PALEOPRODUCTIVITY CHANGES DURING THE LATE QUATERNARY IN THE SOUTHEASTERN BRAZILIAN UPPER CONTINENTAL MARGIN OF THE SOUTHWESTERN ATLANTIC

Changes in the Brazilian continental margin`s oceanic productivity and circulation over the last 27,000 years were reconstructed based on sedimentological and microfaunal analyses. Our results suggest that oceanic paleoproductivity and the supply of terrigenous sediments to the Brazilian continental margin were higher during the Last Glacial Maximum (LGM) than during the Holocene. These changes may have been primarily influenced by significant sea level fluctuations that have occurred since the late Pleistocene. During the LGM, the lower sea level, higher productivity and lower sea-surface paleotemperatures may have been the result of the offshore displacement of the main flow of the Brazil Current. However, during the Holocene, the warm waters of the Brazil Current were displaced toward the coast. This displacement contributed to the increase in water temperature and prevented an increase in oceanic productivity. The decrease in terrigenous supply since the LGM could be related to the increase of the extension of the continental shelf and/or drier climatic conditions.

Paleoenvironmental reconstruction of a Late Quaternary lagoon system in southern Brazil (Jaguaruna region, Santa Catarina state) based on multi-proxy analysis

This paper provides a paleoenvironmental reconstruction of a Late Quaternary lagoon system in the Jaguaruna region of Santa Catarina state, southern Brazil. Integrated results of bulk sedimentary organic matter characterization (delta C-13, delta N-15 and C/N), microfossil (pollen and diatom) and grain-size analysis from three shallow cores (similar to 2.5m depth) allowed us to propose an evolving paleogeographic scenario in this coastal region for the last ca. 5500 cal a BP. The lagoonal system in this area was more extensive during the mid-Holocene than today, with a gradual and continuous lagoon-sea disconnection until the present. We add to the debate regarding relative sea-level (RSL) variations for the Brazilian coast during the Holocene and discuss the importance of sedimentary dynamics for interpreting changes in coastal ecosystems. The multi-proxy analysis suggests that changes in coastal ecosystems could be directly related to local sedimentary processes, which are not necessarily linked to RSL fluctuations and/or to climatic variations. Copyright (c) 2011 John Wiley & Sons, Ltd.

Study of the oxygen vacancy influence on magnetic properties of Fe- and Co-doped SnO2 diluted alloys

Transition-metal (TM)-doped diluted magnetic oxides (DMOs) have attracted attention from both experimental and theoretical points of view due to their potential use in spintronics towards new nanostructured devices and new technologies. In the present work, we study the magnetic properties of Sn0.96TM0.04O2 and Sn0.96TM0.04O1.98(V (O))(0.02), where TM = Fe and Co, focusing in particular in the role played by the presence of O vacancies nearby the TM. The calculated total energy as a function of the total magnetic moment per cell shows a magnetic metastability, corresponding to a ground state, respectively, with 2 and 1 mu(B)/cell, for Fe and Co. Two metastable states, with 0 and 4 mu(B)/cell were found for Fe, and a single value, 3 mu(B)/cell, for Co. The spin-crossover energies (E (S)) were calculated. The values are E (S) (0/2) = 107 meV and E (S) (4/2) = 25 meV for Fe. For Co, E (S) (3/1) = 36 meV. By creating O vacancies close to the TM site, we show that the metastablity and E (S) change. For iron, a new state appears, and the state with zero magnetic moment disappears. The ground state is 4 mu(B)/cell instead of 2 mu(B)/cell, and the energy E (S) (2/4) is 30 meV. For cobalt, the ground state is then found with 3 mu(B)/cell and the metastable state with 1 mu(B)/cell. The spin-crossover energy E (S) (1/3) is 21 meV. Our results suggest that these materials may be used in devices for spintronic applications that require different magnetization states.

LIZARDS AND SNAKES (LEPIDOSAURIA, SQUAMATA) FROM THE LATE QUATERNARY OF THE STATE OF CEARA IN NORTHEASTERN BRAZIL

We present the first formal report on the squamate assemblage from Parque Nacional de Ubajara. This park contains the most important cave complex in the state of Ceara in northeastern Brazil, called Provincia Espeleologica de Ubajara. The material comes from the Urso Fossil cave at Pendurado Hill. All previously reported fossil remains found in this cave are tentatively attributed to the Quaternary (late Pleistocene-early Holocene). Probably only Arctotherium brasiliense represents a relictual fossil bear from the late Pleistocene megafauna. The taxa recognized in this paper belong to Tropidurus sp., Ameiva sp., cf. Epicrates, and cf. Crotalus durissus, adding to the knowledge of the Brazilian Quaternary squamate fauna as a whole, and contribute to a major taxonomic refinement of the squamate assemblages from the early Holocene of northeastern Brazil.

