in the acid is achieved in 46-107 minutes and amounts to (0.33-0.68)%. Conclusions. It was revealed that with increasing process duration and increasing temperature, the degree of extraction increases. The maximum transition of chromium into acid from high-carbon ferrochrome slag occurs at a temperature of 76-90 °C and a process duration of 145-180 minutes. The degree of extraction reaches 97.9%. An increase in the temperature of the process of leaching chromium from VUVC with concentrated sulfuric acid initiates the extraction of chromium from the raw material.

Selective Extraction of Lithium Cations from Mixture of Alkali Metal Chlorides Using Electrobaromembrane Process

Selective Extraction of Lithium Cations from Mixture of Alkali Metal Chlorides Using Electrobaromembrane Process

Selective Solid-Liquid Extraction of Lithium Cation Using Tripodal Sulfate-Binding Receptors Driven by Electrostatic Interactions.

Owing to the important role of and increasing demand for lithium resources, lithium extraction is crucial. The use of molecular extractants is a promising strategy for selective lithium recovery, in which the interaction between lithium and the designed extractant can be manipulated at the molecular level. Herein, we demonstrate that anion receptors of tripodal hexaureas can selectively extract Li2SO4 solids into water containing DMSO (0.8% water) compared to other alkali metal sulfates. The hexaurea receptor with terminal hexyl chains displays the best Li+ extraction selectivity at 2-fold over Na+ and 12.5-fold over K+. The driving force underpinning selective lithium extraction is due to the combined interactions of Li+-SO42- electrostatics and the ion-dipole interaction of the lithium-receptor (carbonyl groups and N atoms); the latter was found to be cation size dependent, as supported by computational calculations. This work indicates that anion binding receptors could drive selective cation extraction, thus providing new insights into the design of receptors for ion recognition and separation.

Cation exchange parameters for Opalinus Clay and its confining units

The knowledge of cation exchange parameters is important to understand and model the porewater chemistry in clayrocks. The Opalinus Clay (OPA) is a well-studied formation in view of its importance as host rock for radioactive waste repositories, but uncertainties exist regarding its cation exchange parameters, in particular its selectivity coefficients (Kc). In fact, porewater chemistry models for OPA have so far been based on generic selectivity coefficients.Thanks to a recent extensive siting programme, involving eight vertical deep boreholes in northern Switzerland, a large number of porewater and cation exchange data from the OPA and its clay-rich confining units could be analysed. Thus, from the combination of porewater compositions (obtained from high-pressure squeezing and advective displacement), and exchangeable cation data (obtained from Ni ethylenediamine extraction), reliable selectivity coefficients could be derived. The values for KcNa/K, KcNa/Ca, KcNa/Mg are consistent with those obtained in parallel from the Mont Terri underground rock laboratory although the scatter is somewhat larger in the latter dataset. The derived selectivity coefficients indicate no dependency on ionic strength or in-situ temperature. Minor differences in Kc values between OPA and confining units can be attributed to differences in clay mineralogy. The validity of a two-site cation exchange model including illite and smectite for estimating exchangeable Na, Ca and Mg from measured porewater compositions could be shown, while this simple model underpredicts the share of exchangeable K. The exchangeable cation extraction procedure induces the dissolution of Sr-bearing minerals whose amount is in the same range as exchangeable Sr, thus not enabling the derivation of selectivity coefficients for Sr.Finally, derived selectivity coefficients confirm results of previous studies, thus providing confidence in the applied experimental and modelling protocols on the one hand and in the outcome of those studies on the other hand.

Lead Extraction in a Functionalized and Permeable Silica-Based Porous Liquid.

Silica-based porous liquids (PLs) are innovative and versatile liquid materials with a high potential, although their application is often restricted to gas sorption. In this work, we propose to evaluate their potential to extract metals. For this goal, we have adapted their synthesis to provide PLs functionalized with thiols that are expected to chelate metallic contaminants, such as lead. As the accessibility of liquids and metals to the PL's porous network is one of the key points for their application, we developed an original small-angle neutron scattering experiment to verify that the PL is permeable to polar liquids. Then, preliminary extraction tests have successfully been carried out, with an extraction of lead cations by complexation on one-third of accessible thiol groups. This work demonstrates that the extraction of metal species by a PL is possible and opens many perspectives for optimization.

