Application of gamma-ray spectrometry for the assay of uranium in crude UF4—An input material used for producing nuclear grade U-metal at the natural uranium conversion plants

A -spectrometric method has been developed for the assay of uranium in crude UF₄, which is used as a secondary source of input material for producing nuclear grade U-metal at natural uranium conversion plants. The method makes use of a NaI (Tl) detector coupled with a multichannel analyzer. The 1 MeV -ray of²³⁸U is used for calibration. A method for the fabrication of uniform -assay calibration standards is also suggested, based on the results of this investigation. The calibration standards were prepared by soaking the matrix in uranium solution and then drying the whole material. The amount of²³⁸U in the crude UF₄ sample was directly estimated by comparing the areas under the 1 MeV -ray peak of known calibration standards with the corresponding areas of the samples to be measured. 100 g each of the standard and the sample were counted. 5 crude UF₄ samples were analyzed by this method. The uranium contents in these samples were found to be in the range of 12.2–28.7 g. To compare the -ray spectrometry results with a completely independent method, chemical analysis by potentiometry of all the samples was also done. The -spectrometric results were found to agree within ±18% with the chemical analysis results.     

Sediment dating and groundwater residence time in the lower basin of the Var river by radiochemistry and γ-ray spectrometry methods

A method for dating sediment core layers from the Var riverbed was developed. The signature of the Chernobyl event was detected in the layer sequence by γ-ray spectrometry of ¹³⁷Cs and correlated to the flow amplitude from the historical records.The residence time of groundwater in the aquifer of the lower Var valley was determined by measuring activity ratios of radium isotopes in well water samples.     

Measurement of uranium in small quantities in phosphates by use of γ-ray spectrometry and the 1001 keV peak of <Superscript>234m</Superscript>Pa

Phosphates, naturally containing trace amounts of uranium, were examined using direct γ-ray spectrometry. Both normal and Compton-suppressed counting modes were utilized. The 1001 keV photo peak of the second daughter of ²³⁸U was chosen because of its isolation from other, potentially interfering peaks. The findings suggest that with the aid of Compton suppression, it is possible to quantify low uranium levels in phosphates using samples sizes of order 10 grams within an accuracy of 5%. The uranium content was determined in several sample types and was found to range from 60±4 to 70±8 μg/g, depending on the sample composition. This investigation also considered the effects of sample size, counting time, and counting technique as sources of precision maximization. This work has shown that only a small amount of phosphate is needed to determine the constituent concentration, instead of the standard several hundred grams of material.     

Estimation of the uncertainty components associated with the measurement of radionuclides in air filters using γ-ray spectrometry

This paper discusses and assesses the major sources of uncertainty arising in measurement of radionuclide activity concentrations in air. Besides counting statistics, the main contributors to the overall uncertainty of the activity concentration of long-lived radionuclides are the heterogeneities of the calibration source and the test samples (approximately 4%). In addition, in the case of radionuclides with half-lives of the order of days or shorter, a significant uncertainty results from the variability of the source term because the peak concentration of the radionuclide might occur either at the beginning or at the end of the sampling period. For¹³¹I (T_1/28 days), for instance, the relative standard uncertainty was estimated as 17% owing to this effect. In addition, the uncertainty introduced by the software used for evaluation of the -ray spectra is discussed. Details of the uncertainty components, including their assessed probability distributions and degrees of freedom, and the conversion into standard uncertainties are reported in this paper, following the ISO Guide to the expression of uncertainty in measurement. A standard form for documenting and reporting the uncertainty budged is proposed and illustrated with an example.     

Effect of humic acid on absorption-release processes in the bottom sediments-Yenisei river water system as studied by dual-column ion chromatography and γ-ray spectrometry

