Chemical separation of enriched cadmium target from copper backing in cyclotron production of radioisotope 111In

A radiochemical purification procedure was developed for the separation of enriched cadmium (¹¹¹Cd and ¹¹²Cd) from natural copper that used as backing; and was based upon the chromatographic adsorption. The separation of copper from cadmium was studied in this work. The ions were selectively separated from aqueous solution. Ion-exchange chromatography was employed as a column (1.5 cm i.d. and 15 cm length) with AG1-X8 resin (chloride form, 100–200 mesh) and a flow rate of 1–2 ml/min throughout the separation. 6 M HCl media was used for the adsorption of Cd and Cu on the resin. Then, Cu was eluted by 2 M HCl and Cd by 100 ml 0.5 M HNO₃. The amount of Cu and Cd ions in the final solution (0.5 M HNO₃) were measured by pulse polarographic method and the concentration of Cu was found to be <0.1 ppm. The Cd was quantitatively recovered and the recovery yield from ion-exchange chromatography was greater than 96 %.     

Simultaneous production and separation of no-carrier-added 111In, 109Cd from alpha particle induced silver target

A natural silver foil was bombarded by 30 MeV α-particles which produced ¹¹¹In, ¹⁰⁹Cd and ^106mAg in the target matrix. ¹¹¹In and ¹⁰⁹Cd were separated from the Ag target matrix employing ion-exchange chromatography and liquid–liquid extraction (LLX). In the chromatographic separation, the active solution containing the NCA products were adsorbed in the column containing Dowex 50 and were eluted with HNO₃. Bulk silver and ¹⁰⁹Cd were sequentially eluted with 1 M HNO₃. After complete elution of ¹⁰⁹Cd and the bulk, ¹¹¹In was eluted with 1.5 M HNO₃. In the LLX, the NCA ¹¹¹In was extracted to 1 % HDEHP (di-2(ethylhexyl)phosphoric acid) from 10^?2 M HNO₃ solution, leaving cadmium and bulk silver quantitatively in the aqueous phase. The NCA ¹⁰⁹Cd was separated from the bulk Ag by precipitating Ag as AgCl. NCA ¹¹¹In was stripped back quantitatively from HDEHP phase using 8 M HNO₃.     

Separation of the no-carrier-added 109Cd from Ag, Cu and 65Zn by use of a precipitation and AG1-X8 resin

The ¹⁰⁹Cd radionuclide was produced in the cyclotron via ^natAg(p,n)¹⁰⁹Cd reaction. The radiochemical separation of ¹⁰⁹Cd from silver and non-isotopic impurities comprised of two stages. The optimum conditions of the ¹⁰⁹Cd separation methods were: Ag precipitation with 0.015 M HCl and Cu and ⁶⁵Zn by use of 0.015 M HCl on AG1-X8 strong anion-exchange resin. Chemical and radionuclidic purity of ¹⁰⁹Cd were measured by ICP-AES and gamma-ray spectrometry respectively. Recovery yield and radionuclidic purity were obtained 99.7% and 99%, respectively.     

The production of 103Pd and 109Cd from a proton irradiated tandem natAg/natAg targets

This paper describes a new method for the production of ¹⁰³Pd and ¹⁰⁹Cd using the 66 MeV proton beam of iThemba LABS on a tandem natural silver target (Ag/Ag). The radiochemical separation of the Pd radionuclides (¹⁰³Pd, ¹⁰⁰Pd) from the bulk ^natAg was done using a Chelex-100 chelating resin column. The recovery of ¹⁰³Pd from the irradiated ^natAg target was found to be >98 % without any Ag or Rh impurities detected. The radiochemical separation of ¹⁰⁹Cd from the bulk ^natAg target was done by the precipitation of Ag ions by Cu followed by the separation of ¹⁰⁹Cd, traces of Ag, Cu²⁺ and Rh using a AG1-X10 anion exchange resin column. The recovery yield of ¹⁰⁹Cd was >99 % without any Ag or Rh impurities detected.     

