Sm-Nd system in total rock open versus closed isotopic composition in zones of high deformation

High strain shear zones of Brasiliano age, developed in Paleoproterozoic basement gneiss of the Caicó region, Borborema Province, NE Brazil, were associated with medium- to low-grade metamorphism and deformational processes that transformed porphyritic augen gneiss into muscovite quartzite, modifying their original mineralogy and chemical properties. During the last hydrothermal event mobility of major, minor and trace elements was great, whereas the pattern of Rare Earth Elements was not changed. We carried out a Sm-Nd isotopic study in these rocks in order to understand the behavior of Nd isotopes during mylonite generation. TDM model ages at around 2.6 Ga and εNd (t) values for both protolith and transformed rock suggest that the Nd isotopic system remained closed, recording the original source rock signature, despite undergoing two superposed metamorphic events. These new Sm-Nd results provide important information on the geologic evolution of basement rocks in the central Rio Grande do Norte Terrane of the Borborema Province, NE Brazil.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

Magmatismo há ca. 660 - 640 Ma no Domínio Socorro: Registros de convergência-colisional na Aglutinação do Gondwana Ocidental

Uranium-lead zircon ages between 660 and 640 Ma, obtained from a series of calc-alkaline orthogneisses and plutons in southeast Brazil's Central Mantiqueira Province, suggest that a significant period of magmatism occurred in this region prior to the collisional assembly of West Gondwana (presently constrained in the region between ca. 625 and 580 Ma). While the nature of this earlier magmatism is presently unclear, some preliminary Sm-Nd data suggest that these magmas were not solely derived from the Paleoproterozoic lithosphere, but appear to represent hybrid products of Paleoproterozoic and Neoproterozoic sources. As such hybrid mixtures have been most commonly observed in continental are settings, it is possible that the 660 to 640 Ma magmatism represents are magmatism that resulted from subduction of Neoproterozoic oceanic crust during early precollisional convergence and closure of a branch of either the Adamastor or Goianides oceans.

Metal-insulator transition in Nd1-xEuxNiO 3 compounds

Polycrystalline Nd1-xEuxNiO3 (0≤x≤0.5) compounds were synthesized in order to investigate the character of the metal-insulator (MI) phase transition in this series. Samples were prepared through the sol-gel route and subjected to heat treatments at ∼1000 °C under oxygen pressures as high as 80bar. X-ray diffraction (XRD) and neutron powder diffraction (NPD), electrical resistivity ρ(T), and magnetization M(T) measurements were performed on these compounds. The NPD and XRD results indicated that the samples crystallize in an orthorhombic distorted perovskite structure, space group Pbnm. The analysis of the structural parameters revealed a sudden and small expansion of ∼0.2% of the unit cell volume when electronic localization occurs. This expansion was attributed to a small increase of ∼0.003 of the average Ni-O distance and a simultaneous decrease of ∼-0.5° of the Ni-O-Ni superexchange angle. The ρ(T) measurements revealed a MI transition occurring at temperatures ranging from TMI∼193 to 336K for samples with x ≤ 0 and 0.50, respectively. These measurements also show a large thermal hysteresis in NdNiO3 during heating and cooling processes, suggesting a first-order character of the phase transition at TMI. The width of this thermal hysteresis was found to decrease appreciably for the sample Nd 0.7Eu0.3NiO3. The results indicate that cation disorder associated with increasing substitution of Nd by Eu is responsible for changing the first-order character of the transition in NdNiO3. © 2006 IOP Publishing Ltd.

Evidence for 2.35 to 2.30 Ga juvenile crustal growth in the northwest Borborema Province, NE Brazil

The c. 600 Ma Brasiliano Borborema Province of NE Brazil comprises a complex collage of Precambrian crustal blocks cut by a series of continental-scale shear zones. The predominant basement rocks in the province are 2.1-2.0 Ga Transamazonian gneisses of both juvenile and reworked nature. U-Pb zircon and Sm-Nd whole-rock studies of tonalite-trondhjemite-granodiorite basement gneisses in the NW Ceará or Médio Coreaú domain in the northwestern part of the Borborema Province indicate that this represents a continental fragment formed by 2.35-2.30 Ga juvenile crust. This block has no apparent genetic affinity with any other basement gneisses in the Borborema Province, and it does not represent the tectonized margin of the c. 2.1-2.0 Ga São Luis Craton to the NW. The petrological and geochemical characteristics, as well as the Nd-isotopic signatures of these gneisses, are consistent with their genesis in an island arc setting. This finding documents a period of crustal growth during a period of the Earth's history which is known for its tectonic quiescence and paucity of crust formation. © Geological Society of London 2009.

