Columnar joints in the Patino Formation sandstones, Eastern Paraguay: a dynamic interaction between dyke intrusion, quartz dissolution and cooling-induced fractures

The Patino Formation sandstones, which crop out in Aregua neighborhood in Eastern Paraguay and show columnar joints near the contact zone with a nephelinite dyke, have as their main characteristics the high proportion of syntaxial quartz overgrowth and a porosity originated from different processes, initially by dissolution and later by partial filling and fracturing. Features like the presence of floating grains in the syntaxial cement, the transitional interpenetrative contact between the silica-rich cement and grains as well as the intense fracture porosity are strong indications that the cement has been formed by dissolution and reprecipitation of quartz from the framework under the effect of thermal expansion followed by rapid contraction. The increase of the silica-rich cement towards the dyke in association with the orthogonal disposition of the columns relative to dyke walls are indicative that the igneous body may represent the main heat source for the interstitial aqueous solutions previously existing in the sediments. At macroscopic scale, the increasing of internal tensions in the sandstones is responsible for the nucleation of polygons, leading to the individualization of prisms, which are interconnected by a system of joints, formed firstly on isotherm surfaces of low temperature and later on successive adjacent planes towards the dyke heat source.

Correlation between thermoluminescence sensitivity and crystallization temperatures of quartz: Potential application in geothermometry

The thermoluminescence (TL) characteristics of quartz are highly dependent of its thermal history. Based on the enhancement of quartz luminescence occurred after heating, some authors proposed to use quartz TL to recover thermal events that affected quartz crystals. However, little is know about the influence of the temperature of quartz crystallization on its TL characteristics. In the present study, we evaluate the TL sensitivity and dose response curves of hydrothermal and metamorphic quartz with crystallization temperatures from 209 +/- 15 to 633 +/- 27 degrees C determined through fluid inclusion and mineral chemistry analysis. The studied crystals present a cooling thermal history, which allow the acquiring of their natural TL without influence of heating after crystallization. The TL curves of the studied samples present two main components formed by different peaks overlapped around 110 C and 200-400 degrees C. The TL sensitivity in the 200-400 degrees C region increases linearly with the temperature of quartz crystallization. No relationship was observed between temperatures of quartz crystallization and saturation doses (<100 Gy). The elevated TL sensitivity of the high temperature quartz is attributed to the control exerted by the temperature of crystallization on the substitution of Si(4+) by ions such as Al(3+) and Ti(4+), which produce defects responsible for luminescence phenomena. The linear relationship observed between TL in the 200-400 degrees C region and crystallization temperature has potential use as a quartz geothermometer. The relative abundance of quartz in the earth crust and the easiness to measure TL are advantageous in relation to geothermometry methods based on chemistry of other minerals. (C) 2010 Elsevier Ltd. All rights reserved.

U-Pb zircon and (40)Ar-(39)Ar K-feldspar dating of syn-sedimentary volcanism of the Neoproterozoic Marica Formation: constraining the age of foreland basin inception and inversion in the Camaqua Basin of southern Brazil

New U-Pb zircon and (40)Ar-(39)Ar K-feldspar data are presented for syn-sedimentary volcanogenic rocks from the Neoproterozoic Marica Formation, located in the southern Brazilian shield. Seven (of nine) U-Pb sensitive high-resolution ion microprobe analyses of zircons from pyroclastic cobbles yield an age of 630.2 +/- 3.4 Ma (2 sigma), interpreted as the age of syn-sedimentary volcanism, and thus of the deposition itself. This result indicates that the Marica Formation was deposited during the main collisional phase (640-620 Ma) of the Brasiliano II orogenic system, probably as a forebulge or back-bulge, craton-derived foreland succession. Thus, this unit is possibly correlative of younger portions of the Porongos, Brusque, Passo Feio, Abapa (Itaiacoca) and Lavalleja (Fuente del Puma) metamorphic complexes. Well-defined, step-heating (40)Ar-(39)Ar K-feldspar plateau ages obtained from volcanogenic beds and pyroclastic cobbles of the lower and upper successions of the Marica Formation yielded 507.3 +/- 1.8 Ma and 506.7 +/- 1.4 Ma (2 sigma), respectively. These data are interpreted to reflect total isotopic resetting during deep burial and thermal effects related to magmatic events. Late Middle Cambrian cooling below ca. 200 degrees C, probably related to uplift, is tentatively associated with intraplate effects of the Rio Doce and/or Pampean orogenies (Brasiliano III system). In the southern Brazilian shield, these intraplate stresses are possibly related to the dominantly extensional opening of a rift or a pull-apart basin, where sedimentary rocks of the Camaqua Group (Santa Barbara and Guaritas Formations) accumulated.