Synthesis of maghemite nano-particles and its application as radionuclidic adsorbant to purify <Superscript>109</Superscript>Cd radionuclide

Maghemite nano-particles were synthesized by a solid-state chemical reaction for its highly selective use as, cyclotron-produced, ¹⁰⁹Cd (462.9 days) purification method of choice. ¹⁰⁹Cd radiochemical separation starts with Ag activities precipitated with HCl 0.0015 M followed by, on a second step, ¹⁰⁹Cd separation from Cu carrier and ⁶⁵Zn (243.8 days) using Ca (NO₃)₂ 0.01 M. Experimental parameters such, pH and sorbent concentration, on ¹⁰⁹Cd extraction efficiency were investigated. Phase morphology, nanostructure and size of nano-particles were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). A 10–20 nm average grain size was derived from XRD line broadening and SEM data. Heat treatment on Fe³⁺:Fe²⁺ ratios equal to 2:1, produced powders, resulting in tetragonal (maghemite) structure at 300 °C and rhombohedra (hematite) at 600 °C. ¹⁰⁹Cd chemical and radionuclidic purity were determined by ICP-AES and HPGe detector gamma-ray spectrometry. The overall recovery and radionuclide purity were 80.0% from obtained 129.63 kBq/C MeV (70 kBq/μAh) initial activity and 91.4%, respectively.     

Development of cadmium/silver/palladium separation by ion chromatography with quadrupole inductively coupled plasma mass spectrometry detection for off-line cadmium isotopic measurements

A separation method was investigated to perform off-line cadmium isotopic measurements on a ¹⁰⁹Ag transmutation target. Ion chromatography (IC) with Q ICPMS detection (quadrupole inductively coupled plasma mass spectrometry detection) was chosen to separate cadmium from the isobarically interfering elements, silver and palladium, present in the sample. The optimization of chromatographic conditions was particularly studied. Several anion and cation columns (Dionex AG11^®, CS10^® and CS12^®) were compared with different mobile phases (HNO₃, HCl). The separation procedure was achieved with a carboxylate-functionalized cation exchange CS12 column using 0.5 M HNO₃ as eluent. The developed technique yielded satisfactory results in terms of separation factors (greater than 5) and provides an efficient solution to obtain rapidly purified cadmium fractions (decontamination factors higher 100,000 for silver and palladium) which can directly be analyzed by multi collection inductively coupled plasma mass spectrometry (MC ICPMS). By applying the proposed procedure, accurate and precise cadmium isotope ratios were determined for the irradiated ¹⁰⁹Ag transmutation target.     

Separation of no-carrier-added 109Cd from natural silver target using RTIL 1-butyl-3-methylimidazolium hexafluorophosphate

The room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆] has various applications in the separation of a range of metal ions replacing volatile and toxic traditional organic solvents in liquid–liquid extraction systems. In this study, the RTIL [C₄mim][PF₆] was used to separate no-carrier-added (NCA) ¹⁰⁹Cd from α-particle irradiated Ag target. A natural Ag foil was bombarded by 30 MeV α-particles to produce ¹⁰⁹Cd. After the decay of all co-produced short-lived products, NCA ¹⁰⁹Cd was separated from the bulk Ag using [C₄mim][PF₆] as extractant from HNO₃ medium. Ammoniumpyrrolidine dithiocarbamate (APDC) was used as a complexing agent. At the optimum condition, 3 M HNO₃, 0.01 M APDC in presence of [C₄mim][PF₆], ~99 % bulk Ag was extracted to the IL phase, leaving NCA ¹⁰⁹Cd in the aqueous phase. The amount of Ag became negligibly small after re-extraction in the same condition. The ionic liquid was recovered by washing it with 1 M HCl.     

Ionic liquid-salt based aqueous biphasic system for separation of 109Cd from silver target

Aqueous biphasic system (ABS) is greener alternative to the conventional liquid liquid extraction as ABS does not involve any organic or volatile reagents. Generally ABS systems are composed of polymer and salt rich phases. In this paper a new ABS system is proposed replacing polymer rich phase by water soluble room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium Chloride ([bmim]Cl) and kosmotropic salt K₂HPO₄. The system has been applied to separate the no-carrier-added (NCA) ¹⁰⁹Cd (T _1/2 = 462.6 days) from the α-particle irradiated bulk Ag target. The optimum separation condition was achieved with the addition of 6 M HNO₃ to the ABS, where ~87 % of the bulk Ag was extracted in the IL phase, leaving ~96 % NCA ¹⁰⁹Cd in the salt rich phase. The salt rich phase was re-extracted twice with the RTIL to free from bulk Ag. This process achieved an overall separation of 91 % NCA ¹⁰⁹Cd free from bulk Ag. The developed method demonstrates minimum requirement of RTIL to carry out the separation. The method is environmentally benign and cost effective.     

