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.     

Massenspektrometrische Bestimmung von ppm-Mengen Thorium in Uranerzen durch Isotopenverdünnungsanalyse

Thorium is chemically separated from uranium ores in a non-quantitative way. In one sample the isotopic ratio ²³⁰Th/²³²Th is determined in a mass spectrometer. In another sample ionium is added as indicator for the isotopic dilution; the thorium of this particular sample is also analysed in a mass spectrometer. The content of ²³⁰Th and ²³²Th is calculated from the measurements of the isotopic ratios and the amount of the ionium indicator. The results are compared with the results obtained by other methods.     

Thorium series disequilibrium and geochemical processes in estuarine sediments of Mandovi river

The measurements of natural radioactivity due to thorium isotopes have been carried out in estuarine sediments of Mandovi river (Goa). The geochemical behaviour of these sediments has been studied by leaching the samples with 5 % ethylenediaminetetraacetic acid at pH 3.0 in order to investigate the processes occurring on the surface of the sediment particles and the distribution of natural thorium in estuarine sediments. The²²⁸Th/²³²Th activity ratios have been found to be in the range of 2.00 to 2.12. This anomaly between²³²Th and²²⁸Th has been attributed to the preferential leaching of²²⁸Ra by water flowing over these sediments. The activities of²²⁸Ra on the surface labile layers of the sediments have also been determined. The²³⁰Th/²³²Th activity ratios have been found to be in the range of 0.94 to 1.04. These ratios are mainly dependent on the precipitation action of²³⁰Th on adjacent sediments.     

Interlaboratory comoparison of analytical methods for the determination of natural series uranium and thorium isotopes in rock samples

Results are repoerted for²³⁸U,²³⁴U,²³²Th, and²³⁰Th determinations in 19 rock samples from a uranium mine, performed independently, byb three different laboratories. Uranium and thorium isotopoic activities were determkined by alpha spectrometry, after different pre-concentration and counting sample preparation techniques., Additionally, total concentrations of uranium were determined by fluorimetry and gamma spectreometry. the folloing conclusions could be drawn from this intercomparison test: (1) The results for²³⁸U specific activity agreed with the amjority of results within 10%. Lincar correlation coefficients between the three data sets were 0.999. However, for a few samples of much higher uranium concentrations, large deviations were observed, indicating problems of, sample heterogencity. (2) For the²³⁴U/²³⁸U activity ratio data, a still closer agreement was obtained (5%), as computation of the activity ratios did not, require information on the yield of the used tracer spike (²³²U). (3) The results for²³²Th specific activities and²³⁰Th/²³⁴U activity ratios showed larger deviastions between the three laboratories (typically up to 15%, in some cases still ore). Different Th-isotopes (²²⁸Th,²³⁴Th and²²⁹Th) have been used as yield tracers. The data indicates, however, that the observed deviations are not simply a consequence of a systematic difference in the calibration of the different spikes, but, probably cased by other errors such as incomplete sample dissolution, sample heterogencity, tec. The limitations of alpha spectrometry will be discussed and an application of the developed methods shown.     

Concentration of232Th,230Th and228Th in various tissues of Japanese subjects

The concentration of²³²Th,²³⁰Th and²²⁸Th in various human tissues of Japanese subjects obtained at autopsies are reported. The tissue samples were weighed, spiked with²³⁴Th tracer and ashed by acid. The solution was dried on a hot-plate. Separation of thorium radionuclides was accomplished through cation-exchange resin chromatography and electrodeposition. The concentrations of thorium isotopes were measured by -spectrometry. Thorium-232 and²³⁰Th concentrations were found to be highest in lung, followed by bone. The maximum concentration of²²⁸Th was in bone. The lowest concentrations of thorium isotopes were in muscle.     

Preparation and certification of new thorium isotopic reference materials

Preparation of two Isotopic Reference Materials of thorium has been performed, starting from highly enriched ²³²Th (99.99%) and ²³⁰Th (99.8%). After full characterization (chemical and isotopic) of these purified base materials the thorium nitrate was transformed to thorium dioxide. Accurately weighed amounts of the two isotopes in the dioxide form were subsequently dissolved in nitric acid and resulted in solutions with amount ratios n(²³⁰Th)/n(²³²Th) close to 10^–5 (IRMM-035) and 3 · 10^–6 (IRMM-036). These gravimetrically prepared ratios were finally verified by means of Thermal Ionization Mass Spectrometry (TIMS). The purpose of the Reference Materials is to calibrate thorium isotope amount ratio measurements. Received: 7 July 1997 / Revised: 1 December 1997 / Accepted: 7 December 1997     

Preparation and certification of new thorium isotopic reference materials

Preparation of two Isotopic Reference Materials of thorium has been performed, starting from highly enriched ²³²Th (99.99%) and ²³⁰Th (99.8%). After full characterization (chemical and isotopic) of these purified base materials the thorium nitrate was transformed to thorium dioxide. Accurately weighed amounts of the two isotopes in the dioxide form were subsequently dissolved in nitric acid and resulted in solutions with amount ratios n(²³⁰Th)/n(²³²Th) close to 10^–5 (IRMM-035) and 3 · 10^–6 (IRMM-036). These gravimetrically prepared ratios were finally verified by means of Thermal Ionization Mass Spectrometry (TIMS). The purpose of the Reference Materials is to calibrate thorium isotope amount ratio measurements. Received: 7 July 1997 / Revised: 1 December 1997 / Accepted: 7 December 1997     

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.     

