Interplay of Late Cenozoic Siliciclastic Supply and Carbonate Response on the Southeast Florida Platform

High-resolution seismic-reflection data collected along the length of the Caloosahatchee River in southwestern Florida have been correlated to nannofossil biostratigraphy and strontium-isotope chemostratigraphy at six continuously cored boreholes. These data are interpreted to show a major Late Miocene(?) to Early Pliocene fluvial– deltaic depositional system that prograded southward across the carbonate Florida Platform, interrupting nearly continuous carbonate deposition since early in the Cretaceous. Connection of the platform top to a continental source of siliciclastics and significant paleotopography combined to focus accumulation of an immense supply of siliciclastics on the southeastern part of the Florida Platform. The remarkably thick (> 100 m), sand-rich depositional system, which is characterized by clinoformal progradation, filled in deep accommodation, while antecedent paleotopography directed deltaic progradation southward within the middle of the present-day Florida Peninsula. The deltaic depositional system may have prograded about 200 km southward to the middle and upper Florida Keys, where Late Miocene to Pliocene siliciclastics form the foundation of the Quaternary carbonate shelf and shelf margin of the Florida Keys. These far-traveled siliciclastic deposits filled accommodation on the southeastern part of the Florida Platform so that paleobathymetry was sufficiently shallow to allow Quaternary recovery of carbonate sedimentation in the area of southern peninsular Florida and the Florida Keys.

A macroscopic kinetic model for DNA polymerase elongation and high-fidelity nucleotide election

The enzymatically catalyzed template-directed extension of ssDNA/primer complex is an impor-tant reaction of extraordinary complexity. The DNA polymerase does not merely facilitate the insertion of dNMP, but it also performs rapid screening of substrates to ensure a high degree of fidelity. Several kinetic studies have determined rate constants and equilibrium constants for the elementary steps that make up the overall pathway. The information is used to develop a macro-scopic kinetic model, using an approach described by Ninio [Ninio J., 1987. Alternative to the steady-state method: derivation of reaction rates from first-passage times and pathway probabili-ties. Proc. Natl. Acad. Sci. U.S.A. 84, 663–667]. The principle idea of the Ninio approach is to track a single template/primer complex over time and to identify the expected behavior. The average time to insert a single nucleotide is a weighted sum of several terms, in-cluding the actual time to insert a nucleotide plus delays due to polymerase detachment from ei-ther the ternary (template-primer-polymerase) or quaternary (+nucleotide) complexes and time delays associated with the identification and ultimate rejection of an incorrect nucleotide from the binding site. The passage times of all events and their probability of occurrence are ex-pressed in terms of the rate constants of the elementary steps of the reaction pathway. The model accounts for variations in the average insertion time with different nucleotides as well as the in-fluence of G+C content of the sequence in the vicinity of the insertion site. Furthermore the model provides estimates of error frequencies. If nucleotide extension is recognized as a compe-tition between successful insertions and time delaying events, it can be described as a binomial process with a probability distribution. The distribution gives the probability to extend a primer/template complex with a certain number of base pairs and in general it maps annealed complexes into extension products.

Phylogeographic analysis in populations of Protonectarina sylveirae (Saussure, 1854) (Hymenoptera, Vespidae, Polistinae)

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

Estudo da resistência à corrosão de ligas Ni-Cr-Mo-Ta E Ni-Cr-Mo-W em solução NaF 0,08 mol/L, pH 4,7 para aplicações odontológicas

