Solid-state compounds of 2-methoxybenzylidenepyruvate and 2-methoxycinnamyllidenepyruvate with thorium (IV) Preparation and thermal studies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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).

Solid-state compounds of 4-methoxybenzylidenepyruvate and cinnamylidenepyruvates with thorium (IV) - Preparation and thermal studies

By close control of experimental variables affecting precipitation, solid-state compounds of the type Th(OH)(m)L4-m.nH(2)O, where L stands for 4-methoxy-benzylidenepyruvate, cinnamylidenepyruvate or 4-dimethylaminocinnamylidene-pyruvate; m=0 to 3 and n=0.5-3 were isolated. Chemical analysis, TG, DTG, DSC and X-ray powder diffractometry have been employed to characterize and to study the thermal behavior of these compounds in dynamic air atmosphere. In all cases, hydration water is slowly lost between 30 and 160degreesC; a continuous, slow rate, mass loss is observed thereafter and beyond 280-400degreesC the rate of decomposition/oxidation increased rapidly, to give ThO2 as the final product, beginning at 412-510degreesC. The results associated with the hydroxo-compounds indicate that the loss of constitution water (OH ions) and the decomposition / oxidation of the organic moieties occur as simultaneous process.

Durango apatite fission-track dating using length-based age corrections and neutron fluence measurements by natural thorium thin films and natural U-doped glasses calibrated through natural uranium thin films

In this work, we present an approach for neutron fluence measurements based on natural thorium thin films and natural uranium-doped glasses calibrated through natural uranium thin films to be used for dating with the Fission-Track Method (FTM). This neutron dosimetry approach allows the employment of FTM even when dating is carried out using low neutron themalization facilities. Besides, it makes possible the determination of the Th/U ratio of the mineral to be dated. Durango apatite which is often employed in FTM as an age standard was analyzed. This apatite presented a fairly high Th/U ratio, 29.9 +/- 1.7. Th fissions were 18%, 12% and 10% of the total for irradiations where thermal to fast neutron flux ratios were 2.4, 4.4 and 5,2, respectively. These results show that Th fission must be considered for this apatite, when not well-thermalized irradiation facilities are used. The ratio between spontaneous and induced track length, L(S)/L(1), close to 0.89, indicates a certain amount of rejuvenation of the age of Durango apatite. Therefore, its apparent age should be corrected, the application of a technique based on track-length measurements produced a corrected age of 29.7 +/- 1.1 Ma, consistent with the independent reference age of this apatite (31.4 +/- 0.5 Ma). This result represents a support for viability of the neutron dosimetry approach studied in this work for FTM.(C) 2002 Elsevier B.V. B.V. All rights reserved.

The behavior of dissolved uranium in groundwaters of the Morro do Ferro thorium deposit, Brazil

Groundwater samples were collected for several months in boreholes drilled at Morro do Ferro, a thorium and rare earth deposit located on the Poços de Caldas Plateau, Minas Gerais State, Brazil. An aquifer system has developed in the weathered mantle due to in situ intense alteration. The weathered zone includes a thick argillaceous laterite greater than 100 m thick. The U content and 324U/238U activity ratio were measured in the groundwater samples and in spoil samples of a borehole drilled in the ore body. Some possible mechanisms related to the mobilization of uranium are considered such as complexation with humic substances and adsorption by clays. © 1989.

Complexation of some trivalent lanthanides, scandium(III) and thorium(IV) by benzylidenepyruvates in aqueous solution

The protonation constants of 4-methylbenzylidenepyruvate (4Me-BP) and 4-isopropylbenzylidenepyruvate (4IP-BP) as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Eu(III), Yb(III), Sc(III) and Th(IV) have been determined spectrophotometrically in aqueous solution at 25°C and ionic strength 0.500 M, maintained with sodium perchlorate. For all metal ions considered, the stability changes move in the same direction as the pKa of the ligands. Linear free energy relationships, as applied to oxygen donor substances, suggest the -COCOO- moiety as the metal binding site of the ligands. The results are discussed mainly taking into account that benzylidenepyruvates, besides the α-keto canonical form, may display other forms in aqueous solution with changing pH and the possible occurrence of extra intra-ligand charge polarization, induced by metal ions.