Ein Trennverfahren zur Bestimmung von Ag, Cd, Hg und Zn in biologischem Material durch radiochemische Neutronenaktivierungsanalyse

Zusammenfassung Es wurde ein einfaches Trennverfahren für die radiochemische NAA von biologischem Material entwickelt, mit dem aus einem komplexen Nuklidgemisch die Indicator-Radionuklide ^110mAg, ¹⁹⁸Au, ¹¹⁵Cd, ²⁰³Hg und ⁶⁵Zn als eine Gruppe mit Ausbeuten >99% abgetrennt werden können. Besonders geeignet ist dieses Verfahren für die Trennung des ²⁰³Hg von ⁷⁵Se und ⁶⁵Zn von ⁴⁶Sc, die sich bei einer gammaspektrometrischen Messung in der instrumentellen NAA gegenseitig stören. Gleichzeitig können die Nachweisgrenzen für Ag, Au und Cd wesentlich gesteigert werden. Das Verfahren basiert auf dem Aufschluß der bestrahlten Probe in einem Gemisch von HNO₃, HCl und H₂O₂, und auf der Trennung von Ag, Au, Cd, Hg und Zn an Dowex 1X8 aus 1,5 M salzsaurer Probelösung. Die Leistungsfähigkeit dieses Verfahrens wurde an Beispielen der Analyse von Flechten und verschiedenen Pilzarten demonstriert. Bei den verwendeten experimentellen Bedingungen liegen die Nachweisgrenzen in der Größenordnung von 10 ng/g.

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A separation procedure for the determination of Ag, Cd, Hg and Zn in biological material by radiochemical neutron activation analysis

Summary A simple separation procedure for the determination of Ag, Au, Cd, Hg and Zn in biological material by radiochemical neutron activation analysis was developed. It enables the separation of the indicator radionuclides ^110mAg, ¹⁹⁸Au, ¹¹⁵Cd, ²⁰³Hg and ⁶⁵Zn in a group with yields >99% and is well suited for the separation of ²⁰³Hg from ⁷⁵Se and ⁶⁵Zn from ⁴⁶Sc. The separation of these radionuclides is often necessary because of the occurrence of instrumental interferences in the instrumental neutron activation analysis. Simultaneously, the limits of detection for Ag, Au and Cd can significantly be improved. The method is based on the decomposition of the sample in the mixture of HNO₃/HCl/H₂O₂ and on the separation of Ag, Au, Cd, Hg and Zn on Dowex 1X8 from a sample solution being 1.5 M with HCl. The applicability of this method is demonstrated by the analysis of lichens and several kinds of fungi. For the experimental conditions used, the limits of detection are of the order of magnitude of 10 ng/g.

     

A109Cd/109mAg generator

Sorption of Cd and Ag by a cation exchange resin has been studied at different molarities of nitric acid. The sorption capacity of Cd on a cation exchanger has been determined. A¹⁰⁹Cd/^109mAg generator is suggested, based on the sorption of Cd on AG 50W-X8 organic cation exchanger at 0.01M HNO₃.^109mAg is eluted with 0.2M NaCl, physiologically compatible for human use.     

The extraction of mercury(II), silver(I), cobalt(II) and cadmium(II) by dioctylarsinic acid in chloroform

Dioctylarsinic acid (HDOAA) in chloroform solution has been investigated as a reagent for the extraction of Hg(II), Ag(I), Co(II), and Cd(II). Silver, cobalt and cadmium are not extracted below pH 7. An extraction coefficient of 1.1, constant over the pH range 1–6.5, was observed for Hg(II). With HCl concentrations of 1–8 M the extractability of mercury decreased slowly, reaching E_a⁰ = 0.05 at 8 M HCl. Silver formed a silver dioctylarsinate precipitate which collected at the interface. The extraction coefficients for Hg(II), Co(II) and Cd(II) increased above pH 7 to values of 20 (pH 9.1), 30 (pH 8.0), and 23 (pH 10), respectively. Reagent- and pH-dependence studies indicated that Co(II) and Cd(II) are extracted as M(DOAA)₂ or M(DOAA)Cl through interaction of HDOAA with M(OH)₂ or M(OH)⁺. Mercury was extracted from solutions of pH 1–6.5 as HgCl₂ (HDOAA)_2.5.     

