Rapid radiochemical separation of radium from environmental samples using ion-exchanger Zeokarb-225

A rapid radiochemical method has been developed for the separation of radium in the presence of excess calcium from environmental samples such as spring waters and marine sediments. Radium is preconcentrated by co-precipitation as carbonates along with other alkaline earths. Subsequently, most of the alkaline earths are complexed with EDTA at pH 7.5 and the solution is passed through a column of Zeokarb-225 (NH ₄ ⁺ ). Radium, along with traces of calcium, is sorbed on the exchanger. Radium is desorbed with 2N HNO₃ and finally coprecipitated with 400 μg of barium as isulfate. The alphas of²²⁶Ra are counted in a silicon surface barrier detector and²²⁸Ra betas are counted in an end-window GM Counter.     

Separation of Ra and Th from rock matrices for alpha-spectrometry

Dating rocks using²²⁶Ra/²³⁰Th isochrons demands radiochemical purification of radium and thorium. This paper presents an improved method. Rocks are solubilised by nitric/nydrofluoric digestion followed by dissolution of insoluble fluorides by boric/nitric acids, and Th is extracted by passing the 8M nitric solution through an anion column in nitrate form. The eluant contains Ra and Ba which are precipitated as sulphate and redissolved in alkaline EDTA. Complete separation of Ba and Ra from sulphate is on an AG 1×8 anion column in EDTA form, which was found better than the chloride form. The Ba+Ra is separated on an AG 50W×8 cation column, and uses CDTA as an eluant for Ba. Careful pH control is essential. Ra elutes later with EDTA or 4M HCl and is precipitated with 125 g barium as sulphate to yield a source suitable for -spectrometry, or further treated to electroplate the Ra. The yield tracers used are²²⁸Th and²²⁴Ra. Because the sample contains natural²²⁴Ra a correction must be applied, calculated from the amount of natural²³²Th in the Th spectrum. Th may be precipitated with 100 g of ferric iron and gives a spectrometry-quality source, but further purification and electrodeposition was found to be preferable. Variations on the method for the case of analysis of calcium-rich fish otoliths are described.     

Rapid determination of radium isotopes by alpha spectrometry

An efficient analytical method for the determination of low-levels of²²⁶Ra and²²⁴Ra by alpha spectrometry is described. A cation exchange column was used to separate the analyte from other constituents in the sample (1–50 mL). After preconcentration and separation, the radium was electrodeposited onto a stainless steel disc from a solution of ammonium oxalate and hydrochloric acid. The electrodeposition was accomplished by the addition of platinum in microgram amounts. Linear responses were greater than two orders of magnitude. Detection limits of the procedure, taken as three times the standard deviation of several reagent blank analyses, were (1.8±0.3)×10^–4 Bq and (2.9±0.3)×10^–4 Bq for²²⁶Ra and²²⁴Ra, respectively. Recoveries of²²⁶Ra and²²⁴Ra ranged from 90% to 100% when samples of drinking water, well water, and dissolved bones were analyzed. Precision was calculated to be less than 5% for the determination of²²⁶Ra. Matrix effects were studied for salts of barium, magnesium, iron, and calcium.     

226RA analysis in sea and river water by adsorption on specific adsorbers

A method to analyse 226Ra in sea water Ra in sea water was investigated. The chemical procedure is based on adsorption of radium and barium, used as a carrier, on the specific adsorber PRTD at pH 9.5. The main interference is due to magnesium. The magnesium concentration is depleted by precipitating barium (carrier) and radium with calcium carbonate at pH 8 before the adsorption step. The proposed chemical procedure is simple and easily performed. The overall chemical yield is evaluated on the basis of the 133Ba spike. The sensitivity of the method is related to the volume of sea water. Under the experimental conditions used, 5 L of sea water, the limit was 1 226Ra mBq/L of water. The method may be also applied to the analysis of radium in river water, by omitting the carbonate precipitation.     

Contribution to the simultaneous determination of228Ra and226Ra by using 3M's EMPORETM radium rad disks

New method for simultaneous determination of²²⁸Ra and²²⁶Ra by using 3M's EMPORE^TM Radium Rad Disks in water has been developed. Both radionuclides²²⁶Ra and²²⁸Ra were counted through their daughter products,²²⁶Ra by conventional radon emanation techniques and²²⁸Ra through its daughter²²⁸Ac by using a proportional counter. Different molarity of diammonium hydrogen citrate were used for elution of²²⁸Ac and²²⁶Ra from EMPORE^TM Radium Rad Disks. 79% of²²⁸Ac was eluted in 10 ml of 0.0003M diammonium hydrogen citrate. The recovery of²²⁶Ra was 99% by using 40 ml of 0.2M diammonium hydrogen citrate adjusted by ammonium to pH 7.8.     