4-Dimethylaminocinnamylidenepyruvic acid: Synthesis, characterization and complexation with trivalent lanthanides, yttrium(III), scandium(III), thorium(IV) and uranium(VI) in aqueous solution

4-Dimethylaminocinnamylidenepyruvic acid (H-DMCP)and its sodium salt (Na-DMCP) have been synthesized and characterized. The protonation constant of DMCP as well as the stability constants of its binary 1:1 complexes with trivalent lanthanides (except Pm), Yttrium(III), Scandium(III), Thorium(IV) and Uranium(VI) were determined in an aqueous medium at 25°C and ionic strength 0.500 M. The mode of coordination of this ligand is discussed.

Complexation of some trivalent lanthanides, scandium(III) and thorium(IV) by benzylidenepyruvates and cinnamylidenepyruvate in aqueous solution

The protonation constants of benzylidenepyruvate, 2-chloro-, 4-chlorobenzylidinepyruvate and cinnamylidenepyruvate as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Lu(III), Sc(III) and Th(IV) have been determined spectrophotometrically in an aqueous medium at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. Coordination centres in the aforementioned ligands are suggested. © 1995.

Fission-track dating of Macusanite glasses with plateau and size correction methods

Two Macusanite pebbles (MB1 and MB2) were dated with the fission-track method. Six irradiations were carried out in different nuclear reactors: Pavia (Italy), IPEN-CNEN (Brazil) and IPEN-Lima (Peru). Measurements of the thorium and uranium induced-fission per target nucleus using natural thorium thin films and natural U-doped glasses calibrated against natural uranium thin films, together with lambda(F) of 8.46 x 10(-17) a(-1) were used to determine the ages. The apparent ages were corrected using the plateau and size correction methods. Track measurements were performed by different analysts, using different counting criteria. In addition, tracks were measured on samples which had been submitted to thermal treatment as well as on samples which had not been heated. Thermal treatments were carried out to erase the fossil tracks before neutron irradiation. No significant differences have been found in individual results, using the two Macusanite pebbles and the different nuclear reactors, age correction techniques, analysts, track-counting criteria, and thermal treatments before neutron irradiation. The great majority of the results (14/17) is compatible with the Ar-Ar ages of 5.12 +/- 0.11 and 5.10 +/- 0.11 Ma, Macusanite MB1 and MB2, respectively. However, the fission-track ages are systematically less (similar to8%) than the Ar-Ar ages of the two Macusanite samples studied. (C) 2003 Published by Elsevier Ltd.

Radioactivity distribution in some Permian sediments from the Irati and Corumbatal formations of the Parana basin, southeastern Brazil

in the city of Limeira, southeastern Brazil, an important exposure of Permian sediments of the Parana basin was revealed by an open pit mine that exploits limestone for production of soil correction compounds and raw materials for the ceramic industry. The radioactivity of these sediments was investigated in some detail and the results provided a general view of the vertical distributions of uranium, thorium and potassium concentrations and of the element ratios U/K, U/Th and Th/K. In general, the concentrations of the main natural radioactive elements are low, with uranium being enriched in some limestone and shale levels. In addition the results showed that the U-238 series is in radioactive disequilibrium in many of the analyzed samples. Although the origin of the observed disequilibrium has not been investigated, the results suggest that it is due to weathering processes and water interaction with the rock matrix. (C) 2003 Elsevier Ltd. All rights reserved.

Implications of groundwater weathered profile interactions to the mobilization of radionuclides

