Determination of indium in metallic tin and cadmium by substoichiometric neutron activation analysis

The paper deseribes the determination of indium in metallic tin and cadmium metals by the direct method, which is a variant of substoichiometric radioactivation analysis. It is based on substoichiometric extraction of indium diethyldithiocarbamate into carbon tetrachloride. Indium in tin metal was determined by^116mIn (T=54 min), while^115mIn (T=4.5 h), formed by the reaction¹¹⁴Cd(n, γ)¹¹⁵Cd was used for cadmium samples. The irradiated sample was dissolved and the radioactivity of^116mIn or^115mIn, A, was measured. After the separation of indium from the matrix, a known amount of indium, m, was separated substoichiometrically and the radioactivity, a, was measured. Indium was calculated as M_x=m A/a. If a known amount of the element, M, is added to the irradiated sample in advance, the equation for calculation is given as M_x-m A/a−M. By this method, indium can be determined without any consideration of self-shielding and secondary nuclear reaction of the matrix.     

The determination of tin in rocks by thermal neutron activation

A fast routine method for the determination of tin in rocks is discussed. The method is based on coprecipitation of tetravalent tin with ferric hydroxide, followed by a short irradiation in a high thermal neutron flux, extraction in toluene from 1∶1 sulphuric acid which is 5N in potassium iodide, and counting of^123mSn (T=40 m) or^125mSn (T=9.7 m) with a well-type NaI detector. In the present work^125mSn was used. The lower limit of determination is governed by the blank of the reagents. For a sample of at least one gram it is ≌ 0.2 μg Sn·g⁻¹.     

Simple indium generators

Very economical, rapid and pure methods for the production of^115mIn and^113mIn from¹¹⁵Cd and¹¹³Sn, respectively are described. The methods are based on the extraction of^115mIn by o-xylene from 7.2M H₂SO₄ −0.06M HBr, and its reextraction with ≈11M H₂SO₄ −0.06M HBr from n-hexane. The γ-spectra of the generated^115mIn and^113mIn indicate that they are free from any other interferences.     

115Cd photonuclear production for115Cd−115mIn generator

Production of¹¹⁵Cd by means of photonuclear reaction and preparation of a^115mIn generator, based on the genetic sequence of¹¹⁵Cd^115mIn, were studied. The production rates of¹¹⁵Cd by the¹¹⁶Cd(γ, n)¹¹⁵Cd reaction were determined as a function of the maximum bremsstrahlung energies between 35 and 60 MeV. Then the parent,¹¹⁵Cd, was produced by irradiating about 0.15g of CdO with the bremsstrahlung from a 60 MeV-150 μA electron beam. After the parent in the Cd ₄ ²⁻ form was adsorbed on the Dowex 1x8 resin column, the daughter was eluted with a physiologic saline adjusted to pH 1. The generator was milked over a period of 3 days, during which time about 900 ml of eluent were allowed to flow through the column. Even after the milkings were repeated 15 times with 60 ml of the eluent, no¹¹⁵Cd was found in the^115mIn fractions (the detection limit of inactive cadmium: 0.02 μg).     

Determination of113mCd in natural water

A method has been developed for the determination of^113mCd from fallout in large-volume environmental water samples. In the analytical procedure a known amount of cadmium carrier is added to the sample and the cadmium is preconcentrated as insoluble hydroxide by coprecipitation with ferric hydroxide. The separated cadmium is purified from other interfering elements by an anion—exchange procedure. Finally, cadmium is coprecipitated with copper sulfide, and the radioactivity of^113mCd is measured in a lowbackground, gas-flow proportional beta counter. The cadmium recovery is established by determining the amount of Cd in the precipitate using an energy dispersive x-ray fluorescence spectrometer. For a 24hr counting period a lower limit of detection around 50μBq^113mCd/1 of sample has been attained. Samples of Lake Michigan water were analyzed: the concentration of^113mCd in 1980 was 177±5 μBq/l.     

