Determination of radium isotopes in soil samples by alpha-spectrometry

A sensitive and accurate method for determination of radium isotopes in soil samples by α-spectrometry has been developed ²²⁵Ra, which is in equilibrium with its mother ²²⁹Th, was used as a yield tracer. Radium in soil samples was fused together with Na₂CO₃ and Na₂O₂ at 600 °C, leached with HNO₃, HCl and HF, preconcentrated by coprecipitation with BaSO₄, separated from uranium, thorium and iron using a Microthene-TOPO chromatographic column, isolated from barium in a cation-exchange resin column using 0.05M 1,2-cyclohexylene-dinitrilo-tetraacetic acid monohydrate as an eluant, electrodeposited on a stainless steel disc, and counted by α-spectrometry. The detection limit of the method is 0.43 Bq·kg⁻¹ for ²²⁶Ra, ²²⁸Ra and ²²⁴Ra if 0.50 g of soil sample are analyzed. The method was checked with two certified reference materials supplied by the IAEA, and reliable results were obtained Fourteen soil samples collected from the refractory industry in Italy were also analyzed. The mean radiochemical yields for radium were 85.7±4.3%, and the obtained radium concentrations in the soil samples were in the range of 8.08–3878 Bq·kg⁻¹ for ²²⁶Ra, of 1.60–678 Bq·kg⁻¹ for ²²⁸Ra and 1.25–550 Bq·kg⁻¹ for ²²⁴Ra, with ²²⁸Ra/²²⁶Ra and ²²⁴Ra/²²⁶Ra ratios ranged from 0.159–0.821 and from 0.142 to 0.525, respectively.     

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.     

Improvement of quality in the evaluation of radium isotopes 224,226,228Ra in oil scale samples

Elevated concentrations of the radium isotopes ^224,226,228Ra exist in the scale and produced water in oil exploration. The activity concentration of ²²⁶Ra was calculated from 186.2 keV peak with no usual spectral interference of 185.7 from ²³⁵U. The activity concentration of ²²⁸Ra was calculated from its first daughter product ²²⁸Ac using the 911.2 keV gamma rays since it is a pure beta emitter. The activity concentration of ²²⁴Ra was calculated from ²¹²Pb using the 238.6 keV gamma-ray and the secular equilibrium equation with ²²⁸Ra. The IAEA 448 (oil contaminated field soil) reference material was used as a quality control for ^226,228Ra and but was unreliable for ²²⁴Ra using ²¹²Pb.

     

Bulk optode sensors for batch and flow-through determinations of lead ion in water samples

A sensitive optode consisting of highly lead-selective ionophore (Lead IV), proton-selective chromoionophore (ETH 5294) and lipophilic anionic sites (KTpClPB) in plasticized polyvinyl chloride (PVC) membrane was fabricated. The optode membranes were used for determination of Pb²⁺ by absorption spectrophotometry in batch and flow-through systems. The influence parameters such as pH, type of buffer solution, response time and concentration of regenerating solution were optimized. The membrane responded to Pb²⁺ by changing its color from blue to pinkish purple in Tris buffer containing different concentration of Pb²⁺ at pH 7.0. The optode provided the response range of 3.16 × 10⁻⁸ to 5.00 × 10⁻⁵ mol L⁻¹ Pb²⁺ with the detection limit of 2.49 × 10⁻⁸ mol L⁻¹ in the batch system within the response time of 30 min. The dynamic range of 1.26 × 10⁻⁸ to 3.16 × 10⁻⁵ mol L⁻¹ Pb²⁺ with detection limit of 8.97 × 10⁻⁹ mol L⁻¹ were obtained in the flow-through system within the response time of 15 min. Moreover, the proposed optode sensors showed good selectivity towards Pb²⁺ over Na⁺, K⁺, Mg²⁺, Cd²⁺, Hg²⁺ and Ag⁺. It was successfully applied to determine Pb²⁺ in real water samples and the results were compared with well-established inductively coupled plasma optical emission spectrometry (ICP-OES). No significant different value (t_critical = 4.30 > t_exp = 1.00-3.42, n = 3 at 95% of confidence level) was found.     