Development and validation of a methodology for uranium radiochronometry reference material preparation

The paper describes a methodology for a reference material preparation to be used for the determination of the production date (i.e. the time elapsed since the last chemical processing) of uranium materials based on the ²³⁰Th/²³⁴U radiochronometer. The reference material was prepared from highly enriched uranium by a complete separation of thorium decay products, thus zeroing the initial daughter nuclide concentration at known time. The complete elimination of thorium from the starting material was verified by gamma spectrometric measurements and by addition of a ²³²Th tracer to the material and its re-measurement in the final product after the separation. The validation of the methodology was carried out subsequently by comparing the ingrown daughter nuclide ²³⁰Th and the measured ²³⁰Th/²³⁴U ratio after recorded times following the last chemical separation with the calculated values obtained on the basis of their respective half-lives. The prepared reference material can be used as a quality control material for age determination of uranium in nuclear forensics and safeguards as well as for method validation.     

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 Uranium and Thorium Isotope Ratios by Inductively Coupled Plasma Mass Spectrometry

Measurement conditions were selected and a procedure was proposed for determining the ²³⁴U/²³⁸U and ²³⁰Th/²³²Th isotope ratios using an ELEMENT single-channel double-focusing inductively coupled plasma mass spectrometer. The procedure was tested in analyzing bottom sediments from Lake Baikal with the extraction preconcentration of uranium and thorium. The accuracy of the procedure was verified using certified reference materials and a model solution by comparing the results obtained with the data of spectrometry.     

Separation of thorium from uranium ore

Thorium-230 has many research applications, but there is not a commercial source of this isotope. However, since ²³⁰Th is part of the ²³⁸U decay chain, it can be separated from naturally occurring uranium. In this work, a novel procedure was developed to separate thorium from uranium ore, consisting of leaching, liquid–liquid extraction, precipitations and ion exchange chromatography. The final product was 91.32?±?0.77 mg of thorium with a purity of 99.5?±?1.2 wt%. Of that, 7.65?±?0.10 mg was ²³⁰Th and the remainder ²³²Th. The total yield of ²³⁰Th was 71.1?±?5.4%. Ways to improve the yield by further processing the back-extraction solution are suggested.

     

Determination of uranium and thorium isotopes in mineral spring waters

Concentrations levels of uranium and thorium isotopes have been analyzed in the m mineral spring waters of a high background region of Brazil: Poços de Caldas and Águas da Prata. The procedure was based on the determination of²³⁸U,²³⁴U,²³²Th,²³⁰Th and²²⁸Th by -spectrometry after separation and purification of the isotopes of interest by using anion-exchange chromatography and preparation of the samples for -measurements by electrodeposition. The concentration varied from <1.1 to 28.4 mBq.l^–1 and from <1.6 to 141 mBq.l^–1 for²³⁸U and²³⁴U, respectively. Thorium isotope measurements varied from <0.2 to 1.8 mBq.l^–1 from <0.3 to 4.9 mBq.l^–1 and from <0.8 to 19.9 mBq.l^–1 for²³²Th,²³⁰Th and²²⁸Th, respectively. Calculations of thorium and uranium isotopic activity ratios were carried out giving values ranging from 1.9 to 7.2, from 1.2 to 3.0 and from 7.7 to 15.3 for²³⁴U/²³⁸U,²³⁰Th/²³²Th and²²⁸Th/²³²Th, respectively. The effective doses due to the intake of²³⁸U and²³⁴U present in these waters are expected to reach values up to 1.4×10^–3 mSv y^–1 and 8.0×10^–3 mSv y^–1, respectively.     

Natural radioactivity in bioassay by alpha-spectrometry measurements

Personnel of nuclear facilities are checked regularly for internal contamination by bioassay measurements. Although these persons are generally not involved in any incident, natural radioactivity from U, Th and Ra can be found in their urine or faeces. Uranium total activity in urine has been found with a range of 0.051 to 3.0 mBq/24 h and in faeces from 14.5 to 380 mBq/d. ²³⁴U/²³⁸U ratio for urine is 1.48 but this ratio varies from 0.47 to 19. By comparison, the ²³⁴U/²³⁸U ratio found in urine from workers in volved with natural uranium or 4.5% enriched uranium is 1.0 and around 4.0 respectively. ²³⁰Th, ²²⁸Th and sometimes ²³²Th have also been detected. The total thorium activity varies from 0.137 to 5.6 mBq/24 h in urine and from 9 to 183 mBq/d in faeces. ²²⁸Th has generally been found in excess of ²³²Th. All these measurements were performed by alpha-spectrometry. The few ²²⁶Ra results have been measured using the Lucas or emanation method.     

