Determination of228Th,230Th,and232Th in environmental samples from uranium mining and milling operations

A method is described for the determination of²²⁸Th,²³⁰Th, and²³²Th in environmental samples from uranium mining and milling operations. The analytical procedure is based on the direct determination of²²⁸Th in the sample by high resolution γ-spectrometry followed by extraction and purification of the thorium fraction using high molecular weight amines and an anion-exchange technique, respectively, prior to α-spectrometry to determine isotopic ratios. The lowest level of detection for each thorium isotope is 0.01 pCi/g for solid samples and 20 pCi/l for aqueous samples. Replicate analyses of a typical mine waste stream gave a standard deviation of ±3% for²²⁸Th. Standard deviations of the²³⁰Th and²³²Th increased to ±11% apparently due to traces of²¹⁰Po interfering in the α-spectrometry.     

Radioactivity of coal and ashes from Figueira coal power plant in Brazil

Summary The Figueira coal-fired power plant (CFPP) is among the Brazilian CFPP which presents higher uranium concentration. Gamma-ray spectrometry was used to determine ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²³² Th and ⁴⁰K contents in pulverized coal, furnace bottom ash and fly ash samples. The natural radionuclide concentrations in pulverized coal ranged from 813 to 2609 Bq ^. kg^-1 for U series and from 22 to 40 Bq ^. kg^-1 for ²³² Th. The fly ash fraction gave concentrations ranging from 1442 to 14641 Bq ^. kg^-1, for uranium series. The same enrichment factor was observed for ²³⁸U, ²²⁶Ra and ²³² Th. Only ²¹⁰Pb and stable Pb presented a high enrichment factor for the last stage filter fly ash. The concentration of the uranium series found in the ashes is close to the limit adopted by the Brazilian guideline (CNEN-NN-4.01).²² Therefore, it is advisable to evaluate the environmental impact of the installation.     

Effect of humic acid,pH and ionic strength on the sorption of Eu(III) on red earth and its solid component

A highly sensitive separation procedure has been developed to investigate uranium and thorium activities and their isotopic ratios in environmental water samples in Tokushima, Japan. Uranium and thorium isotopes in environmental water samples were simultaneously isolated from interfering elements with extraction chromatography using an Eichrom UTEVA™ resin column. After the chemical separation, activities of U and Th isotopes coprecipitated with samarium fluoride (SmF₃) were measured by α-spectrometry. It has been confirmed that uranium isotopes are isolated successfully from thorium decay chains by analyzing a test aqueous solution as a simulation of an environmental water sample. The separation procedure has been first applicable to the determination of U and Th activities and their isotopic ratios in a drinking well water named “Kurashimizu” in Tokushima City, Japan. The specific activities of ²³⁸U and ²³²Th in “Kurashimizu” were deduced to be within the upper limits of <0.31 and <0.19 mBq/l, respectively.     

Studies on226Ra and210Pb activities and the concentration factors of226Ra in the surface organic layers of the estuarine sediments of Mindola and Purna rivers in India

The sediment samples have been collected from estuarine regions of Mindola and Purna of Gujarat State. These samples are found to contain less than 3% of organic matter which scavange and carry most of the activity of²²⁶Ra, etc., to the sediment floor. The activities of²²⁶Ra are found to vary from 0.1 to 0.5 pCi/g, while²¹⁰Pb activities lie in the range of 3 to 8 pCi/g. These activities find their way into the organisms present in sea water and then into fish which is finally consumed by humans. This paper gives in detail the sampling techniques, experimental procedures and the distribution of the isotopes of²²⁶Ra and²¹⁰Pb in the estuarine regions and the concentration factors of²²⁶Ra in the region.     

Development of a sequential method for the determination of238U,234U,232Th,230Th,228Th,228Ra,226Ra,and210Pb. in environmental samples

A sequential analytical method for the determination of²³⁸U,²³⁴U,²³²Th,²³⁰Th,²²⁸Th,²²⁸Ra,²²⁶Ra and²¹⁰Pb in environmental samples was developed. Uranium and thorium isotopes are first chromatographically sepaaated using tri-n-octyl phosphine oxide (TOPO) supported on silica gel. The uranium isotopes are determined by alpha-spectrometry following extraction with TOPO onto a polymeric membrane. Thorium isotopes are co-precipitated with lanthanum fluoride before counting in an alpha spectrometer. Radium isotopes and²¹⁰Pb are separated by co-precipitation/precipitation with mixed barium/lead sulphate. Radium-226 is determined by gross alpha counting of the final BaSO₄ precipitate and²²⁸Ra by gross beta counting of the same source. Lead-210 is determined through beta counting of its daughter product²¹⁰Bi.     