A large number of metal alloys are used in Dentistry for the manufacture of fixed and removable dentures. In the oral cavity, these structures are exposed to a chemically aggressive medium, like saliva and mechanical efforts, like mastication. In addition, acidic solutions containing fluoride ions are also frequently used in dental treatments to prevent dental plates and decays development. In this context, it was considered important to investigate the influence that a fourth element could exert when added to the ternary alloy Ni-Cr-Mo, largely used in Brazil. Therefore, electrochemical tests were done to evaluate the resistance to corrosion of quaternary alloy 65Ni-25Cr-5Mo-5Ta and 65Ni-25Cr-5Mo-5W in NaF solution 0,08mol / L, pH = 4.7. For greater understanding the microstructure and morphology of alloys were studied, through metallographic analysis, using optics microscopy and electron microscopy scanning. For the electrochemical tests were applied techniques traditionally used in corrosion researches, such as: potential measures in open circuit (OCP) and cyclic polarization (CP). It was found that both quaternary alloys showed very similar results. Comparing these quaternary alloys with the ternary 65Ni-25Cr-10Mo, it was found that the quaternary alloys exhibit greater resistance to corrosion, in other words, less passivation current density than the ternary alloy, showing that it is advantageous to add a fourth element in the alloy

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.

New insights on reaction pathway selectivity promoted by crown ether phase-transfer catalysis: Model ab initio calculations of nucleophilic fluorination

Crown ethers have the ability of solubilizing inorganic salts in apolar solvents and to promote chemical reactions by phase-transfer catalysis. However, details on how crown ethers catalyze ionic S(N)2 reactions and control selectivity are not well understood. In this work, we have used high level theoretical calculations to shed light on the details of phase-transfer catalysis mechanism of KF reaction with alkyl halides promoted by 18-crown-6. A complete analysis of the of the model reaction between KF(18-crown-6) and ethyl bromide reveals that the calculations can accurately predict the product ratio and the overall kinetics. Our results point out the importance of the K* ion and of the crown ether ring in determining product selectivity. While the K* ion favors the S(N)2 over the E2 anti pathway, the crown ether ring favors the S(N)2 over E2 syn route. The combination effects lead to a predicted 94% for the S(N)2 pathway in excellent agreement with the experimental value of 92%. A detailed analysis of the overall mechanism of the reaction under phase-transfer conditions also reveals that the KBr product generated in the nucleophilic fluorination acts as an inhibitor of the 18-crown-6 catalyst and it is responsible for the observed slow reaction rate. (C) 2012 Elsevier B.V. All rights reserved.

Peat palynomorphs from Eugenio de Melo, middle valley of Paraiba do Sul River, Sao Paulo, Brazil.

Peat palynomorphs from Eugenio de Melo, middle valley of Paraiba do Sul River, Sao Paulo, Brazil. This paper presents palynomorphs identified in the peats of the Eugenio de Melo region, the middle valley of the Paraiba do Sul River, Sao Paulo State. The samples were collected at intervals of 10 cm from a core with 3.90 m deep, aged between 11400-11220 and 490-290 cal. years B.P. Three types of algae were identified and presented, and ten spores, two gymnosperm pollen grains and thirty-nine angiosperms were described, with their own ecological information.

Divide to conquer: a complex pattern of biodiversity depicted by vertebrate components in the Brazilian Atlantic Forest

The identification of northern and southern components in different vertebrate species led researchers to accept a two-component hypothesis for the Brazilian Atlantic forest (BAF). Nevertheless, neither a formal proposal nor a meta-analysis to confirm this coincidence was ever made. Our main objective here was therefore to systematically test in how many vertebrate components the BAF could be divided by analysing existing empirical data. We used two approaches: (1) mapping and comparing the proposed areas of vertebrate endemism in the BAF and (2) analysing studies mentioning spatial subdivisions in distinct forest-dependent vertebrates within the biome, by the use of panbiogeography. The four large-scale endemism area components together with the six small-scale panbiogeographical ones allowed the definition of three BAF greater regions, subdivided into nine vertebrate components, latitudinally and longitudinally organized. Empirical time estimates of the diversification events within the BAF were also reviewed. Diversification of these vertebrates occurred not only in the Pleistocene but also throughout the Miocene. Our results confirm the BAF's complex history, both in space and time. We propose that future research should be small-scale and focused in the vertebrate components identified herein. Given the BAF's heterogeneity, studying via sections will be much more useful in identifying the BAF's historical biogeography. (c) 2012 The Linnean Society of London, Biological Journal of the Linnean Society, 2012, 107, 39-55.