Behavior of uranium and thorium isotopes in soils of the Boréon area, Mercantour Massif (S.E. France): Leaching and weathering rate modeling

Four cores were collected in weathered rocks and soils in the Boréon forest area (1765 m, Mercantour Massif, France). The samples were analyzed for the isotopes ²³⁰Th, ²³²Th, ²³⁴U and ²³⁸U. The activity and isotopic ratio profiles suggest that uranium was mobilized (leaching and precipitation) during the weathering process, as well as thorium but in a much less proportion. A model was drawn up to evaluate the U leaching rate and the time that some levels of the weathered rocks have been subjected to weathering. It utilizes LATHAM and SCHWARCZ’s two equations,¹⁵ expressed as ²³⁴U/²³⁸U and ²³⁰Th/²³⁸U activity ratios, which assume that the alpha recoil effect allows easier leaching for ²³⁴U than ²³⁸U and no Th mobility. But this last assumption does not correspond to the observations made in the Boréon area, since it appears that in some soil deeper layers ²³⁰Th and ²²⁸Th are in radioactive deficit relatively to their parents. As there are four unknown quantities (the time, the leaching rates of ²³⁸U, ²³⁴U, ²³⁰Th), the problem to be solved requires two more equations; these can be obtained utilizing the U activity ratio in water, and taking into account the ²³²Th behavior. In some sites the ²³⁸U leaching rate is high in deeper soil levels (near the fresh rocks); this would correspond to a loss of half the U amount in less than 24 000 years.     

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.     

Radioactive series disequilibria in underground uranium deposits of the Singhbhum Shear Zone, Eastern India

Radionuclides of the ²³⁸U series (²²⁶Ra, ²¹⁰Pb, ²³⁴Th and ²³⁴U), ²³⁵U series (²²⁷Ac and ²³¹Pa) and ²³²Th series (²²⁸Th and ²²⁸Ra) series were measured by High Resolution Gamma Spectrometry system in twenty-five uranium ore samples from underground uranium deposits in the Singhbhum Shear Zone of Eastern India. The activity concentrations were observed to vary within a wide range in most of the deposits, as is the case in most rocks of crustal origin. The uranium ore from these deposits were not of high ore grade (U concentrations ranged from 0.015 to 0.082%). Activity ratios of key daughter–parent pairs from the decay chains, viz. ²²⁶Ra/²³⁸U, ²²⁶Ra/²¹⁰Pb, ²³¹Pa/²³⁵U, ²²⁷Ac/²³⁵U, ²³⁰Th/²³⁸U, ²³⁴U/²³⁸U, ²²⁶Ra/²³⁰Th and ²²⁸Th/²²⁸Ra indicated migration/accumulation of uranium and radium in some samples. The ²²⁶Ra/²³⁰Th ARs suggested that the deposits were not closed to groundwater movement for a maximum time period of 8ky. Thiel plot of the ²³⁴U/²³⁸U vs. ²³⁰Th/²³⁸U activity ratios indicated uranium accumulation and complex processes of uranium redistribution.     

Synthetic mixtures of thorium isotopes

A series of synthetic mixtures of thorium isotopes was prepared on a gravimetrical basis. The starting compounds consisted of natural thorium ²³²Th (99.99%) and highly enriched ²³⁰Th (99.8%). These materials were chemically purified and characterized for isotopic composition and chemical purity. Thorium dioxide (ThO₂) was demonstrated to be a suitable compound for gravimetrical blending. The isotope amount ratios in the mixtures ranged from 10⁻² to 3 × 10⁻⁶. These synthetic isotope mixtures are to our knowledge, the first ever prepared for thorium and may serve for calibration purposes.     

The microenvironment of iron in (Ba,Ca)(Fe,Co)O3−δ catalyst system: A Mössbauer study

Undisturbed, non-fertilized woodland soil (“loamy sandy soil” type) from 1 m below surface was dry and wet sieved. Sieving fractions of <10–1000 μm were analyzed for total alpha-activity. Thorium and uranium contents were determined by alpha-spectrometry after radiochemical separation. Soluble and insoluble parts of thorium and uranium were determined in the sieved fractions indicating that the isotope distribution in soil correlates with the particle size distribution: The smaller the size fraction the higher the isotope content. Isotope ratios of²²⁸Th/²³²Th, and²³⁴U/²³⁸U are discussed.