Determination of 226Ra in biological samples by adsorption on specific adsorbers

The determination of 226Ra in biological samples, such as milk and grass, was studied. 226Ra analysis of cow's milk was studied starting from de-fatted milk. The proteins were eliminated by coagulation of the colloidal phase with trichloroacetic acid. Phosphorus was then removed by precipitating it as molybdophosphate and finally adsorption was carried out by using two different adsorbers in order to concentrate and purify radium. Lead rhodizonate (LEHRO) adsorbed on charcoal and partially reduced tin dioxide (PRTD) were utilised. A method for the determination of 226Ra in grass ashes was also investigated. The main interference, due to magnesium, hinders the use of LERHO, so the proposed procedure is based on adsorption of radium on PRTD at pH 9.5. The magnesium concentration was depleted by precipitating barium (carrier) and radium with calcium carbonate at pH 8 before the adsorption step. The high phosphorus concentration in grass also interferes in the determination of 226Ra; phosphorus was eliminated as above via molybdophosphate precipitation. The radium was carried by barium and spiked with 133Ba. The yield of the chemical procedure was evaluated on the basis of 133Ba activity. Radium samples were alpha-counted and the activity was evaluated with a suitable calibration curve. Both exchangers in the milk analysis and PRTD in grass analysis were shown to be helpful in order to set up an easily performed procedure, which allows many samples to be processed simultaneously. All the methods adopted were shown to be very sensitive. Under the experimental conditions used, with 1 L of milk or 5 g of grass ashes, the limit was about 3 mBq 226Ra L-1 milk and < 1 mBq 226Ra g-1 grass ashes.     

Use of inorganic adsorbers in radium analysis

Two new simple methods were studied for the analysis of radium in fresh waters by concentration and purification. Both methods are based on the use of an inorganic selective adsorber, namely basic lead rhodizonate, LERHO, and partially reduced tin dioxide (PRTD). The procedures were checked by using filtered fresh waters spiked with 0.1 Bq of²²⁶Ra, and in the presence of few μg/l of barium. In each experiment¹³³Ba radioisotope was added to water samples to measure the yield of the overall procedure by γ-counting. Barium and radium were adsorbed from basic solutions on LERHO packed chromatographic column in the first procedure, while batch experiments were preferred for the adsorption on PRTD. After separation,²²⁶Ra and barium were eluted from the exchangers and co-precipitated onto small filters as thin film, supported on an inactive barium sulphate substrate, to be submitted to alpha-and gamma-spectrometry. Both methods gave promising results.     

The titrimetric determination of calcium and magnesium in silicate rocks

A cation-exchange scheme is described for the separation of calcium and magnesium from interfering elements in rapid silicate analysis. Interfering elements can be eluted from the ammonium form of Zeo-Karb 225 with a solution of the ammonium salt of ethylenediaminetetraacetic acid at pH 4.5. Calcium and magnesium are not eluted with this reagent but can be eluted consecutively with ammonium chloride solution and titrated photometrically with EDTA. Calcium and magnesium can be separated quantitatively from Al, Fe, Ti, Mn, Bi, Cd, Cr, Co, Cu, Pb, Mo, Ni, U, V, rare earths, and Zn.     

Determination of radium isotopes in mineral and environmental water samples by alpha-spectrometry

Summary A method for the determination of low-level radium isotopes in mineral and environmental water samples by alpha-spectrometry has been developed. Radium-225, which is in equilibrium with its mother ²²⁹Th, was used as a yield tracer. Radium were preconcentrated from water samples by coprecipitation with BaSO₄and iron (III) hydroxide at pH 8-9 using ammonia solution, then isolated from uranium, thorium and iron using a Microthene-TOPO chromatography column at 8M HCl, separated from barium in a cation-exchange resin column using 0.05M 1,2-cyclohexylenedinitrilotetraacetic acid monohydrate at pH 8.5 as an eluant, and finally electrodeposited on a stainless steel disc in a medium of 0.17M (NH₄)₂C₂O₄at pH 2.6 and current density of 400 mA^. cm^-2, and counted bya-spectrometry. Optimum experimental conditions for radium separation, purification and electrodeposition have been studied and discussed in the paper. The lower limits of detection of the method are 0.11 mBq^. l^-1for ²²⁶Ra, ²²⁸Ra and ²²⁴Ra, respectively, if 2 l of water are analyzed. The method has been checked with a certified reference material IAEA-Soil-6 supplied by the International Atomic Energy Agency and reliable results were obtained. Eighteen water samples collected in Italy have been analyzed with the method, the mean radiochemical yields for radium were 86.2±6.5%. The obtained radium concentrations were in the range of 0.50-60.8 mBq^. l^-1for ²²⁶Ra, of 0.10-25.7 mBq^. l^-1for ²²⁸Ra, and of￡LLD-7.97 mBq^. l^-1for ²²⁴Ra. The ²²⁸Ra/²²⁶Ra and ²²⁴Ra/²²⁶Ra ratios were in the range of 0.189-4.45 and￡LLD-0.941, respectively.     