Highly effective emulsion liquid membrane based on Triethylamine for extraction of heavy metals: Investigation of extraction, de-extraction, swelling, and osmotic pressure gradient

The aim of this work is to produce a stable W/O primary emulsion which is able to extract a wide variety of heavy metals, namely Cu2+, Zn2+, Pb2+, Ni2+, Co2+ and Hg2+. The appropriate conditions through which a better extraction was obtained are: concentration of Span 80 (4 wt%); concentration of TEA (10 wt%); internal phase (HCl 0.5 M); emulsification time (4 min); Vmemb/Vint (2.08); Vemul/Vext (0.1); pH of the external solution (4.7) and stirring speed (150 rpm). A second recycling of the emulsion resulted in a drop in extraction about 40 %. The morphological study confirmed a good dispersion of internal globules and a good stability of emulsion for up to 60 days. The extraction of metal cations showed very high extraction (> 90 %) with very fast kinetics. However, it has been shown that the type of anion to which the metal cation is bound, only affects the extraction efficiency above 100 mg/L. Results extraction of heavy metals are in good analogy with evolution of the osmotic pressure difference between the internal and external phases, leading to a significant swelling of emulsion, while de-extraction also appears to be in accord with extraction with a slightly slower rate.

Solvent extraction separation of Au(III) from Pd(II), Cu(II), Ni(II) in HCl solution using cationic, neutral and basic extractants

AbstractBACKGROUNDEtching solutions of spent printed circuit boards (PCBs) contain precious metal ions like Au(III) and Pd(II) together with Cu(II). Therefore, it is crucial to recover Au(III) and Pd(II) from these solutions. To investigate the possibility of separating Au(III) from the etching solutions, solvent extraction experiments were conducted using synthetic hydrochloric acid solutions containing Au(III), Pd(II), Cu(II), and Ni(II). The solvent extraction behavior of these four metal ions was investigated by using cationic (Cyanex 301, LIX 63), neutral (Cyanex 923 and TBP), and basic (Alamine 336 and Aliquat 336) extractants in the HCl concentration range from 1 to 9 M.RESULTSTBP and Cyanex 923 were successful in separating Au(III) from other metal ions when the HCl concentration was higher than 7 M. When the concentrations of Au(III) and Pd(II) changed from 0.1 to 5 g L−1, TBP was able to selectively extract Au(III) from 7 M HCl solution, while Cyanex 923 was effective in separating Au(III) from 9 M HCl solution. However, Au(III) and Pd(II) were co‐extracted by Alamine 336 and Aliquat 336 from 1 M HCl solution. Thiourea or a mixture of thiourea and HCl solution effectively stripped Au(III) from the loaded organic phases of TBP, Cyanex 923, and amines.CONCLUSIONSAmong the six kinds of the extractants employed in this work, TBP was recommended as an extractant for the selective extraction of Au(III) from the HCl solutions containing Cu(II), Ni(II) and Pd(II) on the basis of high separation degree. © 2023 Society of Chemical Industry (SCI).

P-317 - A Comparison of Cation Exchange and Extraction Resin Column-based Chromatography Methods for Isolating MURR Produced 161Tb

P-317 - A Comparison of Cation Exchange and Extraction Resin Column-based Chromatography Methods for Isolating MURR Produced 161Tb

Electrodeposited Poly(5-Amino-2-Naphthalenesulfonic Acid-co-o-Aminophenol) as the Electrode Material for Flexible Supercapacitor.

Copolymers of 5-amino-2-naphthalenesulfonic acid (ANS) and o-aminophenol (oAP) are electropolymerized on carbon cloth substrate from aqueous solutions, and the electropolymerization process is investigated using electrochemical quartz-crystal microbalance. The surface of the copolymer (PANS-co-oAP) appears rough and is capable to store charge as the battery-type electrode in 1m H2 SO4 (102.9mAhg-1 at 1Ag-1 ) or in 1m ZnSO4 (79.75mAhg-1 at 1Ag-1 ) aqueous solutions. Compared with PANS and PoAP, the high specific capacity of the PANS-co-oAP is originated from the increased number of electrochemically active sites and increased diffusion rates of ions. Evidence of amino/imino and hydroxyl/carbonyl groups redox processes and cation insertion and extraction are given by ex situ X-ray photoelectron spectroscopy. When used as the electrode material in the flexible solid-state supercapacitors, the specific capacitance is at 37.9Fg-1 which does not significantly alter with the bending angle. The flexible solid-state supercapacitor shows a specific energy of 5.4Whkg-1 and a power density of 250.3Wkg-1 at 0.5Ag-1 , and a high capacitance retention (88.2%) after 3000 cycles at 5Ag-1 is achieved.

