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.     

Rapid determination of 226Ra in emergency urine samples

A new method has been developed at the Savannah River National Laboratory (SRNL) that can be used for the rapid determination of ²²⁶Ra in emergency urine samples following a radiological incident. If a radiological dispersive device event or a nuclear accident occurs, there will be an urgent need for rapid analyses of radionuclides in urine samples to ensure the safety of the public. Large numbers of urine samples will have to be analyzed very quickly. This new SRNL method was applied to 100 mL urine aliquots, however this method can be applied to smaller or larger sample aliquots as needed. The method was optimized for rapid turnaround times; urine samples may be prepared for counting in <3 h. A rapid calcium phosphate precipitation method was used to pre-concentrate ²²⁶Ra from the urine sample matrix, followed by removal of calcium by cation exchange separation. A stacked elution method using DGA Resin was used to purify the ²²⁶Ra during the cation exchange elution step. This approach combines the cation resin elution step with the simultaneous purification of ²²⁶Ra with DGA Resin, saving time. ¹³³Ba was used instead of ²²⁵Ra as tracer to allow immediate counting; however, ²²⁵Ra can still be used as an option. The rapid purification of ²²⁶Ra to remove interferences using DGA Resin was compared with a slightly longer Ln Resin approach. A final barium sulfate micro-precipitation step was used with isopropanol present to reduce solubility; producing alpha spectrometry sources with peaks typically <40 keV FWHM (full width half max). This new rapid method is fast, has very high tracer yield (>90 %), and removes interferences effectively. The sample preparation method can also be adapted to ICP-MS measurement of ²²⁶Ra, with rapid removal of isobaric interferences.     

On the determination of226Ra in soils and uranium ores by direct gamma-ray spectrometry

The evaluation of the source term in facilities related to the first stages of nuclear fuel involves the determination of radium concentration, as well as those from other radionuclides members of the uranium series. These activities are often required within a short time period, making impossible the use of radiochemical methods or the gamma-ray spectrometry of radium daughters. In those situations it can be very convenient to determine the²²⁶Ra activity by means of its 186 keV gamma-ray line. For this purpose it is necessary to estimate the interference due to²³⁵U, also present in natural samples. This method has been applied successfully to several soil samples from an old uranium factory in Southern Spain.     

Assessment of 226Ra and 228Ra activity concentration in west coast of India

An investigation on the distribution of ²²⁶Ra and ²²⁸Ra activity concentration in coastal surface sea water from Okha in Gujarat to Ratnagiri in Maharashtra state along the west coast of India was carried out. In-situ pre-concentration technique was used to measure radium isotopes by passing 1,000 L of seawater through MnO₂ impregnated polypropylene filter cartridges at all the locations. ²²⁶Ra was estimated using gamma ray peak of its daughter radionuclides ²¹⁴Bi and ²¹⁴Pb. ²²⁸Ra was estimated from its daughter ²²⁸Ac. In the coastal waters, ²²⁶Ra and ²²⁸Ra activity concentration were observed to be in the range of 1.5–2.9 and 2.5–8.6 Bq m^?3 with a mean of 2.2 and 4.9 Bq m^?3 respectively. The activity of ²²⁸Ra was observed to be more than ²²⁶Ra in all the locations. The variation in spatial distribution of the radium isotopes activity concentration and its ratio with respect to location is discussed in the paper. The radioactive database obtained represents reference values for coastal environment of India.     

Rapid method for 226Ra and 228Ra analysis in water samples

Summary The measurement of radium isotopes in natural waters is important for oceanographic studies and for public health reasons. Radium-226 (T_1/2 = 1620 y) 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 analysis of ²²⁶Ra and ²²⁸Ra in natural waters can be tedious and time-consuming. Different sample preparation methods are often required to prepare ²²⁶Ra and ²²⁸Ra for separate analyses. A rapid method has been developed at the Savannah River Environmental Laboratory that effectively separates both ²²⁶Ra and ²²⁸Ra (via ²²⁸Ac) for assay. This method uses MnO₂ Resin from Eichrom Technologies (Darien, IL, USA) to preconcentrate ²²⁶Ra and ²²⁸Ra rapidly from water samples, along with ¹³³Ba tracer. DGA Resin^ò (Eichrom) and Ln-Resin^ò (Eichrom) are employed in tandem to prepare ²²⁶Ra for assay by alpha-spectrometry and to determine ²²⁸Ra via the measurement of ²²⁸Ac by gas proportional counting. After preconcentration, the manganese dioxide is dissolved from the resin and passed through stacked Ln-Resin-DGA Resin cartridges that remove uranium and thorium interferences and retain ²²⁸Ac on DGA Resin. The eluate that passed through this column is evaporated, redissolved in a lower acidity and passed through Ln-Resin again to further remove interferences before performing a barium sulfate microprecipitation. The ²²⁸Ac is stripped from the resin, collected using cerium fluoride microprecipitation and counted by gas proportional counting. By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized.     

