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.

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.

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.

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.

Characterization of quaternary tufas in the Serra do Andre Lopes karst, southeastern Brazil

Active tufas in the form of waterfalls and dams occur along drainage channels in the Serra do Andre Lopes region (State of Sao Paulo, southeastern Brazil) and are associated with the karst system that developed on a dolomitic plateau with a superhumid subtropical climate. The predominance of autogenic waters enables the groundwater to become enriched in calcium carbonate, with low terrigenous sediment content. The tufas that were studied are composed of calcite and have high calcium contents and low magnesium contents. Eroded tufa beds that originate from changes in the position of fluvial channels or river flow rates also occur in this region. In the Sapatu deposit, phytohermal tufas with complex morphologies are arranged in levels constituting various temporally repeated sequences that were deposited between 10,570 and 4,972 cal years BP. In the Frias deposit, distal fluvial deposits of tufa are massive with a relatively greater quantity of terrigenous material and show evidence of dissolution and reprecipitation. The base of this deposit is composed of a cemented breccia dated at 25,390 years BP, which is younger than the overlying tufas ([42,000 years BP). In the two deposits, the levels of terrigenous sediments (quartz sand and lithic pebbles) and terrestrial gastropod shells are interpreted as phases of increased flow rate of rivers during intervals of higher rainfall.

Mid- to late-Holocene paleoceanographic changes on the southeastern Brazilian shelf based on grain size records

; High-resolution grain size analyses of three AMS (14)C-dated cores from the Southeastern Brazilian shelf provide a detailed record of mid- to late-Holocene environmental changes in the Southwestern Atlantic Margin. The cores exhibit millennial variability that we associate with the previously described southward shift of the Inter Tropical Convergence Zone (ITCZ) average latitudinal position over the South American continent during the Holocene climatic maximum. This generated changes in the wind-driven current system of the SW Atlantic margin and modified the grain size characteristics of the sediments deposited there. Centennial variations in the grain size are associated with a previously described late-Holocene enhancement of the El Nino-Southern Oscillation (ENSO) amplitude, which led to stronger NNE trade winds off eastern Brazil, favouring SW transport of sediments from the Paraiba do Sul River. This is recorded in a core from off Cabo Frio as a coarsening trend from 3000 cal. BP onwards. The ENSO enhancement also caused changes in precipitation and wind pattern in southern Brazil, allowing high discharge events and northward extensions of the low-saline water plume from Rio de la Plata. We propose that this resulted in a net increase in northward alongshore transport of fine sediments, seen as a prominent fine-shift at 2000 cal. BP in a core from similar to 24 degrees S on the Brazilian shelf. Wavelet-and spectral analysis of the sortable silt records show a significant similar to 1000-yr periodicity, which we attribute to solar forcing. If correct, this is one of the first indications of solar forcing of this timescale on the Southwestern Atlantic margin.

The Oligocene-Neogene deep-sea Columbia Channel system in the South Brazilian Basin: Seismic stratigraphy and environmental changes

The Columbia Channel (CCS) system is a depositional system located in the South Brazilian Basin, south of the Vitoria-Trindade volcanic chain. It lies in a WNW-ESE direction on the continental rise and abyssal plain, at a depth of between 4200 and 5200 m. It is formed by two depocenters elongated respectively south and north of the channel that show different sediment patterns. The area is swept by a deep western boundary current formed by AABW. The system has been previously interpreted has a mixed turbidite-contourite system. More detailed study of seismic data permits a more precise definition of the modern channel morphology, the system stratigraphy as well as the sedimentary processes and control. The modern CCS presents active erosion and/or transport along the channel. The ancient Oligo-Neogene system overlies a ""upper Cretaceous-Paleogene"" sedimentary substratum (Unit U1) bounded at the top by a major erosive ""late Eocene-early Oligocene"" discordance (D2). This ancient system is subdivided into 2 seismic units (U2 and U3). The thick basal U2 unit constitutes the larger part of the system. It consists of three subunits bounded by unconformities: D3 (""Oligocene-Miocene boundary""), D4 (""late Miocene"") and D5 (""late Pliocene""). The subunits have a fairly tabular geometry in the shallow NW depocenter associated with predominant turbidite deposits. They present a mounded shape in the deep NE depocenter, and are interpreted as forming a contourite drift. South of the channel, the deposits are interpreted as a contourite sheet drift. The surficial U3 unit forms a thin carpet of deposits. The beginning of the channel occurs at the end of U1 and during the formation of D2. Its location seems to have been determined by active faults. The channel has been active throughout the late Oligocene and Neogene and its depth increased continuously as a consequence of erosion of the channel floor and deposit aggradation along its margins. Such a mixed turbidite-contourite system (or fan drift) is characterized by frequent, rapid lateral facies variations and by unconformities that cross the whole system and are associated with increased AABW circulation. (C) 2009 Elsevier B.V. All rights reserved.