Study of biosorption of rare earth metals (La, Nd, Eu, Gd) by Sargassum sp. biomass in batch systems: Physicochemical evaluation of kinetics and adsorption models

This work evaluated kinetic and adsorption physicochemical models for the biosorption process of lanthanum, neodymium, europium, and gadolinium by Sargassum sp. in batch systems. The results showed: (a) the pseudo-second order kinetic model was the best approximation for the experimental data with the metal adsorption initial velocity parameter in 0.042-0.055 mmol.g -1.min-1 (La < Nd < Gd < Eu); (b) the Langmuir adsorption model presented adequate correlation with maximum metal uptake at 0.60-0.70 mmol g-1 (Eu < La < Gd < Nd) and the metal-biomass affinity parameter showed distinct values (Gd < Nd < Eu < La: 183.1, 192.5, 678.3, and 837.3 L g-1, respectively); and (c) preliminarily, the kinetics and adsorption evaluation did not reveal a well-defined metal selectivity behavior for the RE biosorption in Sargassum sp., but they indicate a possible partition among RE studied. © (2009) Trans Tech Publications.

Optical and transport properties of rare-earth trivalent ions located at different sites in sol-gel SnO2

Photoluminescence and photo-excited conductivity data as well as structural analysis are presented for sol-gel SnO2 thin films doped with rare earth ions Eu3+ and Er3+, deposited by sol-gel-dip-coating technique. Photoluminescence spectra are obtained under excitation with various types of monochromatic light sources, such as Kr+, Ar+ and Nd:YAG lasers, besides a Xe lamp plus a selective monochromator with UV grating. The luminescence fine structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at the asymmetric grain boundary layer sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference in the capture energy is not so evident in these materials with nanoscocopic crystallites, even though the luminescence spectra are rather distinct. It seems that grain boundary scattering plays a major role in Eu-doped SnO2 films. Structural evaluation helps to interpret the electro-optical data. © 2010 IOP Publishing Ltd.

Upconversion ultraviolet random lasing in Nd 3+ doped fluoroindate glass powder

An upconversion random laser (RL) operating in the ultraviolet is reported for Nd 3+ doped fluoroindate glass powder pumped at 575 nm. The RL is obtained by the resonant excitation of the Nd 3+ state 2G 7/2 followed by energy transfer among two excited ions such that one ion in the pair decays to a lower energy state and the other is promoted to state 4D 7/2 from where it decays emitting light at 381 nm. The RL threshold of 30 kW/cm 2 was determined by monitoring the photoluminescence intensity as a function of the pump laser intensity. The RL pulses have time duration of 29 ns that is 50 times smaller than the decay time of the upconversion signal when the sample is pumped with intensities below the RL laser threshold. © 2011 Optical Society of America.

Nd:YAG Laser Irradiation effect on apical intracanal dentin-a microleakage and SEM evaluation

The purpose of this in vitro study was to evaluate the effect of neodymium:yttrium-aluminum-garnet (Nd:YAG) laser irradiation on intracanal dentin surface by SEM analysis and its interference in the apical seal of filled canals. After endodontic treatment procedures, 34 maxillary human incisors were randomly assigned to 2 groups. In the negative control group (n=17), no additional treatment was performed and teeth were filled with vertically condensed gutta-percha; in the laser-treated group (n=17), the root canals were irradiated with Nd:YAG laser (1.5 W, 100 mJ, 15 Hz) before filling as described for the control group. Two specimens of each group were prepared for SEM analysis to evaluate the presence and extent of morphological changes and removal of debris; the other specimens were immersed in 0.5% methylene blue dye (pH 7.2) for 24 h for evaluation of the linear dye leakage at the apical third. SEM analysis of the laser-treated group showed dentin fusion and resolidification without smear layer or debris. The Student's t-test showed that the laser-treated group had significantly less leakage in apical third than the control group. Within the limitations of this study, it may be concluded that the morphological changes on the apical intraradicular dentin surface caused by Nd:YAG laser resulted in less linear dye apical leakage.

Thermal and spectroscopic studies of solid oxamate of light trivalent lanthanides

Solid-state LnL3·1.25H2O compounds, where L is oxamate and Ln is light trivalent lanthanides, have been synthesized. Simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), experimental and theoretical infrared spectroscopy, TG-DSC coupled to FTIR, elemental analysis, complexometry, and X-ray powder diffractometry were used to characterize and to study the thermal behavior of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition, and gaseous products evolved during the thermal decomposition of these compounds in dynamic air atmosphere. The dehydration occurs in a single step and through a slow process. The thermal decomposition of the anhydrous compounds occur in a single (Ce), two (Pr), and three (La, Nd to Gd) steps with the formation of the respective oxides, CeO2, Pr 6O11, and Ln2O3 (Ln = La, Nd to Gd). The theoretical and experimental spectroscopic study suggests that the carboxylate group and amide carbonyl group of oxamate are coordinate to the metals in a bidentate chelating mode. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Giant enhancement of phonon-assisted one-photon excited frequency upconversion in a Nd3+-doped tellurite glass

Changing the sample's temperature from 200 K to 535 K, we observed 670-fold enhancement of a phonon-assisted upconversion emission at ≈754 nm obtained from a Nd3+-doped tellurite glass excited by 5 ns laser pulses at 805 nm. A rate-equation model, including the relevant energy levels and temperature dependent transition rates, is proposed to describe the process. The results fit well with the data when one considers the nonradiative transitions contributing for the 754 nm luminescence are promoted by an effective phonon mode with energy of 700 cm-1. © 2013 American Institute of Physics.