224Ra correction for determination of 226Ra in environmental materials

The most commonly available 226Ra determination was too time-consuming to be suited to 226Ra monitoring for the accidental release. The formula for determination of 226Ra was derived by 224Ra correction for WHO's equation. A rapid determination of 226Ra in environmental materials was made possible by using this formula. The 226Ra values of the soil and natural water at Ningyoh-Tohge obtained by the present method were in good agreement with those by the conventional WHO method. It was demonstrated that 226Ra of more than about 37 mBq (1 pCi) in the sample could be determined within 4 days by this method.     

Precise determination of the intensity of 226Ra alpha decay to the 186 keV excited state

There is a significant discrepancy in the reported values for the emission probability of the 186 keV gamma-ray resulting from the alpha decay of ²²⁶ Ra to 186 keV excited state of ²²² Rn. Published values fall in the range of 3.28 to 3.59 gamma-rays per 100 alpha-decays. An interesting observation is that the lower value, 3.28, is based on measuring the 186 keV gamma-ray intensity relative to the ²²⁶ Ra alpha-branch to the 186 keV level. The higher values, which are close to 3.59, are based on measuring the gamma-ray intensity from mass standards of ²²⁶ Ra that are traceable to the mass standards prepared by HÓNIGSCHMID in the early 1930's. This discrepancy was resolved in this work by carefully measuring the ²²⁶ Ra alpha-branch intensities, then applying the theoretical E2 multipolarity internal conversion coefficient of 0.692±0.007 to calculate the 186 keV gamma-ray emission probability. The measured value for the alpha branch to the 186 keV excited state was (6.16±0.03)%, which gives a 186 keV gamma-ray emission probability of (3.64±0.04)%. This value is in excellent agreement with the most recently reported 186 keV gamma-ray emission probabilities determined using ²²⁶ Ra mass standards.     

Marine radioactivity concentration in the Exclusive Economic Zone of Peninsular Malaysia: 226Ra, 228Ra and 228Ra/226Ra

The present occurrence of ²²⁶Ra and ²²⁸Ra in marine sediment core and fish from the Exclusive Economic Zone in the east coast of Peninsular Malaysia were studied. Sediment core and biota in respectively was collected using multicorer device and purchased from local fishermen at identified stations during the cruise expedition conducted in 2008. The purpose of this study was to determine and to make available an inventory of activity concentration levels and activity ratio for these radionuclides in this region. The activity concentrations of ²²⁶Ra and ²²⁸Ra in sediment core and edible part of fish were ranged between 15.9–46.5 and 27.7–87.1 Bq/kg dry wt and; 0.80–2.13 and <0.95–3.57 Bq/kg fresh wt, respectively. Meanwhile, the activity ratios of ²²⁸Ra/²²⁶Ra in sediment core and fish were varied with the range between 1.63–2.09 and 0.45–2.38, respectively. Refer to those ranges the activity concentrations of radium isotopes were comparable with other region. Thus, it can be concluded that the occurrence of radium isotopes mainly supplied from terrestrial sources and the factors of assimilation efficiency and transfer coefficient of radium may probably effect to the variation activity concentration of ²²⁶Ra and ²²⁸Ra and its activity ratio in edible part of pelagic and demersal fish obtained in this study.     

A new method for simultaneous determination of 226Ra and uranium in aqueous samples by liquid scintillation using chemometrics

In this work, simultaneous determination of low levels of ²²⁶Ra and uranium in aqueous samples were performed by alpha-liquid scintillation counting (LSC) in conjunction with artificial neural network (ANN) and partial least squares (PLS). The counting rates at 73 channels, which were selected by genetic algorithm, were used for training. A PLS model with four latent variables and a principle component ANN model (4-4-2) with linear transfer function after hidden and output layers were created. Total relative error of prediction for PLS and ANN in synthetic mixtures was 18.05% and 24.78%, respectively. The matrix effect was studied by spiking the real samples with radium and uranium. Laser induced fluorescence was used for assessment of uranium prediction results in real samples.     