Removal of 226Ra from aqueous media and its thermodynamics and kinetics

The composite adsorbent prepared by mixing of polyacrylonitrile and clinoptilolite was used for investigating the adsorption behaviour of ²²⁶Ra in column system. The effective parameters like initial activity concentration, pH of the solution, contact time and temperature for adsorption behaviour of ²²⁶Ra were studied. Adsorption efficiency of ²²⁶Ra on composite adsorbent from aqueous solution was determined to 98.73 ± 0.59 % at pH 5.0 and 30 °C in a short time. The isotherm models were studied to evaluated adsorption characteristics of ²²⁶Ra onto composite adsorbent. The thermodynamic parameters were showing that the processes for ²²⁶Ra were exothermic. Adsorption kinetics of the radium is also studied.

     

Ion exchange of radium and barium in zeolites

The sorption of radium, barium and mixture of both elements has been studied in the zeolites 3A, 5A and Y. The ratio zeolite; solution was 100 mg: 10 cm³ and the pH was 3. Carrier-free radium was completely retained in all studied zeolites. When 0.0016 meq of barium/cm³ were added, the sorption of radium decreased in the zeolite 5A only and when 0.014 meq of barium/cm³, the radium sorption was reduced in all the studied zeolites. The sorption of barium was similar to that of radium. The amounts of sodium and calcium removed from the zeolites and the proton quantity fixed to them allowed us propose the ion exchange mechaniosm. The changes and ionic radii of the species exchanged did not play an important role. However, the location of the ions in the crystalline network of each zeolite is probably an important parameter for the exchange.     

Treatment of an aqueous radioactive waste solution with elevated levels of226Ra and228Ra

Treatment of an aqueous radioactive waste solution to remove radium prior to discharge was conducted at a laboratory scale. The actual solution is mainly composed of combined radium (²²⁶Ra and²²⁸Ra) with high concentrations of manganese, iron and calcium, which are present as chlorides in dilute hydrochloric acid. Direct precipitation by sulfate anions was selected to be the more viable treatment technique. Sulfate anion concentration, free acidity, temperature and aging of the sulfate precipitate in the supernate prior to filtration are factors that were investigated for their effect on the separation efficiency. The data obtained are discussed in detail.     

Influence of Ba on the electrodeposition of226Ra

A detailed study of the influence of barium on the electrodeposition of²²⁶Ra was made using two different procedures. High yields (80–90%) were attained when the amounts of barium were not very significant. However, the²²⁶Ra yields fell drastically for amounts slightly greater than 0.10–0.15 mg of Ba, according to the electrodeposition procedure. Samples containing trace amounts of barium less than 100–150 g can thus be treated with no barium-radium separation being required.²¹⁰Po was also deposited, although practically no influence of barium on the Po plating was observed. The²²⁵Ra resolution rose uniformly (25 to 55 keV) as the amount of barium rose up to 1 mg. These resolutions allow one to make a direct accurate determination of²²⁶Ra as well as an indirect determination of²²⁴Ra and²²³Ra via measurement of their daughter products.     

Rapid determination of 226Ra in environmental samples

A new rapid method for the determination of ²²⁶Ra in environmental samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used for emergency response or routine sample analyses. The need for rapid analyses in the event of a Radiological Dispersive Device or Improvised Nuclear Device event is well-known. In addition, the recent accident at Fukushima Nuclear Power Plant in March, 2011 reinforces the need to have rapid analyses for radionuclides in environmental samples in the event of a nuclear accident. ²²⁶Ra (T1/2?=?1,620?years) is one of the most toxic of the long-lived alpha-emitters present in the environment due to its long life and its tendency to concentrate in bones, which increases the internal radiation dose of individuals. The new method to determine ²²⁶Ra in environmental samples utilizes a rapid sodium hydroxide fusion method for solid samples, calcium carbonate precipitation to preconcentrate Ra, and rapid column separation steps to remove interferences. The column separation process uses cation exchange resin to remove large amounts of calcium, Sr Resin to remove barium and Ln Resin as a final purification step to remove ²²⁵Ac and potential interferences. The purified ²²⁶Ra sample test sources are prepared using barium sulfate microprecipitation in the presence of isopropanol for counting by alpha spectrometry. The method showed good chemical recoveries and effective removal of interferences. The determination of ²²⁶Ra in environmental samples can be performed in less than 16?h for vegetation, concrete, brick, soil, and air filter samples with excellent quality for emergency or routine analyses. The sample preparation work takes less than 6?h. ²²⁵Ra (T1/2?=?14.9?day) tracer is used and the ²²⁵Ra progeny ²¹⁷At is used to determine chemical yield via alpha spectrometry. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory radium particles are effectively digested. The preconcentration and column separation steps can also be applied to aqueous samples with good results.     