Piezoresponse force microscopy characterization of rare-earth doped BiFeO3 thin films grown by the soft chemical method

The multiferroic behavior with ion modification using rare-earth cations on crystal structures, along with the insulating properties of BiFeO3 (BFO) thin films was investigated using piezoresponse force microscopy. Rare-earth-substituted BFO films with chemical compositions of (Bi 1.00-xRExFe1.00O3 (x=0; 0.15), RE=La and Nd were fabricated on Pt (111)/Ti/SiO2/Si substrates using a chemical solution deposition technique. A crystalline phase of tetragonal BFO was obtained by heat treatment in ambient atmosphere at 500 °C for 2 h. Ion modification using La3+ and Nd3+ cations lowered the leakage current density of the BFO films at room temperature from approximately 10-6 down to 10-8 A/cm2. The observed improved magnetism of the Nd3+ substituted BFO thin films can be related to the plate-like morphology in a nanometer scale. We observed that various types of domain behavior such as 71° and 180° domain switching, and pinned domain formation occurred. The maximum magnetoelectric coefficient in the longitudinal direction was close to 12 V/cm Oe. © 2012 Elsevier Ltd and Techna Group S.r.l.

Synthesis, thermal behavior and spectroscopic study of trivalentlanthanide and yttrium(III) α-hydroxyisobutyrates, in solid state

Thermal and spectroscopic studies on solid trivalent lanthanides and yttrium(III) α-hydroxyisobutyrates, Ln(C4H7O 3)3·nH2O were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), elemental analysis, X-ray diffractometry, complexometry, experimental and theoretical infrared spectroscopy and TG-DSC coupled to FTIR. The dehydration of lanthanum to neodymium and terbium to thulium and yttrium compounds occurs in a single step while for samarium, europium and gadolinium ones it occurs in three consecutives steps. Ytterbium and lutetium compounds were obtained in the anhydrous state. The thermal decomposition of the anhydrous compounds occursin two consecutives steps, except lanthanum (five steps) and cerium (single step), with formation of the respective oxides CeO2, Pr6O 11, Tb4O7 and Ln2O3 (Ln = La, Nd to Lu and Y), as final residue. The resultsalso provided information concerning the composition, thermal behavior, crystallinity and gaseous products evolved during the thermal decomposition. The theoretical and experimental spectroscopic data suggested the possible modes of coordination of the ligand with the lanthanides.© 2013 Elsevier B.V.

Sr-Nd-Pb isotopic constraints on the nature of the mantle sources involved in the genesis of the high-Ti tholeiites from northern Paraná Continental Flood Basalts (Brazil)

There has been little research on geochemistry and isotopic compositions in tholeiites of the Northern region from the Paraná Continental Flood Basalts (PCFB), one of the largest continental provinces of the world. In order to examine the mantle sources involved in the high-Ti (Pitanga and Paranapanema) basalt genesis, we studied Sr, Nd, and Pb isotopic systematics, and major, minor and incompatible trace element abundances. The REE patterns of the investigated samples (Pitanga and Paranapanema magma type) are similar (parallel to) to those of Island Arc Basalts' REE patterns. The high-Ti basalts investigated in this study have initial (133Ma) 87Sr/86Sr ratios of 0.70538-0.70642, 143Nd/144Nd of 0.51233-0.51218, 206Pb/204Pb of 17.74-18.25, 207Pb/204Pb of 15.51-15.57, and 208Pb/204Pb of 38.18-38.45. These isotopic compositions do not display any correlation with Nb/Th, Nb/La or P2O5/K2O ratios, which also reflect that these rocks were not significantly affected by low-pressure crustal contamination. The incompatible trace element ratios and Sr-Nd-Pb isotopic compositions of the PCFB tholeiites are different to those found in Tristan da Cunha ocean island rocks, showing that this plume did not play a substantial role in the PCFB genesis. This interpretation is corroborated by previously published osmium isotopic data (initial γOs values range from+1.0 to+2.0 for high-Ti basalts), which also preclude basalt generation by melting of ancient subcontinental lithospheric mantle. The geochemical composition of the northern PCFB may be explained through the involvement of fluids and/or small volume melts related to metasomatic processes. In this context, we propose that the source of these magmas is a mixture of sublithospheric peridotite veined and/or interlayered with mafic components (e.g., pyroxenites or eclogites). The sublithospheric mantle (dominating the osmium isotopic compositions) was very probably enriched by fluids and/or magmas related to the Neoproterozoic subduction processes. This sublithospheric mantle region may have been frozen and coupled to the base of the Parana basin lithospheric plate above which the Paleozoic subsidence and subsequent Early Cretaceous magmatism occurred. © 2013 Elsevier Ltd.

Estudo comprarativo da biossorção dos metais terras-raras ('ND POT. +3', 'LA POT. +3', 'CE POT. +3') pela biomassa melanizada e pigmento, na forma livre e imobilizada, obtidos do fungo Aspergillus nidulans

Pós-graduação em Biotecnologia - IQ