Preconcentration Ultra Trace of Cd(II) in Water Samples Using Dispersive Liquid‐Liquid Microextraction with Salen(N,N′‐Bis(Salicylidene)‐Ethylenediamine) and Determination Graphite Furnace Atomic Absorption Spectrometry

Dispersive liquid–liquid microextraction (DLLME) technique was successfully used as a sample preparation method for graphite furnace atomic absorption spectrometry (GF AAS). In this extraction method, 500 μL methanol (disperser solvent) containing 34 μL carbon tetrachloride (extraction solvent) and 0.00010 g Salen(N,N′‐bis(salicylidene)ethylenediamine) (chelating agent) was rapidly injected by syringe into the water sample containing cadmium ions (interest analyte). Thereby, a cloudy solution formed. The cloudy state resulted from the formation of fine droplets of carbon tetrachloride, which have been dispersed, in bulk aqueous sample. At this stage, cadmium reacts with Salen(N,N′‐bis(salicylidene)‐ethylenediamine), and therefore, hydrophobic complex forms which is extracted into the fine droplets of carbon tetrachloride. After centrifugation (2 min at 5000 rpm), these droplets were sedimented at the bottom of the conical test tube (25 ± 1 μL). Then a 20 μL of sedimented phase containing enriched analyte was determined by GF AAS. Some effective parameters on extraction and complex formation, such as extraction and disperser solvent type and their volume, extraction time, salt effect, pH and concentration of the chelating agent have been optimized. Under the optimum conditions, the enrichment factor 122 was obtained from only 5.00 mL of water sample. The calibration graph was linear in the range of 2‐21 ng L^?1 with a detection limit of 0.5 ng L^?1. The relative standard deviation (R.S.D._s) for ten replicate measurements of 20 ng L^?1 of cadmium was 2.9%. The relative recoveries of cadmium in tap, sea and rain water samples at a spiking level of 5 and 10 ng L^?1 are 99, 94, 97 and 96%, respectively. The characteristics of the proposed method have been compared with cloud point extraction (CPE), on‐line liquid‐liquid extraction, single drop microextraction (SDME), on‐line solid phase extraction (SPE) and co‐precipitation based on bibliographic data. Therefore, DLLME combined with GF AAS is a very simple, rapid and sensitive method, which requires low volume of sample (5.00 mL).     

Separation of carrier-free115mIn from115Cd and132I from132Te over the zirconium oxide column

A new way of radiochemical separation of carrier-free^115mIn from¹¹⁵Cd and¹³²I from¹³²Te over the column of zirconium oxide is described. Activities of Cd and In in equilibrium in dilute acetic acid solution were bufferred with dilute sodium acetate and fed into the column at a pH 7, when cadmium activity passed out unadsorbed and the^115mIn was adsorbed in the column. A study of the γ-ray peak of the separated^115mIn showed that the product is of high radionuclidic purity. Te-I pair was separated by passing the weakly acidic solution of¹³²Te and¹³²I in the presence of AgNO₃ and Na₂SO₃, through the column where both activities were adsorbed. Iodine was washed outh with 5% sodium thiosulphate solution and the retained tellurium activity was later washed out with 6M HNO₃. The β-decay study showed that the separated¹³²I product is of high radiochemical purity. The processes took less than half an hour and the yields were quantitative.     

Extraction and spectrophotometric determination of vanadium(V) with ferron

Various metal complexes of 7-iodo-8-hydroxyquinoline-5-sulphonic acid (ferron) were found to be selectively extracted into immiscible alcohols. Vanadium(V) is almost completely extracted into n-butanol in a single extraction from solutions which are 0.05 M in sulphuric acid. A sensitive and selective spectrophotometric method can be based on this extraction. Beer's law is obeyed up to 15.3 μg of vanadium per ml; the sensitivity of the color reaction is 0.011 μg of vanadium per cm² at 430 mμ. The interference of iron(III) can be eliminated by adding excess pyrophosphate. The extracted species appears to contain vanadium, ferron and n-butanol in the ratio 1:2:4.     

Radiochemical separation of110mAg,210Pb,127Te and131I from aqueous nitric acid solution by bis-2-(butoxyethyl ether)

A bis-2-(butoxyethyl ether) (DBC) solvent extraction method has been developed for the radiochemical separation of^110mAg,²¹⁰Pb,¹²⁷Te and¹³¹I in varying concentrations of aqueous HNO₃. Various factors were examined to determine the optimum conditions of extraction. The effect of various masking agents has been studied. The extraction of¹³¹I is enhanced to 99% at 2.4M HNO₃ in the presence of KSCN.¹³¹I was stripped into aqueous sodium hydroxide from the oxygenated organic extractant. The method was then applied for the recovery of¹³¹I from neutron irradiated tellurium metal. The mechanism and reactivity of DBC with metal ions is described.     