Radiochemical separation of <Superscript>67</Superscript>Ga from Zn and Cu using the adsorbent resin Amberlite XAD-7

Summary A column chromatography was developed using a nonionic, polar adsorbent resin Amberlite XAD-7 for routine radiochemical separation of ⁶⁷Ga from Zn and Cu. 7M HCl was found to be the optimum concentration for adsorption of ⁶⁷Ga and elution of both Zn and Cu. Distilled water was used for elution of ⁶⁷Ga from the column. The optimum flow rate of the solutions on to the column was 5 ml/min. The concentrations of Zn and Cu in the final product (30 ml), measured by a polarography method, were 2.0 and 0.5 ppm, respectively. A solvent extraction method, using diisopropyl ether/7M HCl system was also tested to perform the same separation and a comparison between the two methods was made. The radiochemical chromatographic separation system is simple in design and easy to operate for separations in a hot cell.     

Improved separation of cadmium-109 from silver cyclotron targets by anion-exchange chromatography in nitric acid—hydrobromic acid mixtures

A method is presented for improved separation of ¹⁰⁹Cd from silver cyclotron targets. After dissolution of the target material in nitric acid and removal of silver by precipitation with copper metal, at pH 5, the cadmium is separated from zinc, copper and other elements by anion exchange chromatography. The solution in 0.5 M nitric acid plus 0.1 M hydrobromic acid is percolated through a column containing 4 ml of AG1-X8 anion-exchange resin (100–200 mesh), equilibrated with the same acid mixture. Zinc, copper(II) and other elements are eluted with 50 ml of this mixture. Cadmium is retained and finally eluted with 50 ml of 3 M nitric acid. The cadmium is retained much more strongly from the hydrobromic acid mixture than from the 0.02 M hydrochloric acid used for such separations previously; the presence of the strongly absorbed nitrate anion in fairly high concentration completely eliminates the tailing of zinc observed in 0.02 M hydrochloric acid. A typical elution curve and results of quantitative separations are presented.     

Radiochemical neutron activation analysis for determination of Au,Ag, Pt and Pd in geological samples

A procedure for separation of Au, Ag, Pt, and Pd in geological samples has been developed. After irradiation, samples were fused with Na₂O₂ and silver was separated by filtering through a PbCl₂ filter in 4M nitric acid solution. Au, Pt and Pd were concentrated with rhodium and thiourea as rhodium sulfide and the separation process of these elements was carried out by a chromatographic method. Au, Pt and Pd were retained on a Dowex-1×8 anion column in 1M HCl. Pd was eluted from the column by using a mixture of 75% HCl acid-25% acetone. Au was eluted by using a mixture of 10% HCl-90% acetone. In the gold fraction, Pt was also determined through the photopeak of¹⁹⁹Au radionuclide (158 keV). The method was simple and rapid.     

Radiochemical separation of 88Y from a SrCl2 target using chelating resin Chelex 100

Summary Yttrium-88 was produced from irradiation of a SrCl₂ target (4.8 g, pressed into a 19 mm disc) by 33 MeV proton beam at a current of up to 90 mA. Chelating resin Chelex 100 (H⁺ form, 100-200 mesh) was used for the separation of yttrium radionuclides (including ⁸⁸Y) from strontium. 0.01M nitric acid was used for the dissolution of target (100 ml), retention of Y and elution of Sr (200 ml). For the elution of yttrium, 25 ml 1M HNO₃ was employed. The column was 4 cm long with internal diameter of 1.6 cm. The flow rate was 1 ml/min throughout the separation procedure. The ⁸⁸Y recovery yield was 94% average and the stable Sr content in the final product (5 ml 0.1M HCl) was estimated to be less than 3 ppm.     

Separating Ag, B, Cd, Dy, Eu, and Sm in a Gd matrix using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction chromatography for ICP-AES analysis

The separation procedure for Ag, B, Cd, Dy, Eu and Sm as impurities in Gd matrix using ICP-AES technique with an extraction chromatographic column has been developed. The spectral interference of the Gd matrix on the elements was eliminated using a chromatography technique with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) as the mobile phase and XAD-16 resin as the stationary phase. Ag⁺, B₄O₇²⁻, and Cd²⁺ were eluted with 0.1 M HNO₃, while rare earth ions were not. The best eluent for separating Eu and Sm in the Gd matrix was 0.3 M HNO₃. The limit of quantitation for these elements was 0.6-3.0 ng mL⁻¹. The recovery of Ag, B, and Cd was 90-104% using 0.1 M HNO₃ as the eluent, while that of Eu, Gd, and Sm ranged from 100 to 102% with 0.3 M HNO₃. Dy was recovered quantitatively with 4 M HNO₃. The relative standard deviation of the methods for a set of three replicates was between 1.0 and 15.4% for the synthetic and standard Gd solutions. The proposed separation procedure was used to measure Ag, B, Cd, Dy, Eu, and Sm in a standard Gd solution.     