This study reports the nature and extent of open-system interaction between groundwater and a weathered profile developed in the high grade thorium and REE ore body in Morro do Ferro, Pocos de Caldas plateau. The radioelement mobility in the shallow oxidizing environment was considered by using chemical data in conjunction with U-234/U-238, Ra-226/Th-230, Th-230/U-234, Th-228/Th-232, Ra-228/Th-232 and Th-230/Ra-228 activity ratios (AR's) for borehole spoil and groundwater samples.Recharging groundwater from the studied borehole has low salinity values, with total dissolved solids content of 14.7 mg/l and total ionic strength of 0.00018. The ratio of the weight of dissolved radioelement per unit volume of solution to the weight of radioelement in solid phase per unit weight of solid phase showed that the radioelement solubility in the studied waters varied according to the following order: radium> uranium >thorium.U-234/U-238 AR's less than 1 were measured in solid phase and can justify the enhancement of U-234 in solution. Ra-226/Th-230 AR's greater than 1 and Th-230/U-234 AR'S less than 1 were evaluated between 20 and 27 m in depth, where a 2.1-m thick magnetite dike was intersected. These ratios could be justified by deposition of U and Ra associated with Fe-Mn oxides and kaolinite, where mineral saturation indices evaluated from the available data confirm this possibility. Covariations among disequilibria involving Th-228/(228) Ra and Ra-228/Th-232 AR's showed the preferential removal of Ra-228 relative to Tn isotopes, Th-228 and Th-232. The recent deposition of radium within the timescale of at least the last 35 years also is suggested. (C) 1998 Elsevier B.V. Ltd. All rights reserved.

The natural radioactivity in Guarani aquifer groundwater, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Health risk related to radon in a thermal spa utilizing waters from Guarani aquifer

This investigation was carried out within the Parana sedimentary basin, Brazil, involved the sampling of groundwater and air, and was realized with the purpose of evaluating the radioactivity, due to radon gas, in a thermal spa utilizing the waters from Guarani (Botucatu-Piramboia) aquifer. The results reported here provide additional information relative to that of previous studies focusing on the presence of radionuclides in the aquifer, which have mainly characterized those belonging to uranium and thorium series decay, such as the uranium isotopes (U-238 and U-234), radium isotopes (Ra-226 and Ra-228), radon daughters (Bi-214 and Pb-214) and radon (Rn-222) itself the results obtained were compared with the maximum permissible concentration limits in air and drinking water defined by international standards, such as the guidelines for drinking water quality established by the World Health Organization. The possible processes responsible for the presence of radon in the aquifer were also considered in order to evaluate the data obtained.

Geo(anthropo)genic factors affecting the radioactivity in groundwaters from Guarani aquifer, Brazil

This investigation was carried out within the Paraná sedimentary basin, involved the sampling of 77 pumped tubular wells, and was realized with the puipose of evaluating the radioactivity in the Brazilian part of Guarani (Botucatu-Pirambóia, Tacuarembó, Misiones) aquifer. The radioactivity due to nuclides belonging to uranium and thorium series decay was investigated in terms of the uranium isotopes 234U and 238U, radon (222Rn), and the radium isotopes 226Ra and 228Ra. The obtained results were compared with the maximum permissible concentration limits in drinking water defined by the Brazilian national standard, as well with the guidelines for drinking water quality established by the World Health Organization. The importance of water-rock/soil interactions was considered in order to explain most of the obtained data.

Geochemical and radioactivity characterization of rocks from the Rio Preto (Go) Project

The Rio Preto Project, developed by the extinct Brazilian nuclear state company, Nuclebrás, during the late 70s and early 80s, consisted of basic geological mapping and radiometric characterization by aerogeophysical gamma-ray spectrometry, without channel discrimination, of a surface area of 650 km2 located to the west of the Chapada dos Veadeiros National Park on the northeastern of Goiás State, Brazil, including the confluence area of Claro and Preto Rivers. Additionally, the natural radioelements U, Th and 40K were determined by gamma-ray spectrometry in 300 rock samples from cores of the Rio Preto Project area. The tests were conducted at LABIDRO-Isotopes and Hydrochemistry Laboratory of the Departament of Petrology and Metallogeny (DPM) of the Institute of Geosciences and Exact Sciences, UNESP, in Rio Claro, SP, Brazil. This paper reports the results of petrographic characterization and chemical analyses of major oxides (SiO2, TiO2, Al2O3, Fe2O3, MgO, MnO, K2O, Na2O, CaO and P2O5) for all samples used to determine the natural radioelements present in the region. The organic matter content results obtained by colorimetry are also reported for selected cores of different lithotypes in order to investigate the possible relationship between graphite and the radioelements uranium and thorium. Finally, uranium content and 234U/238U activity ratio data for selected samples of schists and gneisses of the Lower Member of the Ticunzal Formation suggest the influence of weathering processes in the area. © 2012 Sociedade Brasileira de Geofísica.