A high-resolution Holocene record on the Southern Brazilian shelf: Paleoenvironmental implications

A high-resolution, multi-proxy record has been used to determine the environmental changes during the Holocene on the southern Brazilian shelf Present oceanographic conditions reveal wind and freshwater input as the determinants of short-term productivity changes in the study area. Magnetic susceptibility and grain-size variations, together with proxies of productivity (organic carbon, carbon accumulation rate, Ba, Sr, and Ca content, Ba/Al, Ba/Ti, and Al/Ti ratios) were analyzed and compared with proxies of redox condition (V/Ti ratio), terrigenous input (Fe/Ca and Ti/Ca ratios), as well as other Element/Ti ratios, to evaluate the paleoceanographic and paleoclimatic changes over the period. The core covers a time interval of about 7650 years, with sedimentation rates varying from 0.025 to 0.250 cm a(-1), which represent time intervals of between 8 and 80 a per sample. There is a clear change in the sedimentation rate at about 2800 B.P. All grain-size and elemental results indicate the occurrence of conspicuous changes between 5200 and 5000 cal. B.P., as well as between 3000 and 2800 cal. B.P. A comparison of the results with the palynological information available from the adjacent continental areas suggests that the sedimentary changes in this last interval may be correlated with the onset of modern climatic conditions in South America, and especially, with the onset of the Plata Plume Water, a water mass that carries cold, less saline waters towards the north. However, minor changes are observed at ca. 1500 B.P. and are correlated with an increase in the atmospheric humidity. Furthermore, a time-series analysis undertaken using several proxies indicated the occurrence of Sub-Milankovitch cycles, which may be compared with those reported worldwide. (C) 2008 Elsevier Ltd and INQUA. All rights reserved.

Paleoproductivity changes during the Holocene in the inner shelf of Cabo Frio, southeastern Brazilian continental margin: Benthic foraminifera and sedimentological proxies

Sedimentological and benthic foraminifera analyses carried out on a core (length 4.15 in, collected at 22 degrees 56`31 `` S and 41 degrees 58`48 `` W, at a water depth of 43 in) sampled from the inner shelf of Cabo Frio, southeastern Brazilian continental margin, allowed identification of different hydrodynamic and productivity regimes related to sea-level fluctuations and/or climatic changes, during the last 9.4 ka cal BP. Prior to 7.0 ka cal BP, a less intense hydrodynamic and lower productivity regime occurred at lower sea levels and under drier climatic conditions. Between 7.0 and 5.0 ka cal BP, relatively stronger local oceanic circulation and relatively high productivity were observed, in a scenario of rising sea levels and more humid conditions. From 5.0 to 3.0 ka cal BP, bottom currents weakened and input of nutrients increased, with productivity levels similar to the previous phase at lower sea level and in a drier climate. From 3.0 ka cal BP up to the present, stronger hydrodynamic conditions and a higher productivity regime are linked to the establishment of the upwelling process in Cabo Frio. From 2.5 ka cal BP to the present, upwelling enhancement has been recognized, resulting from the combined action of NE winds and the intensification of the meandering pattern of the Brazil Current (BC). (C) 2008 Elsevier Ltd and INQUA. All rights reserved.

Lapa das boleiras rockshelter: stratigraphy and formation processes at a paleoamerican site in Central Brazil

Lapa clas Boleiras rockshelter, a Paleoamerican archaeological site in Central Brazil, was intensely occupied by humans from 10,000 C-14 BP (11.8 cal kyr BP), until approximately 7500 C-14 BP (8.4 cal kyr BP). In this paper we present some interpretations about the formation processes operating on the site. One of our main conclusions is that the bulk of accumulated sediments at the site is of anthropogenic origin: they are constituted by volumetrically significant quantities of plant ash remains, what is somewhat unexpectedly in view of prevailing models about the lifestyle of Paleoamerican hunter-gatherers in South America. The evidence we discuss below is also consistent with paleoenvironmental data that suggest a dry period during the mid-Holocene in the region, probably leading to a decrease in human occupation [Araujo, A.G.M., Neves, W., Pilo, L.B., Atui, J.P., 2005. Holocene dryness and human Occupation in Brazil during the `Archaic Gap`. Quaternary Research 64, 298-307]. We surmise that both factors underpin a surprising reduction in sediment accumulation at the site during the mid-Holocene. (C) 2008 Published by Elsevier Ltd.