Investigation of radioactive lead,uranium, and thorium in environmental waters by extraction chromatography resins

A time-saving and sensitive method for monitoring low concentration (activities) of ²¹⁰Pb, ²³²Th, and ²³⁰Th and ²³⁸U, ²³⁴U, and ²³⁵U in water samples has been developed. Through the combination of co-precipitation and extraction chromatography by 3M RAD disks and UTEVA (Eichrom) columns effective radiochemical separation of the analytes was carried out. Thorium and uranium activities were determined by alpha spectrometry and lead activity by LSC, respectively. The minimal detectable activities obtained were 0.6?Bq?m^?3 for uranium, 0.29?Bq?m^?3 for thorium, and 2.5?Bq?m^?3 for ²¹⁰Pb. More than 150 different waters were analysed for uranium content and only 30 for lead and thorium. The investigations are still in progress.     

Determination of alpha-emitting isotopes of uranium and thorium in vegetables and excreta

A radiochemical procedure for the determination of alpha-emitting isotopes of uranium and thorium in vegetables and excreta has been optimized, involving sample dissolution, separation by ionic exchange resin, electrodeposition and alpha-spectroscopy. Uranium and thorium isotopes were determined separately to prevent interference of ²²⁸Th from ²³²U tracer with ²²⁸Th from natural series of 232Th. This procedure was applied to faeces from people living in the Poços de Caldas plateau, a high natural radioactivity region of Brazil, and vegetables from the Laboratory of Environmental Monitoring (EML/DOE). Results show a chemical recovery of 80–95% for uranium and 46–72% for thorium.     

Extraction Preconcentration of Uranium and Thorium Traces in the Analysis of Bottom Sediments by Inductively Coupled Plasma Mass Spectrometry

A procedure was developed for determining trace amounts of uranium and thorium isotopes in bottom sediments from Lake Baikal. This procedure involves sample decomposition, the coextraction of uranium and thorium with trioctylphosphine oxide, the quantitative back extraction after diluting the extract with caprylic acid, and the ICP MS analysis of the back extract. The procedure was verified by analyzing a BIL-1 Lake Baikal bottom silt standard reference material using the developed procedure and independent methods. The detection limits of abundant uranium and thorium isotopes are restricted by blank measures and equal to 1 × 10^–7 mass %. The detection limits for²³⁴U and ²³⁰Th are 4 × 10^–10 and 6 × 10^–10 mass %, respectively.     

Radioactive radium and lead isotopes determinations in biota samples

²¹⁰Pb and radium’s isotopes were determined in biota samples by two different radiochemical techniques—Fe(OH)₃ co-precipitation and calcium phosphate precipitation. The applied procedures were adapted for very small amount (0.25 g) of sample material and were checked in actual biota samples. Measurements were made by liquid scintillation counting, α- and γ-spectrometry. All the results show that Ca₃(PO₄)₂ precipitation technique is better for determination of trace radionuclide concentrations in biota. The procedure of separation is stable with significant yield for the both ²¹⁰Pb and radium’s isotopes and can be successfully used for assessment of environmental stressors in field of bio-monitoring.     

A modified method for the sequential determination of 210Po and 210Pb in Ca-rich material using liquid scintillation counting

This research describes methods for the sequential determination of ²¹⁰Pb and ²¹⁰Po activity concentrations in Ca-rich ash samples collected from oil shale-fired power plants in Estonia. The procedure involves digestion of Ca-rich ash samples in a microwave digestion system, radiochemical separation of ²¹⁰Pb and ²¹⁰Po and their measurements. All samples, blanks and standards were measured by liquid scintillation counting (Quantulus 1220). The method was tested using IAEA (International Atomic Energy Agency) RGU-1 and IAEA-444 reference materials. Spectral calibration/peak identification which included the optimization of α/β discrimination system (pulse shape analyser), and recovery have been made by ²⁰⁹Po and ²¹⁰Pb standard solutions.

     

Determination of thorium,uranium and plutonium isotopes in atmospheric samples

A new procedure for the radiochemical measurements of thorium, uranium and plutonium in atmospheric samples is described. Analysis involves coprecipitation of these actinides with iron hydroxide from a 40-to 50-dm³ sample of rainwater, followed by radiochemical separation and purification procedures by the use of ion exchange chromatography (Dowex AG1×8) and solvent extraction. The new procedure enables one to determine the isotopes of thorium, uranium and plutonium, which are found in rainwater at extremely low concentrations, with a chemical yield ranging from 60 to 80%.     