Methodological advances for measuring low-level radium isotopes in seawater

A new approach for quantifying radium isotopes in seawater was developed in advance of the international GEOTRACES program, which has the goal of identifying processes and quantifying fluxes that control the distribution of trace elements and isotopes (TEIs) in the ocean. High-resolution water column samples were collected via a commercially available in situ pump modified to accept multiple filter media including a manganese-oxide (MnO₂) impregnated acrylic cartridge for extracting dissolved radionuclides from seawater. The modifications mitigated prefilter clogging and allowed for up to 1,800 L filtrations in 4 h of pumping. Different MnO₂ cartridge preparation methods were investigated to achieve maximum radium (Ra) extraction efficiency under high sample flow rates. Full-ocean depth profiles were measured for short-lived radium isotopes (²²³Ra and ²²⁴Ra) in shipboard laboratories using a delayed coincidence alpha scintillation counter (RaDeCC). Samples were reanalyzed 4 weeks and 2 months after collection for ²²⁸Th and ²²⁷Ac to correct for supported ²²⁴Ra and ²²³Ra, respectively. Finally, the cartridges were measured on a gamma-ray spectrometer for the long-lived radium isotopes (²²⁶Ra and ²²⁸Ra). Parallel 20 L samples at each pumping depth were collected from Niskin bottles and analyzed via alpha scintillation for ²²⁶Ra to determine radium extraction efficiencies for the cartridges. These modified methods will allow for increased sample throughput, and hence higher spatial resolution for radium isotopes in the ocean. Such resolution will greatly improve the determination of oceanic vertical and horizontal mixing rates over small and large scales, which in turn can be used to calculate fluxes of TEIs into the ocean.     

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.     

The accumulation of radium,barium and lead in algae

A mixture of radium-224, lead-212 and barium-133 as well as a mixture of lead-210 and bismuth-210 were used for the investigation of these elements in algae Scenedesmus obliquus in dependence of equilibrium pH in the absence and in the presence of other salts. It has been found that the affinity constant K_M decreases in the following order (lg K_M values are given in parentheses): Ra²⁺ (5.1), Ba²⁺ (4.8), Sr²⁺ and Ca²⁺ (4.6), Mg²⁺ (4.2), Cs⁺, Rb⁺ and NH ₄ ⁺ (2.9), K⁺ (2.7), Na⁺ (2.6) and Li⁺ (2.4). The uptake of lead and bismuth is more complicated because of the accumulation of free cations as well as hydroxo complexes.     

Simultaneous determinations of alpha-emitting isotopes of uranium and plutonium in bone

A radiochemical procedure has been developed for the simultaneous determinations of alpha-emitting isotopes of uranium and plutonium in bovine bone. The radiochemical recoveries ranged from 61 to 93% with a mean of 80±10% for uranium and 57 to 88% with a mean of 75±11% for plutonium. The method was successfully used for human bone.     

Determination of uranium isotopes in environmental samples

The determination of isotopes of uranium by alpha spectrometry in different environmental components (sediments, soil, water, plants and phosphogypsum) is presented and discussed in this paper. The alpha spectrometry is a very convenient and good technique for activity concentration of natural uranium isotopes (²³⁴U, ²³⁵U, ²³⁸U) in environmental samples and provides the most accurate determination of isotopic activity ratios between ²³⁴U and ²³⁸U. The analysis were provided information about possible sources of high concentrations of uranium in the examined sites determined by anthropogenic sources. The calculation of values ²³⁴U/²³⁸U in all analyzed samples was applied to identifying natural or anthropogenic uranium origin. Activity concentration of uranium isotopes in analyzed environmental samples shows that measurement of uranium levels is of great importance for environmental and safety assessment especially in contaminated areas (phosphogypsum waste heap).     