Influence of landscape evolution on the distribution of floristic patterns in northern Amazonia revealed by delta 13C data

The Amazonian lowlands include large patches of open vegetation which contrast sharply with the rainforest, and the origin of these patches has been debated. This study focuses on a large area of open vegetation in northern Brazil, where d13C and, in some instances, C/N analyses of the organic matter preserved in late Quaternary sediments were used to achieve floristic reconstructions over time. The main goal was to determine when the modern open vegetation started to develop in this area. The variability in d13C data derived from nine cores ranges from -32.2 to -19.6 parts per thousand, but with nearly 60% of data above -26.5 parts per thousand. The most enriched values were detected only in ecotone and open vegetated areas. The development of open vegetation communities was asynchronous, varying between estimated ages of 6400 and 3000 cal a BP. This suggests that the origin of the studied patches of open vegetation might be linked to sedimentary dynamics of a late Quaternary megafan system. As sedimentation ended, this vegetation type became established over the megafan surface. In addition, the data presented here show that the presence of C4 plants must be used carefully as a proxy to interpret dry paleoclimatic episodes in Amazonian areas. Copyright (c) 2012 John Wiley & Sons, Ltd.

Synthesis and Photodynamic Effect of New Highly Photostable Decacationically Armed [60]- and [70]Fullerene Decaiodide Monoadducts To Target Pathogenic Bacteria and Cancer Cells

Novel water-soluble decacationically armed C-60 and C-70 decaiodide monoadducts, C-60- and C-70[>M(C3N6+C3)(2)], were synthesized, characterized, and applied as photosensitizers and potential nano-PDT agents against pathogenic bacteria and cancer cells. A high number of cationic charges per fullerene cage and H-bonding moieties were designed for rapid binding to the anionic residues displayed on the outer parts of bacterial cell walls. In the presence of a high number of electron-donating iodide anions as parts of quaternary ammonium salts in the arm region, we found that C-70[>M(C3N6+C3)(2)] produced more HO center dot than C-60[>M(C3N6+C3)(2)], in addition to O-1(2). This finding offers an explanation of the preferential killing of Gram-positive and Gram-negative bacteria by C-60[>M(C3N6+C3)(2)] and C-70[>M(C3N6+C3)(2)], respectively. The hypothesis is that O-1(2) can diffuse more easily into porous cell walls of Gram-positive bacteria to reach sensitive sites, while the less permeable Gram-negative bacterial cell wall needs the more reactive HO center dot to cause real damage.

Neotectonics in the northern equatorial Brazilian margin

An increasing volume of publications has addressed the role of tectonics in inland areas of northern Brazil during the Neogene and Quaternary, despite its location in a passive margin. Hence, northern South America plate in this time interval might have not been as passive as usually regarded. This proposal needs further support, particularly including field data. In this work, we applied an integrated approach to reveal tectonic structures in Miocene and late Quaternary strata in a coastal area of the Amazonas lowland. The investigation, undertaken in Marajo Island, mouth of the Amazonas River, consisted of shallow sub-surface geophysical data including vertical electric sounding and ground penetrating radar. These methods were combined with morphostructural analysis and sedimentological/stratigraphic data from shallow cores and a few outcrops. The results revealed two stratigraphic units, a lower one with Miocene age, and an upper one of Late Pleistocene-Holocene age. An abundance of faults and folds were recorded in the Miocene deposits and, to a minor extent, in overlying Late Pleistocene-Holocene strata. In addition to characterize these structures, we discuss their origin, considering three potential mechanisms: Andean tectonics, gravity tectonics related to sediment loading in the Amazon Fan, and rifting at the continental margin. Amongst these hypotheses, the most likely is that the faults and folds recorded in Marajo Island reflect tectonics associated with the history of continental rifting that gave rise to the South Atlantic Ocean. This study supports sediment deposition influenced by transpression and transtension associated with strike-slip divergence along the northern Equatorial Brazilian margin in the Miocene and Late Pleistocene-Holocene. This work records tectonic evidence only for the uppermost few ten of meters of this sedimentary succession. However, available geological data indicate a thickness of up to 6 km, which is remarkably thick for an area regarded as a passive margin. (C) 2012 Elsevier Ltd. All rights reserved.