A rapid separation of radioactive cesium by nitrobenzene extraction using the chromium complex [Cr(aniline)2(NCS)4]−

A rapid separation of radioactive cesium by the solvent extraction method was investigated. Cesium ions are quantitatively extracted with [Cr(NH₂C₆H₅)₂(NCS)₄]⁻ into nitrobenzene. EDTA is an effective masking agent for other polyvalent cations. The extracted cesium can be back-extracted into the aqueous phase by shaking with 6N HCl. The method was applied to samples of a natural mixture of fission products and a reactor coolant. The decontamination factors for other predominant isotopes in fission products were 10²∼10⁴. The separation of^137m Ba from a mixture of¹³⁷Cs and^137m Ba is also described.     

Spectrophotometric Determination of Rhenium(IV) with Thiocyanate,TX-100 and N,N′-Diphenylbenzamidine

A spectrophotometric method to determine rhenium(IV) at trace level is based on the extraction of Re(IV)-SCN^? complex in sulphuric acid media with N,N′-diphenylbenzamidine(DPBA) in presence of a non-ionic surfactant triton X-100 (TX-100) in chloroform. The complex shows maximum absorbance at 435 nm with amolar absorptivity value of 4.24 × 10⁴ L mol^?1 cm^?1 at an acidity range 3.5-6.5 M H₂SO₄. The method followed Beer's Law for the system Re(IV)-SCN^?(TX-100)-DPBA upto 4.0 μg Re(IV) mL^?1. The detection limit of the method is 5 ppb. None of the tested foreign ions, except molybdenum(VI), interfere with the determination of rhenium. The interference due to molybdenum could effectively be removed by prior precipitation with oxine. The effect of various analytical parameters on the extraction of the metal are discussed.     

Carrier-free separation of (115m)In from irradiated Cd by solvent extraction with 1-phenyl-3-methyl-4-caproylpyrazolone-5

A method is presented for the routine milking of the 41 2 -hr half-life nuclide (115m)In from its 2.3 day half-life parent (115m)Cd. The method utilizes the extraction of In and Cd from aqueous solution at various pH values, 1-phenyl-3-methyl-4-caproylpyrazolone-5 in isobutyl methyl ketone being used as extracting agent. A good decontamination factor was obtained and the yield of (115m)In from residual cadmium activity was 85-90%.     

Radiochenical determination of technetium-99 in LLW by chelation with sodium diethyl dithiocarbamate (NaDDC) and extraction with chloroform

A radiochemical method has been developed for the determination of⁹⁹Tc in low-level radioactive, waste from nuclear facilities, using^99mTc as an internal tracer. Radioactive contaminants were removed by carrier hydroxide precipitation and chelating extraction with NaDDC/CHCl₃ system at pH 4. The final technetium was chelated with NaDDC in 3N HCl solution and extracted selectively into chloroform. The average of radiochemical recovery for various types of LLW sample is about 90%. The decontamination factors for most radioactive nuclides are higher than 10⁵. The detection limit for⁹⁹Tc in a sample of about 10 g is 0.17 pCi/g (6.5 Bq·kg^–1) for a 100-minute count.     

Chemical and radiochemical evaluation of the purity of99mTc extracted by MEK

Solvent extraction separation of^99mTc from⁹⁹Mo using methyl ethyl ketone(MEK) has been found to be an effective method of obtaining^99mTc of medicinal purity from low specific activity⁹⁹Mo. The authors have investigated the effect of alkali and molybdenum concentration on the extraction of⁹⁹Mo and^99mTc into methyl ethyl ketone. The possibility of methyl ethyl ketone forming enol and condensation products and its effect on the final extraction efficiency and purity of^99mTc has been studied. Sodium molybdate has been found to have a good salting out effect on^99mTc pertechnetate and hence^99mTc extraction can be better accomplished from low specific activity⁹⁹Mo solutions. The ketone seems to form traces of condensation products in the extraction procedure. These have been found to be coextracted with^99mTc into MEK but did not affect the extractability of^99mTc. It was observed that neutral alumina column removes these condensation products from MEK containing^99mTc. Alternately these could be filtered off by acidification of the final aqueous^99mTc solution. The studies indicate that under optimum experimental conditions methyl ethyl ketone separates^99mTc from⁹⁹Mo with high efficiency and yields^99mTc of high purity suitable for use in nuclear medicine in the form of various labelled compounds.     