Silver cementation with magnesium in cyanide solutions

Contact precipitation of silver with a magnesium powder from 0.0025–0.01 M solutions of the system [Ag(CN)₂]^?-CN^? in the hydrodynamic mode was studied. The dependence of the silver cementation rate in the initial stage on the concentration of the [Ag(CN)₂]^? complex and on the surface area of the cementing agent was examined, and the relationship of the temperature factor with the depolarization of silver reduction on microcathodes and acceleration of magnesium dissolution on microanodes was analyzed.     

Cadmium-109 sources for trace analysis by X-ray fluorescence

Procedures for preparing¹⁰⁹Cd sources suitable for use in trace-element analysis by the X-ray fluorescence method were investigated. Sources were prepared from¹⁰⁹Cd in a 0.1N HCl solution by three different techniques: (a) electrodeposition of¹⁰⁹Cd onto a silver plate, which was then enclosed in a silver housing; (b) electrodeposition onto a lead foil, enclosed in a lead housing; (c) sorption of the¹⁰⁹Cd on a Permutit anionic exchange membrane, which was then enclosed in a silver housing. Using identical test conditions, the best results were obtained with the last-mentioned source, which was used successfully for the determination of Br and Pb in organic materials at concentration levels of ppm.     

Structural characterization of silver dialkylphosphite salts using solid‐state 109Ag and 31P NMR spectroscopy,IR spectroscopy and DFT calculations

High‐resolution solid‐state ¹⁰⁹Ag and ³¹P NMR spectroscopy was used to investigate a series of silver dialkylphosphite salts, Ag(O)P(OR)₂ (R = CH₃, C₂H₅, C₄H₉ and C₈H₁₇), and determine whether they adopt keto, enol or dimer structures in the solid state. The silver chemical shift, CS, tensors and |J(¹⁰⁹Ag, ³¹P)| values for these salts were determined using ¹⁰⁹Ag (Ξ = 4.652%) NMR spectroscopy. The magnitudes of J(¹⁰⁹Ag, ³¹P) range from 1250 ± 10 to 1318 ± 10 Hz and are the largest reported so far. These values indicate that phosphorus is directly bonded to silver for all these salts and thus exclude the enol structure. All ³¹P NMR spectra exhibit splittings due to indirect spin–spin coupling to ¹⁰⁷Ag (I = 1/2, NA = 51.8%) and ¹⁰⁹Ag (I = 1/2, NA = 48.2%). The ¹J(¹⁰⁹Ag, ³¹P) values measured by both ¹⁰⁹Ag and ³¹P NMR spectroscopy agree within experimental error. Analysis of ³¹P NMR spectra of stationary samples for these salts allowed the determination of the phosphorus CS tensors. The absence of characteristic P?O stretching absorption bands near 1250 cm^?1 in the IR spectra for these salts exclude the simple keto tautomer. Thus, the combination of solid‐state NMR and IR results indicate that these silver dialkylphosphite salts probably have a dimer structure. Values of silver and phosphorus CS tensors as well as ¹J(¹⁰⁹Ag, ³¹P) values for a dimer model calculated using the density functional theory (DFT) method are in agreement with the experimental observations. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of heavy metals and iodide by stripping voltammetry in sodium chloride on mercury-graphite electrodes

The behavior of Cd(II), Pb(II), Cu(II), and I⁻ in the aqueous solutions of sodium chloride is studied by stripping voltammetry. A new version of using an indicator electrode from carbon glass ceramics modified with mercury for the consecutive stripping determination of Cd(II), Pb(II), Cu(II), and iodide is proposed. The mercury-graphite electrode was formed in the solution of a supporting electrolyte based on NH₄Cl, HCl, 0.05 M potassium tetraoxalate (KH₃C₄O₃ · 2H₂O), and 5 × 10⁻⁵ M mercury(II). At first, Cd(II), Pb(II), Cu(II), and then iodide were determined by anodic-cathodic stripping voltammetry after adding a sample solution (table salt, 10–100 mg/mL NaCl).