A simple criterion to predict the glass forming ability of metallic alloys

A new and simple criterion with which to quantitatively predict the glass forming ability (GFA) of metallic alloys is proposed. It was found that the critical cooling rate for glass formation (R-C) correlates well with a proper combination of two factors, the minimum topological instability (lambda(min)) and the Delta h parameter, which depends on the average work function difference (Delta phi) and the average electron density difference (Delta n(ws)(1/3)) among the constituent elements of the alloy. A correlation coefficient (R-2) of 0.76 was found between R-c and the new criterion for 68 alloys in 30 different metallic systems. The new criterion and the Uhlmann's approach were used to estimate the critical amorphous thickness (Z(C)) of alloys in the Cu-Zr system. The new criterion underestimated R-C in the Cu-Zr system, producing predicted Z(C) values larger than those observed experimentally. However, when considering a scale factor, a remarkable similarity was observed between the predicted and the experimental behavior of the GFA in the binary Cu-Zr. When using the same scale factor and performing the calculation for the ternary Zr-Cu-Al, good agreement was found between the predicted and the actual best GFA region, as well as between the expected and the observed critical amorphous thickness. (C) 2012 American Institute of Physics. [doi:10.1063/1.3676196]

Gold-platinum alloys and Vegard's law on the nanoscale

The structure of gold-platinum nanoparticles is heavily debated as theoretical calculations predict core-shell particles, whereas x-ray diffraction experiments frequently detect randomly mixed alloys. By calculating the structure of gold-platinum nanoparticles with diameters of up to approximate to 3.5 nm and simulating their x-ray diffraction patterns, we show that these seemingly opposing findings need not be in contradiction: Shells of gold are hardly visible in usual x-ray scattering, and the interpretation of Vegard's law is ambiguous on the nanoscale. DOI: 10.1103/PhysRevB.86.241403

Preparation and characterization of Zircaloy 4-Tantalum alloys for application in corrosive media

Two Zircaloy 4-Ta alloys (14 and 55 wt.% Ta) were produced by arc-melting. The alloys were hot-rolled at 900 degrees C and heat-treated under argon atmosphere for 100 h at 700 degrees C. The alloys were analyzed by scanning electron microscopy and X-ray diffractometry. The microstructure of both rolled and heat-treated alloys is constituted of (beta Zr,Ta)-II Ta-rich precipitates dispersed in a (alpha Zr) matrix. Corrosion tests performed in boiling concentrated H2SO4 solutions showed that the Zircaloy 4-Ta alloys are more corrosion resistant than Zircaloy 4 and that the corrosion resistance increases with increasing Ta content. (c) 2012 Elsevier Ltd. All rights reserved.

Magnetic Tuning of All-Organic Binary Alloys between Two Stable Radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzi-midazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN.) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x >= 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Neel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

The influence of different co-catalysts in Pt-based ternary and quaternary electro-catalysts on the electro-oxidation of methanol and ethanol in acid media

One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.

Does the casting mode influence microstructure, fracture and properties of different metal ceramic alloys?

The aim of the present study was to evaluate the tensile strength, elongation, microhardness, microstructure and fracture pattern of various metal ceramic alloys cast under different casting conditions. Two Ni-Cr alloys, Co-Cr and Pd-Ag were used. The casting conditions were as follows: electromagnetic induction under argon atmosphere, vacuum, using blowtorch without atmosphere control. For each condition, 16 specimens, each measuring 25 mm long and 2.5 mm in diameter, were obtained. Ultimate tensile strength (UTS) and elongation (EL) tests were performed using a Kratos machine. Vickers Microhardness (VM), fracture mode and microstructure were analyzed by SEM. UTS, EL and VM data were statistically analyzed using ANOVA. For UTS, alloy composition had a direct influence on casting condition of alloys (Wiron 99 and Remanium CD), with higher values shown when cast with Flame/Air (p < 0.05). The factors "alloy" and "casting condition" influenced the EL and VM results, generally presenting opposite results, i.e., alloy with high elongation value had lower hardness (Wiron 99), and casting condition with the lowest EL values had the highest VM values (blowtorch). Both factors had significant influence on the properties evaluated, and prosthetic laboratories should select the appropriate casting method for each alloy composition to obtain the desired property.

Development of Plurimetallic Electrocatalysts Prepared by Decomposition of Polymeric Precursors for EtOH/O-2 Fuel Cell

This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal: carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L-1 H2SO4), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt64Sn15Ru13Ni8/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt64Sn15Ru13Ni8/C catalyst displayed the best performance for DEFC.