Analytical methods for the characterization and the leachability evaluation of a solid waste generated in a phosphoric acid production plant

Naturally Occurring Radioactive Materials (NORM) are present in the environment and can be concentrated by technical activities, particularly those involving natural resources. These NORM deposits are highly stable and very insoluble under environmental conditions at the earth's surface. However reducing or oxidant conditions or pH changes may enable a fraction of naturally occurring radionuclides to eventually be released to the environment. In this paper the analytical methods to determine the chemical and radiochemical composition of a solid waste generated in an acid phosphoric production plant was shown. The sample, analysed by gamma spectrometry and radiochemical methods, contained ²¹⁰Pb and ²¹⁰Po and a high activity concentration of uranium isotopes but it shows a very low quantity of ²²⁶Ra. Also a sequential extraction method consisting of five operationally-defined fractions was used to evaluate the leachability of uranium isotopes, ²¹⁰Pb and ²¹⁰Po. The average leaching potential observed in the sample is 97.6% for ²³⁸U, 93.2% for ²¹⁰Pb and 82.4% for ²¹⁰Po. Moreover the results show that ²¹⁰Pb and ²¹⁰Po are leachable under only extreme conditions, whereas uranium is very more soluble.     

Determination of210Pb and210Po in human tissues of Japanese

To determine the levels of²¹⁰Pb and²¹⁰Po in human tissues of people in Japan, various tissue samples were obtained at autopsy from the cadavers of 22 oncologic cases, mainly in Niigata Prefecture in northern Japan, from 1986 to 1988.Wet ashing, followed by electrochemical deposition and alpha spectrometry were used to separate and determine the²¹⁰Pb and²¹⁰Po present. Among the tissues analyzed, the highest concentrations of²¹⁰Pb and²¹⁰Po were observed in bone (sternum), liver, and kidneys. The total body burden of²¹⁰Pb and²¹⁰Po was found to be approximately 427 pCi and 514 pCi, respectively. This estimated²¹⁰Po value did not differ significantly from values found in populations in the U.S.A. and European countries.     

Non-destructive determination of uranium and thorium in geological materials by resonance-neutron activation analysis

A simple method is described for the determination of uranium and thorium in gological materials. The samples are irradiated in a reactor with resonance and fast neutrons behind a cadmium filter. Compared with an irradiation with the whole reactor neutron spectrum, the matrix activities are reduced to about 1%, those of uranium (²³⁹Np) and thorium (²³³Pa) to about only 50 and 25%, respectively. This relative diminution of matrix activities allows the γ-measurement of²³⁹Np and²³³Pa as early as after two days' cooling time; in samples with high uranium contents the determination of²³³Pa requires one month's cooling time. This non-destructive procedure yields a detection limit of 0.1 ppm for uranium and thorium in samples of 200 mg, with an error of ±5%. Dedicated to ProfessorW. Borchert on the occasion of his 60th birthday.     

Precise isotope ratio measurements for uranium, thorium and plutonium by quadrupole-based inductively coupled plasma mass spectrometry

Precise long-term measurements of uranium and thorium isotope ratios was carried out in 1 μg/L solutions using a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS). The isotopic ratios of uranium (²³⁵U/ ²³⁸U = 1, 0.02 and 0.00725) were determined using a cross-flow nebulizer (CFN, at solution uptake rate of 1 mL/min) and a low-flow microconcentric nebulizer (MCN, at solution uptake rate of 0.2 mL/min) over 20 h. For 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) relative external standard deviations (RESDs) of 0.05% and 0.044% using CFN and MCN, respectively, can be achieved. Additional short term isotope ratio measurements using a direct injection high-efficiency nebulizer (DIHEN) of 1 μg/L uranium solution (²³⁵U/²³⁸U = 1) at a solution uptake rate of 0.1 mL/min yielded an RSD of 0.06–0.08%. The sensitivity of solution introduction by DIHEN for uranium, thorium and plutonium (145 MHz/ppm, 150 MHz/ppm and 177 MHz/ppm, respectively) increased significantly compared to CFN and MCN and the solution uptake rate can be reduced to 1 μL/ min in DIHEN-ICP-MS. Isotope ratio measurements at an ultralow concentration level (e.g. determination of ²⁴⁰Pu/ ²³⁹Pu isotope ratio in a 10 ng/L Pu waste solution) were carried out for the characterization of radioactive waste and environmental samples. Received: 1 December 1998 / Revised: 25 January 1999 / Accepted: 31 January 1999     

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil has been developed. Analysis involves total dissolution of the samples to allow equilibration of the natural isotopes with added tracers, followed by radiochemical separation using anion exchange chromatography (BioRad AG 1–X8). Further separation and purification is performed employing solvent extraction techniques. Finally, the U and Th fractions are co-precipitated with lanthanum and cerium fluoride, respectively, and quantified by alpha-particle spectrometry. Overall chemical yields range from 60 to 90%. Under normal operating conditions and present counting set up, the minimum detectable concentration (MDC) is approximately 2 Bq/kg for soil samples. This is based on one gram aliquot of sample, 80% chemical yield, and 1000 minute counting with a detector having about 15% counting efficiency. The procedure has been successfully tested with Standard Reference Materials. Various soil samples were analyzed with high chemical yields and fine quality of alpha-spectra. Decontamination factor studies were performed to determine the extent of the carry over of²¹⁰Po,²²⁵Ac,²²⁶Ra, and²²⁹Th into U fraction and²¹⁰Po,²²⁵Ac,²²⁶Ra, and²³²U into Th fraction.     