On the use of232U and its daughters for the determination of226Ra in water samples

The authors propose a method to determine 226Ra by using a solution of²³²U and its daughters in equilibrium as a tracer.²²⁴Ra of the²³²U solution can be used as yield determinant for²²⁶Ra. The growth of²¹⁴Po from²²⁶Ra and of²¹²Po from²²⁴Ra is measured at different times after the isolation of the radium fraction.     

Transfer of naturally occurring radionuclides to wheat under laboratory controlled conditions

Knowledge of soil–plant transfer of naturally occurring radionuclides can be essential to assure an adequate radiological protection. Available data are mainly for anthropogenic radionuclides and biased for temperate climates. Wheat plantlets were grown using soil collected in Mediterranean regions and transfer factors, TF, for ^234,238U, ²²⁶Ra, ²¹⁰Po and stable elements (K, Na, Ca and Mg) were determined. U, Ra and Po were mainly located in roots. Calcium presented the highest TF values, whereas for radionuclides were much lower. Uranium TFs were correlated with total and exchangeable potassium concentration in soil. Calcium and radium TFs were correlated with total calcium concentration in soil.

     

Flameless atomic absorption determination of barium in natural waters using the technique of standard additions

Summary A simple method for the determination of barium in natural waters by flameless atomic absorption spectrometry using the carbon rod is proposed. Barium in highly salted waters is previously separated from the interfering ions by ion-exchange chromatography, using Dowex 50 W-X8 resin, and eluted with 0.1M EDTA solution. Mineral waters with low salinity are transferred directly to the furnace and the standard addition method is performed. The detection limit is 90 pg Ba for 10l injections. The method was applied to samples from the Atlantic Ocean and from Araruama Lake. Barium in commercially available waters was also determined.

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Bestimmung von Barium in natürlichen Wässern durch flammenlose Atomabsorptionsbestimmung unter Verwendung des Standard-Zugabe- Verfahrens

Zusammenfassung In salzreichen Wässern enthaltenes Barium wird von störenden Ionen durch Ionen-Austausch-Chromatographie über Dowex 50 W-X8 getrennt und mit 0,1M EDTA ausgewaschen. Mineralwässer mit geringem Salzge- halt werden unmittelbar in den Ofen eingebracht und die Standard-Zugabe- Methode angewendet. Die Nachweisgrenze liegt bei 90pg/10l. Die Methode wurde zur Untersuchung von Proben aus dem Atlantischen Ozean sowie aus dem Araruama-See angewendet. Außerdem wurde Barium in handelsüblichen Trinkwässern bestimmt.

     

Cation-exchange separation of strontium from manganese and other elements in citrate media

Mn(IT) can be eluted quantitatively with 0.067M ammonium citrate at pH 7.0 or 7.5 from a column of AG50W-X8 cationexchange resin (200-400 mesh), and separated from Sr which is retained. Mg, Ca, Cu(II), Zn and Co(II) accompany Mn(II). From citric acid solutions up to 1M (20%) and from 5 % citric acid solution at pH 2.2 both Mn(II) and Sr are retained very strongly. This is in agreement with some previous work but disagrees with a recent statement by others that 5 % citric acid at pH 2.2 is an effective eluting agent for Sr.     

The influence of distribution coefficients on the separation factor of lithium isotopes

The influence of distribution coefficients on the separation factor of lithium isotopes was studied with Dowex 50W-X8, 200–400 mesh, ammonium form, strongly acidic cation exchanger by changing the pH and EDTA concentration of the eluent. It was found that the larger the EDTA concentration in the buffer solution, the smaller the distribution coefficients were. The separation factor was increased with decreasing EDTA concentration. The separation factor of lithium isotopes linearly increased up to a distribution coefficient value of 30, and gradually increased above 30. The optimum value of distribution coefficient of lithium to separate litihium isotopes was about 30. The distribution coefficient was increased with increasing pH, but the separation factor of lithium isotopes has no relation with pH.⁶Li concentrated on the resin phase, and⁷Li in the solution phase.     

Separation des alcalino-terreux par l'edta sur resine echangeuse d'ions

The quantitative separation of a few mg of strontium and barium from several g of calcium is described. The alkaline earth carbonates are dissolved in 0.1 M EDTA, fixed at pH 4.8 on an ammoniacal Dowex column, and eluted, also with 0.1 M EDTA, calcium at pH 5.25, strontium at pH 6.0, barium at pH 9.0. The end of the calcium elution can be followed accurately by a sudden pH increase in the eluate(from 4.8 upto 5.25).