The excretion of110mAg by a gastropod species (Natica intricata)

The excretion kinetics of^110mAg in a gastropod species contaminated through water pathway has been studied under laboratory condition. The pattern of the excretion results can be represented by a monophasic linear regression function. The excretion coefficient and biological half-life were calculated. The biological half-life was found to be 33 days. The study suggests that the excretion rate of^110mAg byN. intricata may be considered as a potential biomonitor on the shoreline of the Black Sea marine environment.     

Use of zirconium phosphate as ion exchanger in some parent-daughter radioisotope separations

Zirconium phosphate as ion exchanger suitable for column operation has been prepared by mixing hot metaphosphoric acid solution with a solution of zirconium oxychloride when the white insoluble phosphate separated out which was dried and purified. The ratio of zirconium: phosphate was found to be 1:2. Separation of parent-daughter systems like¹¹⁵Cd-^115mIn,¹⁴⁴Ce-¹⁴⁴Pr and²¹⁰Pb-²¹⁰Bi were carried out with this exchanger. γ-ray spectrum of the separated^115mIn and the β-decay curve of¹⁴⁴Pr and²¹⁰Bi showed that all the daughter activities are radiochemically pure. The separation process in each case takes less than half an hour and the yield is quantitative.     

Radiochemical separation and determination of europium by Ge(Li) detector in biological tissues

A simple neutron activation method has been developed for the determination of europium in biological tissues and applied in the analysis of marine organism samples with ±9% precision at the nanogram level. The method is based on the separation, by ion-exchange, of the rare earth group from dry or ashed irradiated tissues and subsequent determination of^152mEu, by γ-spectrometry using a lithium drifted germanium detector.^152mEu, separated almost completely from other than rare earth elements, with better than 98% chemical yield, is counted on the 121.8 keV photopeak which then is practically free from any other γ-ray energy interfering in this counting.     

Determination of cadmium using radiochemical neutron activation analysis

A method has been developed for the determination of cadmium in samples of food and biological materials using neutron activation analysis with radiochemical separation. The irradiated sample is digested in presence of cadmium carrier, with a nitric-perchloric mixture, evaporated to dryness, dissolved in 6M HCl and placed onto an ion exchange column loaded with Dowex 1-X8 resin in chloride form and conditioned with HCl 6M. The cadmium is retained in the resin. After a washing procedure with several portions of HCl of decreasing concentration, the cadmium is eluted with an ammonia-ammonium chloride buffer. The activity of ^115mIn which is in equilibrium with ¹¹⁵Cd, is measured using a NaI(Tl) well type detector. The method has been evaluated by analyzing certified reference materials with cadmium concentrations covering a range of 0.020 to 200 mg^.kg^-1. The agreement of the results with the certified values is within 95%, which gives an indication of the sensitivity and accuracy of the proposed method.     

Determination of 99Tc in environmental samples by anion exchange and liquid-liquid extraction at controlled valency

A method for collecting ⁹⁹Tc from 200-2-400 1 of sea water by anion exchange has been developed. Further decontamination of ^103.106Ru was achieved by repeated evaporation of RuO₄ from 0.05 M sulphuric acid at 100° C, followed by extraction of TcO^-₄ into 5% triisooctylamine-xylene at controlled valency. ^110mAg was precipitated as AgCl. An average overall radiochemical yield of 70% was found for Tc. Decontamination factors were between 3 10⁵ and 2 10⁷ for Ru and 2 10⁵ for Ag. A method for determining ⁹⁹Tc in seaweed by wet ashing and simple extraction into 5% triisooctylamine-xylene is also presented.     

N-oxides of 4-(5-nonyl)pyridine and trioctylamine as extractants for cerium(IV) and its separation from thorium(IV)

Trace level cerium has been oxidized to the quadrivalent state with potassium dichromate and shown to be preferentially extracted from very dilute mineral acid solutions and also from moderate nitric acid media by 0.1M solutions of 4-(5-nonyl)pyridine oxide and trioctylamine oxide dissolved in xylene. The dependence of extraction on the type of N-oxide, acid concentration and the N-oxide concentration has been investigated. The influence of the concentration of salting-out agents is described. Separation factors for a number of metal ions relative to cerium(IV) are reported for 0.1 M 4-(5-nonyl)pyridine oxide/xylene-0.1M sulphuric acid system. The ratio of the D for Ce(IV) to that of Ce(III) is greater than 10⁵, and the D for Ce(IV) is much greater than that for thorium(IV). Separation of cerium(IV) from thorium has been achieved from 0.1M sulphuric acid solutions using 0.1M 4-(5-nonyl)pyridine oxide/xylene as an extractant.