The effect of humic acid on absorption-release processes in the bottom sediments-Yenisei river water system was studied by dual-column ion chromatography and γ-ray spectrometry. With the use of ion chromatography, it was found that processes related to the absorption of SO ₄ ^2? and Cl^? anions by a solid phase with the release of NO ₃ ^? , PO ₄ ^3? , and F^? to a liquid phase competed in the test systems as the concentration of water-soluble organic carbon (WSOC) was increased. Only the test anions were released in the systems without the introduction of an additional amount of WSOC as humic acid. With the use of γ-ray spectrometry, it was found that the release of ⁶⁰Co, ¹⁵²Eu, and ²⁴¹Am radionuclides to the liquid phase in the systems with added humic acid began much earlier than in the system without the addition of humic acid. In this case, the amount of released radionuclides was greater than the amount of radioisotopes released in the system without the addition of humic acid: ～25% ²⁴¹Am, ～3% ¹⁵²Eu, and ～0.8% ⁶⁰Co in the system with added humic acid or 0.8% ¹⁵²Eu and <0.1% ⁶⁰Co in the system without the addition of humic acid. The ²⁴¹Am radionuclide was not determined in the system without the addition of humic acid. An increase in the concentration of WSOC in the experimental system of bottom sediments-Yenisei river water initiated the release of ⁶⁰Co, ¹⁵²Eu, and ²⁴¹Am anthropogenic radionuclides from bottom sediments because of the formation of soluble complexes capable of migration. An increase in the concentration of WSOC had almost no effect on the release of ⁴⁰K and ¹³⁷Cs radionuclides.     

A semi-empirical method for calculation of true coincidence corrections for the case of a close-in detection in γ-ray spectrometry

In this paper, a semi-empirical method is proposed to determine true coincidence-summing (TCS) correction factors for high resolution γ-ray spectrometry. It needs the knowledge of both full energy peak (FEP) efficiency and total-to-peak (TTP) efficiency curves. The TTP efficiency curve is established from the measurements with a set of coincidence-free point sources. Whereas for a volume source, the coincidence-free FEP efficiency curve is obtained iteratively by using the peaks from almost the coincidence-free nuclides and those from the coincident nuclides in the mixed standard sources. Then the fitting parameters obtained for both TTP and FEP efficiency curves are combined in a freely-available TCS calculation program called TrueCoinc, which yields the TCS correction factors required for any nuclide. As an application, the TCS correction factors were determined for the particular peaks of ²³⁸U, ²²⁶Ra and ²³²Th in the reference materials, measured in the case of a close-in detection geometry using a well-type Ge detector. The present TCS correction method can be applied without difficulty to all Ge detectors for any coincident nuclide.     

Determination of uranium in urine – measurement of isotope ratios and quantification by use of inductively coupled plasma mass spectrometry

For analysis of uranium in urine determination of the isotope ratio and quantification were investigated by high-resolution inductively coupled plasma mass spectrometry (HR ICP-MS). The instrument used (ThermoFinniganMAT ELEMENT2) is a single-collector MS and, therefore, a stable sample-introduction system was chosen. The methodical set-up was optimized to achieve the best precision for both the isotope ratio and the total uranium concentration in the urine matrix.Three spiked urine samples from an European interlaboratory comparison were analyzed to determine the (235)U/(238)U isotope ratio. The ratio was found to be in the range 0.002116 to 0.007222, the latter being the natural uranium isotope ratio. The first ratio indicates the abundance of depleted uranium.The effect of storage conditions and the stability for the matrix urine were investigated by using "real-life" urine samples from unexposed persons in the Netherlands. For samples stored under refrigeration and acidified the results (range 0.8 to 5.3 ng L(-1) U) were in the normal fluctuation range whereas a decrease in uranium concentration was observed for samples stored at room temperature without acidification.     

Determination of U and Th in soil and plants obtained from a high natural radiation area in China using ICP-MS and γ-counting

This study was carried out for the determination of ²³⁸U and ²³²Th concentrations in soil and various foods obtained in high natural radiation areas in China for estimating the internal radiation doses caused by these radionuclides. Knowledge of the daily dietary intakes of the nuclides through foods is essential to evaluate the internal radiation dose. Several analytical methods were evaluated for their applicability and quality assurance. The accuracy and precision of ICP-MS is considerably better for determining trace elements like U and Th in fine powder samples. The estimated annual effective dose is 0.302 μ Sv/y for ²³⁸U and 1.86 μ Sv/y for ²³²Th in the high natural radiation area, and 0.0101 μ Sv/y for ²³⁸U and 0.177 μ Sv/y for ²³²Th in the control area.     