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.     

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.     

Determination of226Ra and uranium in fish samples from waters of the Grand Canyon by alpha spectroscopy without electrodeposition

A previous paper reported the application of a method for determining²²⁶Ra by -spectroscopy. This paper presents important improvements which permit the determination of²²⁶Ra in the presence of large amounts of Ca. The method was applied to the analysis of²²⁶Ra and U isotopes in fish samples from the waters of the Grand Canyon.²²⁶Ra ranged from 0.05 Bq kg^–1 /1.4 pCi kg^–1/ to 0.17 Bq k^–1 /4.7 pCi kg^–1/.²³⁸U values ranged from 0.13 Bq kg^–1 /3.5 pCi kg^–1/ to 0.52 Bq kg^–1 /14 pCi kg^–1/ and²³⁴U values were between 0.23 Bq kg^–1 /6.2 pCi kg^–1/ and 12 Bq kg^–1/ /326. pCi kg^–1/.     

Development of a method for the determination of 226Ra by liquid scintillation counting

Liquid scintillation counting has not been widely applied to a-particle detection because of its poor energy resolution and variable background. In the present work, a time saving and reasonably accurate method for determination of ²²⁶Ra in water has been developed, using liquid scintillation spectrometry and pulse-shape analysis. The effect of three levels of chemical quench on the spillover of alpha interactions into the beta window and vice versa was assessed. The advantages of liquid scintillation in comparison with other methods (radon emanation) for determination of ²²⁶Ra are the high counting efficiency (~100%) and the easier sample preparation, with no need for sample preconcentration.     

222Rn (226Ra) determination in water by scintillation methods

A comparison between the counting parameters of solid and liquid scintillation methods for radon determination in water is attempted. The counting efficiency is better for a toluene-based liquid scintillator but, as the background is considerably higher than in solid scintillators, the figure of merit and the lower limit of the measurable activity are favorable for a scintillation counter based on zinc sulfide (Ag activated) scintillator.     

Direct determination of 226Ra in NORM/TENORM matrices by gamma-spectrometry

Summary The main shortcoming with the procedure to determine ²²⁶Ra in a gamma spectrum of an environmental sample by means of the ²¹⁴Bi and ²¹⁴Pb photopeaks is the likelihood of ²²²Rn leakage from the sample counting vial. An option to make such determination is to disregard the ²²⁶Ra gamma-contributions to the spectrum, other than 186.2 keV (3.5%), subtracting the ²³⁵U contribution to the ²²⁶Ra+²³⁵U peak at 186 keV. The use of this option to determine directly ²²⁶Ra activity concentrations in environmental samples and in NORM/TENORM matrices will be presented and discussed.     

Rapid method for determination of 228Ra in water samples

A new rapid method for the determination of ²²⁸Ra in natural water samples has been developed at the SRNL/EBL (Savannah River National Lab/Environmental Bioassay Laboratory) that can be used for emergency response or routine samples. While gamma spectrometry can be employed with sufficient detection limits to determine ²²⁸Ra in solid samples (via ²²⁸Ac), radiochemical methods that employ gas flow proportional counting techniques typically provide lower minimal detectable activity levels for the determination of ²²⁸Ra in water samples. Most radiochemical methods for ²²⁸Ra collect and purify ²²⁸Ra and allow for ²²⁸Ac daughter ingrowth for ~36 h. In this new SRNL/EBL approach, ²²⁸Ac is collected and purified from the water sample without waiting to eliminate this delay. The sample preparation requires only about 4 h so that ²²⁸Ra assay results on water samples can be achieved in <6 h. The method uses a rapid calcium carbonate precipitation enhanced with a small amount of phosphate added to enhance chemical yields (typically >90 %), followed by rapid cation exchange removal of calcium. Lead, bismuth, uranium, thorium and protactinium isotopes are also removed by the cation exchange separation. ²²⁸Ac is eluted from the cation resin directly onto a DGA Resin cartridge attached to the bottom of the cation column to purify ²²⁸Ac. DGA Resin also removes lead and bismuth isotopes, along with Sr isotopes and ⁹⁰Y. La is used to determine ²²⁸Ac chemical yield via ICP-MS, but ¹³³Ba can also be used instead if ICP-MS assay is not available. Unlike some older methods, no lead or strontium holdback carriers or continual readjustment of sample pH is required.