Development of Ternary and Quaternary Catalysts for the Electrooxidation of Glycerol

This work consisted in the preparation of platinum-based catalysts supported on carbon (Vulcan XC-72) and investigation of their physicochemical and electrochemical properties. Catalysts of the C/Pt-Ni-Sn-Me (Me = Ru or Ir) type were prepared by the Pechini method at temperature of 350 degrees C. Four different compositions were homemade: C/Pt60Sn10Ni30, C/Pt60Sn10Ni20Ru10, C/Pt60Sn10Ni10Ru20, and C/Pt60Sn10Ni10Ir20. These catalysts were electrochemically and physically characterized by cyclic voltammetry (CV), chronoamperometry (CA) in the presence of glycerol 1.0 mol dm(-3), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). XRD results showed the main peaks of face-centered cubic Pt. The particle sizes obtained from XRD and HRTEM experiments were close to values ranging from 3 to 8.5 nm. The CV results indicate behavior typical of Pt-based catalysts in acid medium. The CV and CA data reveal that quaternary catalysts present the highest current density for the electrooxidation of glycerol.

Multiple Quaternary Refugia in the Eastern Guiana Shield Revealed by Comparative Phylogeography of 12 Frog Species

The Guiana Shield (GS) is one of the most pristine regions of Amazonia and biologically one of the richest areas on Earth. How and when this massive diversity arose remains the subject of considerable debate. The prevailing hypothesis of Quaternary glacial refugia suggests that a part of the eastern GS, among other areas in Amazonia, served as stable forested refugia during periods of aridity. However, the recently proposed disturbance-vicariance hypothesis proposes that fluctuations in temperature on orbital timescales, with some associated aridity, have driven Neotropical diversification. The expectations of the temporal and spatial organization of biodiversity differ between these two hypotheses. Here, we compare the genetic structure of 12 leaf-litter inhabiting frog species from the GS lowlands using a combination of mitochondrial and nuclear sequences in an integrative analytical approach that includes phylogenetic reconstructions, molecular dating, and Geographic Information System methods. This comparative and integrated approach overcomes the well-known limitations of phylogeographic inference based on single species and single loci. All of the focal species exhibit distinct phylogeographic patterns highlighting taxon-specific historical distributions, ecological tolerances to climatic disturbance, and dispersal abilities. Nevertheless, all but one species exhibit a history of fragmentation/isolation within the eastern GS during the Quaternary with spatial and temporal concordance among species. The signature of isolation in northern French Guiana (FG) during the early Pleistocene is particularly clear. Approximate Bayesian Computation supports the synchrony of the divergence between northern FG and other GS lineages. Substructure observed throughout the GS suggests further Quaternary fragmentation and a role for rivers. Our findings support fragmentation of moist tropical forest in the eastern GS during this period when the refuge hypothesis would have the region serving as a contiguous wet-forest refuge.

Conduction mechanisms in p-type Pb1-xEuxTe alloys in the insulator regime

Electrical resistivity measurements were performed on p-type Pb1-xEuxTe films with Eu content x = 4%, 5%, 6%, 8%, and 9%. The well-known metal-insulator transition that occurs around 5% at room temperature due to the introduction of Eu is observed, and we used the differential activation energy method to study the conduction mechanisms present in these samples. In the insulator regime (x>6%), we found that band conduction is the dominating conduction mechanism for high temperatures with carriers excitation between the valence band and the 4f levels originated from the Eu atoms. We also verified that mix conduction dominates the low temperatures region. Samples with x = 4% and 5% present a temperature dependent metal insulator transition and we found that this dependence can be related to the relation between the thermal energy k(B)T and the activation energy Delta epsilon(a). The physical description obtained through the activation energy analysis gives a new insight about the conduction mechanisms in insulating p-type Pb1-xEuxTe films and also shed some light over the influence of the 4f levels on the transport process in the insulator region. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4729813]

New constraints on the genesis and long-term stability of Os-rich alloys in the Earth's mantle

A variety of seemingly unrelated processes, such as core-mantle interaction, desulfurization, and direct precipitation from a silicate melt have been proposed to explain the formation of Ru-Os-Ir alloys (here referred to as osmiridiums) found in terrestrial mantle rocks. However, no consensus has yet been reached on how these important micrometer-sized phases form. In this paper we report the results of an experimental study on the solubilities of Ru, Os and Ir in sulfide melts (or mattes) as a function of alloy composition at 1300 degrees C. Considering the low solubilities of Ru, Os, and Ir in silicate melts, coupled with their high matte/silicate-melt partition coefficients, our results indicate that these elements concentrate initially at the ppm level in a matte phase in the mantle source region. During partial melting, the extraction of sulfur into silicate melt leads to a decrease in fS(2) that triggers the exsolution of osmiridiums from the refractory matte in the residue. The newly formed osmiridiums may persist in the terrestrial mantle for periods exceeding billions of years. (C) 2012 Elsevier Ltd. All rights reserved.