The determination of mercury by non-flame atomic absorption and fluorescence spectrometry.

An isotopic dilution method has been developed for the determination of ²²⁶Ra and ²²⁸Ra in sea water and sediments with ²²³Ra as a yield tracer. An alternative procedure which obviates the need for ²²³Ra is demonstrated for sediments by the assay of ²²⁴Ra and ²²⁸Th which occur naturally in sediments. In addition, a direct method for β-counting ²²⁸Ra–²²⁸Ac is proposed. Radium, polonium, thorium and uranium isotopes and ²¹⁰Pb are coprecipitated from sea water with aluminum phosphate carrier. The radium and lead-210 are coprecipitated with lead nitrate in sediment leachings. All radium procedures utilize identical chemical isolation and the cathodic electrodeposition of radium. Subsequently, the α-radiation emitted by ²²⁶Ra, ²²³Ra and ²²⁴Ra is determined by pulse-height analysis: the ²²⁸Ra-²²⁸Ac and ²¹⁰Pb-²¹⁰Bi are measured by low background anticoincidence β-counting techniques. This method was used for samples containing 10^-11–0.5 · 10^-12 g of ²²⁶Ra and 10^-13–10^-15 g of ²²⁸Ra and gave a precision of 3–6% and 5–10% respectively, even though radium levels an order of magnitude less can be measured. The ²²⁶Ra method is applicable to all environmental samples, whereas ²²⁸Ra determinations are limited to applications where the ${}^{228}\text{Ra}{}^{226}\text{Ra}$ activity ratio is greater than 0.1. This method is especially attractive for studies of parent-daughter disequilibria.     

Natural radionuclides and 137Cs activity concentration in the bottom sediment cores from Kuwait Bay

Summary The activity concentration of natural radionuclides and ¹³⁷Cs in the bottom sediments cores from Kuwait Bay have been determined by γ-ray spectrometry. Particular attention was devoted to the exact determination of two uranium isotopes: ²³⁵U and ²³⁸U in order to find any presence of depleted uranium dispersed during the 1991 Gulf War. The calculated ²³⁸U/²³⁵U activity ratios for all the surface (15 cm) as well as the core profile (up to 70 cm in depth) samples were within the limit of one standard deviation close to the value of 21.5 for natural uranium. Simultaneous instrumental determination of the unsupported ²¹⁰Pb and ²²⁶Ra in a few sediment core profiles was used for quantification of sediment accumulation rates. The calculated sedimentation rates (for the constant atmospheric ²¹⁰Pb flux rate - CRS model) ranged from 0.2 to 0.6 cm ^. y^-1 and were close to the data calculated by the Weibull distribution of ¹³⁷Cs in undisturbed sediment cores.     

Determination of 210Po and uranium in high salinity water samples

A method for the determination of uranium and ²¹⁰Po in high salinity water samples has been elaborated. Both radionuclides are preconcentrated from 0.5 dm³ saline media by co-precipitation with hydrated manganese dioxide, followed by dissolution of the precipitate in 200 mL of 1 M HCl. Uranium isotopes ²³⁵U and ²³⁸U can be directly determined by ICP MS method with a detection limit of 0.01 ppb for ²³⁸U. Prior to a selective determination of ²¹⁰Po, the majority of other naturally occurring α-emitting radionuclides (uranium, thorium and protactinium) can be stripped from this solution by their extraction with a 50% solution of HDEHP in toluene. Finally, ²¹⁰Po is simply separated by direct transfer to an extractive scintillator containing 5% of trioctylphosphine oxide in Ultima Gold F cocktail and determined by an α/β separation liquid scintillation technique with detection limit below 0.1 mBq/dm³.     

Extraction of thorium,uranium and cerium from fresh water using manganese dioxide coprecipitation

A manganese dioxide coprecipitation procedure is utilized to replace a time-consuming evaporation step for the extraction of thorium, uranium and cerium from freshwater samples. The average recovery for 20-liter samples is greater than 95% for²³⁴Th and¹⁴⁴Ce. The data indicate that the manganese dioxide coprecipitation process does not affect the recovery of thorium and uranium during our routine analytical procedure.