Aqueous metal ion leaching processes from high sulfur coal fly ash for carbon mineralization: The importance of pH control on cation extraction, carbonate purity, and silicon Q structure

Aqueous metal ion leaching processes from high sulfur coal fly ash for carbon mineralization: The importance of pH control on cation extraction, carbonate purity, and silicon Q structure

Ion-pairing extraction and their reaction modeling of anionic M-Cl species with cationic NTAamide(C6) extractant and comparison with density functional theory calculations

Solvent extraction is conducted using a total of 20 di-, tri-, and tetravalent metals, revealing high stability constants with Cl− and the N,N,N′,N′,N″,N″-hexahexyl-nitrilotriacetamide (NTAamide(C6)) extractant. The metals used here may behave as anions at high Cl− concentrations, and NTAamide(C6), which contains a tertiary N atom, is protonated under acidic conditions. Most of the metal ions in this study display higher distribution ratios (D(M)) from HCl than those from HNO3, although NO3− hardly forms metal-complexes, and exhibit 1:1 stoichiometries with NTAamide, based on the slopes of acid and metal extraction. The high D(M) may be due to ion-pair extraction based on the combination of cationic extractants and anionic metal-chloride ions. Following the experimental results, the association constants and distribution coefficients of the group 12 elements are calculated via ion-pair extraction modeling using density functional theory calculations, and the simulations of D yield calculated values with the same trend as that of the measured values. In the future, it will be possible to calculate the distribution ratio precisely by considering the size effect in the exosphere of metal and chloride ions and the HSAB rule.

Mechanism of inhibition of the oxygen-evolving complex of photosystem II by lanthanide cations

The process of the interaction of La3+and Tb3+ cations with the Ca-binding site of the oxygen-evolving complex of photosystem II samples depleted of calcium has been studied. The binding of cations to the Ca-binding site is irreversible and the bound cations cannot be washed out or replaced by Ca2+ cation. A feature of lanthanides to bind strongly to the Ca-binding site has been used to investigate if the bound Ln3+ cation has an effect on the high-affinity Mn-binding site of the oxygen-evolving complex. Therefore, in this work, hydroquinone was used for the extraction of manganese cations from the oxygen-evolving complex of the calcium-depleted photosystem II membranes with the Ca-binding site blocked by La3+ or Tb3+ and the activity of the high-affinity site was then examined using exogenous electron donors (Mn2+ + H2O2) and 1,5-di-phenylcarbazide. It was found that lanthanide cation bound to the Ca-binding site can significantly inhibit the oxidation rates of electron donors through the high-affinity Mn-binding site. The mechanism of the observed effect is discussed.

Grafting of Crown Ether and Cryptand Macrocycles on Large Pore Stellate Mesoporous Silica for Sodium Cation Extraction.

Regulation of the sodium cations level in the case of renal failure diseases is a very challenging task for clinicians, and new pollutant extractors based on nanomaterials are emerging as potential treatments. In this work, we report different strategies for the chemical functionalization of biocompatible large pore mesoporous silica, denoted stellate mesoporous silica (STMS), with chelating ligands able to selectively capture sodium. We address efficient methods to covalently graft highly chelating macrocycles onto STMS NPs such as crown ethers (CE) and cryptands (C221) through complementary carbodiimidation reactions. Regarding sodium capture in water, C221 cryptand-grafted STMS showed better capture efficiency than CE-STMS due to higher sodium atom chelation in the cryptand cage (Na+ coverage of 15.5% vs. 3.7%). The sodium selectivity was hence tested with C221 cryptand-grafted STMS in a multi-element aqueous solution (metallic cations with the same concentration) and in a solution mimicking peritoneal dialysis solution. Results obtained indicate that C221 cryptand-grafted STMS are relevant nanomaterials to extract sodium cations in such media and allow us to regulate their levels.