Assessment of effective radium content and radon exhalation rates in soil samples

Effective radium content and radon exhalation rates in soil samples have been measured by ??Sealed Can Technique?? using LR-115 type II plastic track detectors. The soil samples were collected from Farrukhabad city of Utter Pradesh, India. The values of effective radium content were found to vary from 5.39 to 34.56?Bq?kg^?1 with an average value of 16.58?Bq?kg^?1 and a standard deviation of 7.16. The mass and surface exhalation rate has been found to vary from 0.41?×?10^?6 to 2.64?×?10^?6?Bq?kg^?1?d^?1 and 1.41?×?10^?6 to 9.10?×?10^?6?Bq?m^?2?d^?1, respectively. All the values of radium content in soil samples of study area were found to be quite lower than the permissible value of 370?Bq?kg^?1 recommended by Organization for Economic Cooperation and Development.     

Deconvolution of liquid scintillation alpha spectra of mixtures of uranium and radium isotopes

A method for the determination of uranium and radium isotopes in water samples is proposed. Liquid scintillation techniques were used for collecting alpha spectra, which were then analyzed by fitting the alpha peaks with overlapping Gaussians. The analysis can quantify the observed isotopes with accuracy depending on the activity of each isotope.In order to simulate the peaks with Gaussian normal distribution functions, the centroid of each peak as well as the full width at half maximum (FWHM) are required, as they depend on the quenching of the sample. For this purpose, samples with known activities of ²²⁶Ra and its decay products and also of the uranium isotopes ²³⁸U and ²³⁴U, at various quenching levels, were used to establish the correlation of the peaks’ shift with the quench effect. In addition, the correlation of the FWHM with the centroid of a peak was determined, using the same procedure.Following the above analysis technique, an average of 97 ± 2% of detection efficiency and a lower limit of detection of 8.2 mBq kg⁻¹ for alpha isotopes were achieved.     

Identification of groundwater discharge in Cuddalore coast,Tamil Nadu using radium isotopes

For the optimal exploitation and management of coastal aquifers of Tamil Nadu, it is essential to evaluate the groundwater outflow into the sea also called as submarine groundwater discharge. In this study, radium isotopes (^223,224Ra) were employed to understand the groundwater discharge in coastal areas of Cuddalore district, Tamil Nadu. Sea water samples (100 L) were collected from various locations of Cuddalore coast in October 2011 and passed through Mn-impregnated acrylic fiber columns. These acrylic columns were analyzed for ^223,224Ra activities using radium delayed coincidence counter. The observed higher activities of ^223,224Ra excess (0.02 ± 0.001–3.28 ± 0.16 and 64 ± 3–380 ± 19 mBq/100 L respectively) indicate that groundwater discharge occurs in this coastal region.     

An isotope dilution method for environmental lead determinations

A method is described for the use of²¹²Pb to measure overall recovery in lead analyses. Other modifications of published procedures are also outlined. Most difficulties occur with samples containing small amounts (<10 μg) of Pb. In addition to low recovery factors, spectra are often obscured by the presence of dithizone oxidation product: a procedure for dealing with this is given.     

Radioactive characteristics and leaching behavior of Ra and Th isotopes on ishikawaite

Uranium determination and speciation in drinking waters consumed in Cyprus has been carried out by means of alpha-spectroscopy and thermodynamic calculations. Sampling included tap waters from different areas as well as local and imported bottled waters. The alpha-spectroscopic analysis was performed after selective separation of uranium by Chelex-100 and the uranium concentration in all waters was found below the WHO guideline. Based on the experimental data the annual radiation exposure of Cypriot population resulting from water consumption has been assessed. Thermodynamic calculations have shown that the ternary CaUO₂(CO₃) ₃ ^2? and Ca₂UO₂(CO₃)_3(aq) complexes are the predominant species in drinking waters.     

