Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study

A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, nBu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [nBu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV–vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc+, followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO22+. NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8]4– is delocalized over all NCS– ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8]4– (An = Th, U) and [UO2(NCS)5]3– has been explored by a combination of DFT and QTAIM analysis, and the U–N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)–NCS ion is more ionic than what was found for U(IV)–Cl complexes.

Uranium series disequilibria in ground waters from a fractured bedrock aquifer (Morungaba Granitoids-Southern Brazil): Implications to the hydrochemical behavior of dissolved U and Ra

Activity concentrations of dissolved U-234, U-238, Ra-226 and Ra-228 were determined in ground waters fromtwo deep wells drilled in Morungaba Granitoids (Southern Brazil). Sampling was done monthly for little longer than 1 year. Significant disequilibrium between U-238, U-234 and Ra-226 were observed in all samples. The variation of U-238 and U-234 activity concentrations and U-234/U-238 activity ratios is related to seasonal changes. Although the distance between the two wells is short (about 900m), systematic differences of activity concentrations of U isotopes, as well as of U-234/U-238, Ra-226/U-234 and Ra-228/Ra-226 activity ratios were noticed, indicating distinct host rock-water interactions. Slightly acidic ground water percolation through heterogeneous host rock, associated with different recharge processes, may explain uranium and radium isotope behavior. (c) 2008 Elsevier Ltd. All rights reserved.

Evaluation of uranium incorporation from contaminated areas using teeth as bioindicators - a case study

The Southwest region of the Bahia state in Brazil hosts the largest uranium reserve of the country (100 kton in uranium, only), plus the cities of Caetite, Lagoa Real and Igapora. In this work, aim was at the investigation of uranium burdens on residents of these cities by using teeth as bioindicators, as a contribution for possible radiation protection measures. Thus, a total of 41 human teeth were collected, plus 50 from an allegedly uranium free area (the control region). Concentrations of uranium in teeth from residents of 5- to 87-y old were determined by means of a high-resolution inductively coupled plasma mass spectrometer (ICP-MS). The highest uranium concentration in teeth was measured from samples belonging to residents of Caetite (median equal to 16 ppb). Assuming that the uranium concentrations in teeth and bones are similar within 10-20% (for children and young adults), it concluded that uranium body levels in residents of Caetite are at least one order of magnitude higher than the worldwide average. This finding led to conclude that daily ingestion of uranium, from food and water, is equally high.

Method design and validation for the determination of uranium levels in human urine using high-resolution alpha spectrometry

Quantification of uranium in human urine is a valuable technique for assessing occupational and public exposure to uranium. A reliable method has been developed and validated in the ARPANSA Radiochemistry Laboratory by means of standard radiochemical separation and purification techniques and measurement using high-resolution alpha spectrometry. This method can be used to evaluate the levels of naturally occurring ²³⁴U, ²³⁵U and ²³⁸U in urine. Method design and validation is the process of defining an analytical requirement, and then confirming that the method under consideration has performance capabilities consistent with what the application requires. The method was designed to measure levels down to 2 mBq/day of total uranium, corresponding to approximately 1/100th of the annual committed effective dose of 20 mSv. Validation tests were developed to assess selectivity, accuracy, recovery and quantification of uncertainty. The radiochemical recovery of this method was measured using ²³²U tracer. The typical minimum detectable concentration for total uranium for 24-h urine samples is approximately 0.6 mBq/day or 0.019 μg/day.