Evaluation of Galvanic and Crevice Corrosion of Watch Case Middle (1.4435 Steel) and Bottom (Panacea® Steel) Assembly Supposed to Be in Prolonged Contact with the Skin

Today, laws protecting the population at the global level aim to minimize the induction risk of allergies to type IV contact dermatitis. In the European population, the prevalence of nickel allergy is at 10%–15% of adult females and 1%–3% of adult males. A total of 30% of nickel-sensitive people in the general population develop hand eczema. This study concerns the possibility of assembling a bottom of nickel-free austenitic steel (Panacea®) in a watch case middle made of a grade of austenitic steels, steel 316L (DIN 1.44359), to avoid the risks of Ni release and to develop a galvanic pile between these two dissimilar materials. Two types of methods were used: direct measurements and prediction techniques (mixed potentials theory). For the degradation of thbottom-middle watch assembly, Nielsen–Tuccillo tests were performed, and Ni release measurements according to EN 1811 completed the study. All direct electrochemical investigations and galvanic current prediction measurements show low current values of 40–400 nA. Measurements of nickel release of Panacea® and 316L reveal small quantities of nickel, much lower than the 0.5 µg/cm2 per week that the European legislation enforces. The nickel-free steel Panacea® in the work hardening conditions 280, 427, and 510 HV0.1s were also studied. The cation extractions reveal the large quantities released from Cr, Mo, Mn, and Fe, so there is a risk of toxicity in contact with the skin.

Specific Ion Effect on the “Water Bridge” Interaction at an Interface: A New Understanding into the Extraction and Separation Selectivity Based upon Competitive Diffusion and Adsorption

Understanding the essence of a specific ion effect on the intermolecular interaction at the near-interface boundary layer during solvent extraction is crucial for developing new approaches to achieve enhanced extraction and separation of various valuable metals from complex aqueous solutions. The present work aims to detect the microscopic effect from competitive diffusion and adsorption of various salt cations in the near-interface boundary layer on their interaction with amphiphilic model molecules, 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (P507), at the air–water interface by using the Langmuir–Blodgett (LB) monolayer technique. It was found that the interaction between cations and P507 molecules through a long-range hydrogen bond “water bridge” confined in the near-interface boundary layer plays a crucial role in determining the difference in the diffusion mass transfer rate of ions with different hydration abilities. Conventional understanding about competitive extraction of various metal cations controlled mainly by their thermodynamic difference in the interaction intensity with the P–O and P═O groups in P507 molecules cannot explain such a kind of specific ion effect on the mass transfer kinetics via ion hydration. Molecular dynamics simulation revealed that the hydration ability of ions is the key factor determining the mass transfer rate and interaction intensity. In the low salt concentration region, the interaction intensity of salt cations with the P–O and P═O groups in P507 molecules is one of the determinants of the competitive adsorption behavior at the interface. However, in a higher salt concentration region, the specific ion salting-out effect via ion hydration becomes significant, causing a decrease in hydration of the target salt cation; therefore, it dominated the diffusion mass transfer rate of ions. This work provides a new insight to understand the kinetic role of competitive diffusion and adsorption of ions in the near-interface boundary layer and their effect on extraction and separation selectivity. It lays the foundation for achieving controllable separation of target metal ions by adjusting the coexisting ion species and their concentrations.

Solvent extraction of Terbium(III) from chloride solution using organophosphorus extractant, its mixture and ionic liquid in the presence of organic acids

Addition of organic acids to dilute hydrochloric acid solution can improve the extraction of rare earth elements by single cationic extractants. However, the correlation between the chemical structure of organic acids and the extraction of REEs as well as the variation in equilibrium pH has not been elucidated. In this study, we investigated the extraction of Tb(III) from dilute HCl solutions containing an organic acid like formic, lactic, fumaric, or maleic acid. As extractants, single Cyanex 272, a mixture of Cyanex 272 and Alamine 336 (Ala336-Cy272), and an ionic liquid (ALi-Cy272) synthesized by Cyanex 272 and Aliquat 336 were used. The speciation of Tb(III) in dilute HCl solutions containing organic acids was analyzed. In extraction of Tb(III), organic acids showed two roles as complexing and buffering agent, which depended on the chemical structure of the acids. There was some difference in the extraction of Tb(III) between single Cyanex 272 and ionic liquid, ALi-Cy272. During extraction with ALi-Cy272, formic and lactic acid negatively affected the extraction of Tb(III). The fact that the chemical structure of organic acids affected the extraction of Tb(III) from dilute HCl solution by the studied extractants can provide important information on the selection of suitable extraction systems.