Automated identification of isotopes in neutron activated samples

A tabulation of about 2000 precise gamma-ray energies of about 250 isotopes formed through neutron activation has been used for the computer-assisted identification of the individual gamma emitters in complex gamma spectra. The identification consists in the calculation of the gamma-ray energies from the peak maximum position by taking into account the deviation from linearity of the spectrometer. Successive comparison of these energies with the energies of the tabulation allows then identification. The identification procedure was tested on a number of samples of varying complexity and satisfactory results were obtained.     

Mapping short-lived radium isotopes in estuarine residential canals (Gold Coast,Australia)

Distributions of short-lived radium isotopes (²²⁴Ra and ²²³Ra) were investigated on the Gold Coast waterways, one of the largest residential estuarine canal systems on Earth, in an attempt to estimate radium-derived residence times and obtain insights into sources of radium isotopes. Surface and bottom canal waters were sampled in 61 locations over ~300 km of waterways. Radium isotope activities were 12-fold higher in groundwater than estuarine waters. Surprisingly, radium activities were usually higher in surface waters than bottom waters implying a radium source associated with tidal pumping in artificial beach sediments. Estimated radium ages were usually younger within artificial canal surface waters than in the natural estuarine waterways. This study shows that the tidally driven groundwater radium source can be enhanced by the extended canal shoreline.     

Determination of alpha-emitting Pu isotopes in environmental samples

This paper presents an improved radiochemical procedure for the determination of alpha-emitting Pu isotopes in environmental samples (soils, sediments, vegetation) by alpha-particle spectrometry. Quantitative Pu recovery yields were obtained (average 60%), 0.1 mBq being the average minimum detectable activity by the complete technique. Special efforts were made to ensure the removal of traces of different natural alpha-emitting radionuclides, which can interfere with the correct determination of 239+240Pu and 238Pu concentrations. The radiochemical procedure was validated by application to reference material and by participation in intercomparison exercises. This radiochemical procedure was applied to the different layers of a high-resolution sediment core taken from a lake in Sweden. The 239+240Pu and 238Pu/239+240Pu profiles obtained in the high-resolution sediment core correctly reproduced the expected evolution of these quantities as observed historically in the atmosphere, validating the procedure for this purpose and showing the power of these radionuclides for dating purposes.     

Characterisation of lead rhodizonate as barium and radium adsorber from fresh water

A series of metal -diketonates were irradiated with bremsstrahlung of maximum energy of 50 MeV and the recoil behavior of⁷Be, formed from¹²C of ligands through¹²C(, n)⁷Be reaction, was investigated.⁷Be nuclides thus formed were detected partially as central metal atoms of the complexes. Complex yields of⁷Be were compared and an anomalously high yield was observed in tris-acetylacetonatocobalt(III) [Co(acac)₃].     

Determination of radium isotopes in mine waters through alpha- and beta-activities measured by liquid scintillation spectrometry

This paper presents a method for the determination of radium isotopes in mineralised mine waters, based on the separation of alpha- and beta-intensities measured in the precipitate by a liquid scintillation spectrometer in two time intervals (1 day and 7 days) after radium precipitation. The count rates of -particles give not only the concentration of alpha emitters (²²⁶Ra and²²⁴Ra), but also make possible to find the -counting efficiency of the system and through that-to determine the concentration of the -emitting radium isotope (²²⁸Ra) with higher accuracy. An improved chemical procedure was elaborated. By this method radium isotopes in different water samples were determined, in wide range of concentrations, from about 0.06 Bq/dm³ in potable water to more than 100 Bq/dm³ in some mine brines. As an example some analytical results are given. The detection limit, defined as three standard deviations, is-for both radium isotopes –0.03 Bq/dm³ (for intial volume of water sample equal to about 1 dm³ and for counting time of each measurement not longer than 1 hour).