Assessment of liquid disposal originated by uranium enrichment at Aramar Experimental Center São Paulo-Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Uranium distribution and radon exhalation from Brazilian dimension stones

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Transfer coefficient measurements of uranium to the organs of Wistar rats, as a function of the uranium content in the food

Groups of animals (Wistar rats) were fed with rations doped with uranyl nitrate at concentrations ranging from 0.5 to 100 ppm. The uranium content in the ashes of the organs was measured by the neutron-fission track counting technique. The most striking result is that the transfer coefficients, as a function of the uranium concentration, exhibit a concave shape with a minimum around 20ppm-U for all organs. Explanations to interpret this finding are tentatively given. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Some constraints on the modeling using the uranium isotopes U-238 and U-234 for dating groundwaters from Guarany aquifer, South America

Groundwaters from the Guarany aquifer located at the South American continent and sampled at four wells with described geological sections in São Paulo State, Brazil, were chemically and isotopically analysed with two aims: to evaluate the quality of this important hydrological resource and to investigate the possibility of using the natural uranium isotopes U-234 and U-238 as a chronological tool, since the U-234/U-238 activity ratio and dissolved U content data in groundwater systems have generated models for dating purposes.

Uranium incorporation biokinetics in poultry bones as function of phytase doses

Neutron activation analysis has been used to study uranium incorporation in poultry bones as function of chow doped with : (a) uranium (20 ppm); (b) U-doped food (20 ppm) plus phytase (120 ppm) and (c) U-doped food (20 ppm) plus phytase (180 ppm). To investigate this situation experiments involving several groups of Cobb broilers was performed. Two animals per group were sacrificed weekly up to their adultness and uranium concentration in the tibia was measured. It was observed that the concentration of uranium (mug U/g bone) is decreasing all along the animal life spanning period of 14-42 days. This behavior suggests that the skeleton mass is growing faster than the corresponding accumulation of uranium. The administration of phytase seems not to alter this scenario.

Uranium in groundwaters from Botucatu-Piramboia aquifer, Brazil

Groundwater from 60 pumped tubular wells of the Botucatu-Piramboia aquifer system located at the Parana sedimentary basin in Brazil were chemically analysed with the aim of evaluating if the mechanisms related to the migration of uranium can generate concentrations greater than the maximum permissible limit in drinking water, as defined by the Brazilian national standards.

Uranium levels in the diet of São Paulo City residents

Natural levels of uranium in the diet of São Paulo City residents were studied, and radionuclide concentrations were measured by the fission track method on samples of typical adult food items. This information was used to evaluate the daily intake of uranium in individuals living in São Paulo City which is, according to our findings, around 0.97 mu g U/day. Using the ICRP Uranium-model, we estimated the uranium accumulation and committed doses in some tissues and organs, as function of time. We compared the output of the ICRP uranium biokinetic model, tailored for the conditions prevailing in São Paulo, with experimental data from other localities. Such comparison was possible by means of a simple method we developed, which allows normalization among experimental results from different regions where distinct values of chronic daily intake are observed. (c) 2006 Elsevier Ltd. All rights reserved.

Potentialities and practical limitations of absolute neutron dosimetry using thin films of uranium and thorium applied to the fission track dating

Neutron dosimetry using natural uranium and thorium thin films makes possible that mineral dating by the fission-track method can be accomplished, even when poor thermalized neutron facilities are employed. In this case, the contributions of the fissions of (235)U, (238)U and (232)Th induced by thermal, epithermal and fast neutrons to the population of tracks produced during irradiation are quantified through the combined use of natural uranium and thorium films.If the Th/U ratio of the sample is known, only one irradiation (where the sample and the films of uranium and thorium are present) is necessary to perform the dating. However, if that ratio is unknown, it can be determined through another irradiation where the mineral to be dated and both films are placed inside a cadmium box.Problems related with film manufacturing and calibration are discussed. Special attention is given to the utilization of thin films having very low uranium content. The problems faced suggest that it may be better to substitute these films by uranium doped standard glasses calibrated with thicker uranium films (thickness greater than 1.5 x 10(13) mu m).

Uranium speciation in groundwaters from Parana basin, Brazil

This paper describes the results of a regional study involving the sampling of 60 pumped tubular wells drilled at the Parana sedimentary basin, Brazil, which was carried out with the purpose of evaluating the U speciation in the Botucatu-Piramboia aquifer. Uranium proved to be intensively dissolved even under the enhanced reducing conditions occurring at the most confined zones of the aquifer, and Eh-pH diagrams were utilized to evaluate the influence of temperature and pressure on the migration of the U-species within the aquifer.