Determination of microcystins in natural blooms and cyanobacterial strain cultures by matrix solid-phase dispersion and liquid chromatography–mass spectrometry

An analytical procedure based on matrix solid-phase dispersion (MSPD) and liquid chromatography–mass spectrometry (LC-MS) was developed for determining three microcystins (MCs) in natural water blooms and cyanobacteria strain cultures. The procedure involves sample homogenization with C₁₈, washed with dichloromethane to eliminate interfering compounds, and elution with acidic methanol. Results were compared to those achieved by using an organic solvent standard method. Mean recoveries of MCs with MSPD were 85–92% with intra-day relative standard deviation (RSDs) of 9–19%, whereas organic solvent extraction resulted in recovery rates of 92–105% with intra-day RSDs ranging from 8 to 18%. Limits of quantification (LOQs) were 1 g g^–1 dry weight for the MCs either by MSPD or organic solvent extraction. The two analytical methods tested were specific and sensitive to the extraction of MCs and were applied to the detection of MCs in water blooms and culture strains. The concentration of MCs varied from 7 to 3,330 g g^–1 of lyophilized cells with MC-LR always showing the highest concentration. MCs levels were higher in culture strains than in water blooms, except for MC-LR, whose concentration in blooms was slightly superior to that determined in culture strains.     

4-Ketoantheraxanthin, a novel carotenoid produced by the combination of the bacterial enzyme β-carotene ketolase CrtW and endogenous carotenoid biosynthetic enzymes in higher plants

Higher plants do not ordinarily possess ketocarotenoids due to the absence of a carotenoid ketolase enzyme. We expressed genes coding for marine-bacterial enzymes β-carotene ketolase (CrtW) and β-carotene hydroxylase (CrtZ) in tobacco plants (Nicotiana tabacum) by transplastomic engineering. A novel carotenoid, 4-ketoantheraxanthin, was isolated from the leaves of the tobacco transformants. The structure of 4-ketoantheraxanthin was determined to be (3S,3′S,5′R,6′S)-5′,6′-epoxy-3,3′-dihydroxy-β,β-caroten-4-one by analysis of the MS, NMR, and CD data. This carotenoid was considered to be synthesized by a 4-ketolation reaction by CrtW of antheraxanthin that had been synthesized by the endogenous carotenoid biosynthetic enzymes present in higher plants and CrtZ. 4-Ketoantheraxanthin was also shown to have potent antioxidative activity against a ¹O₂ suppression model.     

Accurate determination of naturally occurring radionuclides in Philippine coal-fired thermal power plants using inductively coupled plasma mass spectrometry and γ-spectroscopy

There is an increased interest in measuring naturally occurring radioactive materials (NORM) like coal, fly ash considering health hazards caused by naturally occurring radionuclides. This paper presents activity concentration (AC) of ²²⁶Ra, ²²⁸Ra, ²³²Th, ²³⁸U and ⁴⁰K in feed coal, bottom and fly ash samples from Philippines coal-fired thermal power plants using inductively coupled plasma mass spectrometry (ICP-MS) and high-purity germanium gamma spectroscopy (HPGe γ-spectroscopy). Coal, bottom and fly ash samples were digested using a microwave oven with a mixture of HNO₃, HClO₄ and HF. Uranium (²³⁸U) and thorium (²³²Th) ACs were also analyzed from samples using ICP-MS. A good correlation was found for the measurement of U and Th using both techniques (R² = 0.97 and 0.94 respectively). ICP-MS measurements showed the highest AC of ²³²Th and ²³⁸U in fly ash and lowest for feed coal samples. With HPGe γ-spectroscopy measurements, highest AC (in Bq kg^{− 1}) of ²²⁶Ra, ²²⁸Ra, ²²⁸Th and ⁴⁰K, were noticed in fly ash followed by bottom ash and feed coal. ICP-MS method is rapid for the measurement of uranium and thorium in comparison to γ-spectroscopy as secular equilibrium is not required. Activity concentrations of bottom and fly ash samples were found to be within the reported values worldwide and below the International Atomic Energy Agency recommended values for regulatory control.     

Simultaneous analysis of natural pigments and E-141i in olive oils by liquid chromatography–tandem mass spectrometry

Analytical and Bioanalytical Chemistry - This work describes the development of an ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) method for the...     

Release and speciation of uranium in low-ionic-strength groundwaters at an abandoned uranium mine in Val Vedello (Orobic Alp—Italy) by adsorptive cathodic stripping voltammetry

Adsorptive cathodic stripping voltammetry (AdCSV) with HDME and a chloranilic acid ligand was used in the trace analysis of uranyl ions at pH?=?2 in low-ionic-strength groundwaters around mining areas. Upon optimization, the limit of detection around 0.10?µg?L^?1 was found with linearity up to 10?µg?L^?1. In the abandoned mining area of Val Vedello (Orobic Alps, Italy), measured uranium concentrations in water ranged from 0.3?µg?L^?1 above the uranium mineralization levels to 145?µg?L^?1 in groundwaters percolating from mine galleries. Such uranium concentrations are related to natural weathering effects of CO₂ and/or hydrogen carbonate ion on uranium mineralizations under oxic conditions. A marked seasonal dependence was then found, in agreement with literature data on a pre-operational survey dating back to 1980–1981. No significant chemical impact of the abandoned mining activity on groundwater quality could be found. Accordingly, no significant increase in contaminants derived from the heat-burn of explosives, such as chloride and nitrate, in groundwaters from mine galleries was found.     

Evaluation of the uranium concentration in rocks at the μg/g level by a low-background Geiger-Müller counter

A low-background -counter and a simple direct method, based on total -counting, have been developed in order to estimate the concentration of uranium at the g/g level in ordinary rock samples. The method is a relative one; international standards have been used for calibration. Only 3 g of rock powder is needed. Combining this method with -spectrometry, direct determination of²³⁸U (independently of²²⁶Ra) becomes possible near the above concentration level.     

Generation and bleaching of E′-centers induced in a-SiO2 by γ-irradiation

Radiation indicator as well as radiation shielding of extremely high dose have been proposed. Three different types of a-SiO₂ namely, G₁-xerogel, G₂-fused and G₃-natural silica were monitored by EPR before and after γ-irradiation. The E′-center has been used for EPR radiation characterization of a-SiO₂ with assuming that the signal intensity changes with γ-irradiation differently as those of other EPR signals do. Formation and decay of the E′-center are closely related with its precursor, diamagnetic oxygen vacancies. Gamma ray of large dose (500 kGy) creates oxygen vacancies giving up-and-down irradiation effects, which, therefore, might be useful for high dose radiation indicator (G₁) and radiation shielding (G₂ and G₃).     

Preconcentration by coprecipitation of arsenic and tin in natural waters with a Ni–pyrrolidine dithiocarbamate complex and their direct determination by solid-sampling atomic-absorption spectrometry

A method for the determination of trace amounts of arsenic and tin in natural waters is described. Trace amounts of arsenic and tin were preconcentrated by coprecipitation with a Ni–ammonium pyrrolidine dithiocarbamate (APDC) complex. The coprecipitates obtained were directly analyzed by graphite-furnace atomic-absorption spectrometry (GFAAS) using the Ni–APDC complex solid-sampling technique. The coprecipitation conditions used for the trace amounts of arsenic and tin in natural water were investigated in detail. It was found that arsenic and tin at sub-ng mL^–1 levels were both coprecipitated quantitatively by Ni(PDC)₂ in the pH range 2–3. The concentration factors by coprecipitation reached approximately 40,000 when 2 mg nickel was added as a carrier element to 500 mL of the water sample. The proposed method has been applied to the determination of trace amounts of arsenic and tin in river water and seawater reference materials, and the detection limits for arsenic and tin, which were calculated from three times of the standard deviation of the procedural blanks, are 0.02 ng mL^–1 and 0.04 ng mL^–1, respectively, for 500-mL volumes of water sample.     

Synthesis of γ-Cyclodextrin Pyrene-Labeled at the Hetero Rim and Its Use in Fluorescent Molecular Sensing

Fluorogenic active host labeled at the upper and lower rims of -cyclodextrin, namely, mono-3^A-deoxy-3^A-pyrenebutylamido-6^X-O-mono-pyrenebutylate-mono-altro--cyclodetrin (mixture -1,X = A, B, C, D, E, F, G, or H), has been synthesized in order to investigate their host-guest complexation with steroidal compoundsusing fluorescence spectra. Monomer and excimer fluorescence was observed for mixture host. Inclusion of a guest molecule in the cyclodextrin cavity resultedin increased monomer fluorescence and decreased excimer fluorescence. The extent of monomerand excimer fluorescence variations ofmixture -1 with the guestwas used as an indication for the sensing ability. The guest inducedfluorescence changes were measured for 10^-7 M solutions of mixture -1.The values I/I ⁰ , where I ⁰ and I are fluorescence intensities in the absence and presence of a guest, respectively, and I is I ⁰ - I, were then used to describe the sensing ability.     

A rotating disk electrode study of the catalytic waves produced by dismutation of O2− in the presence of superoxide dismutase

An equation is derived for the catalytic currents controlled by different dismutation processes of superoxide ion and by diffusion at a rotating disk electrode. Experimental data confirming the theoretical conclusions are presented for Cu, Zn superoxide dismutase.