Investigation of interfacial processes at tetraruthenated zinc porphyrin films using electrochemical surface plasmon resonance and electrochemical quartz crystal microbalance

In the present work we describe the investigation of interfacial and superficial processes on tetraruthenated zinc porphyrin (ZnTRP) films immobilized on gold electrode surface. In situ and real time measurements employing electrochemical surface plasmon resonance (ESPR)and electrochemical quartz crystal microbalance (EQCM) have given new insights into the electrochemical oxidation of ferrocyanide and phenolic compounds (acetaminophen, dopamine, and catechol) on ZnTRP modified electrodes. The decrease of diode like behavior in the presence of such phenolic species in contrast with ferrocyanide was clearly assigned to the inclusion of those species in the porphyrin film, creating new conduction pathways connecting the gold electrode surface with the film/solution interface. In fact, there are evidences that they can intercalate in the film (catechol > dopamine > acetaminophen), whereas ferrocyanide is completely excluded. Accordingly, the molecular size may play a fundamental role in such a process. (C) 2009 Published by Elsevier Ltd.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

ESR dating of pleistocene mammal teeth and its implications for the biostratigraphy and geological evolution of the coastal plain, Rio Grande do Sul, southern Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Fission-track dating of South American natural glasses: an overview

Although many glass-bearing horizons can be found in South American volcanic complexes or sedimentary series, only a relatively few tephra and obsidian-bearing volcanic fields have been studied using the fission-track (FT) dating method. Among them, the volcanics located in the Sierra de Guamani (east of Quito, Ecuador) were studied by several authors. Based upon their ages, obsidians group into three clusters: (1) very young obsidians, similar to 0.2Ma old, (2) intermediate-age obsidians, similar to 0.4- similar to 0.8 Ma old, and (3) older obsidians, similar to 1.4- similar to 1.6 Ma old. The FT method is also an efficient alternative technique for identification of the sources of prehistoric obsidian artefacts. Provenance studies carried out in South America have shown that the Sierra de Guamani obsidian occurrences were important sources of raw material for toot making during pre-Columbian times. Glasses originated from these sources were identified in sites distributed over relatively wide areas of Ecuador and Colombia.Only a few systematic studies on obsidians in other sectors were carried out. Nevertheless, very singular glasses have been recognised in South America, such as Macusanite (Peru) and obsidian Quiron (Argentina), which are being proposed as additional reference materials for FT dating. Analyses of tephra beds interstratified with sedimentary deposits revealed the performance of FT dating in tephrochronological studies. A remarkable example is the famous deposit outcropping at Farola Monte Hermoso, near Bahia Blanca (Buenos Aires Province), described for the first time by the middle of the 19th century by Charles Darwin.Considering the large number of volcanic glasses that were recognised in volcanic complexes and in sedimentary series, South America is a very promising region for the application of FT dating. The examples given above show that this technique may yield important results in different disciplinary fields. (c) 2005 Elsevier Ltd. All rights reserved.

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.

New constraints on ages of glasses proposed as reference materials for fission-track dating

New analyses have been performed in order to enhance the data-set on the independent ages of four glasses that have been proposed as reference materials for fission-track dating. The results are as follows. Moldavite - repeated (40)Ar/(39)Ar age determinations on samples from deposits from Bohemia and Moravia yielded an average of 14.34 +/- 0.08 Ma. This datum agrees with other recent determinations and is significantly younger than the (40)Ar/(39)Ar age of 15.21 +/- 0.15 Ma determined in the early 1980s. Macusanite (Peru) -four K-Ar ages ranging from 5.44 +/- 0.06 to 5.72 +/- 0.12 Ma have been published previously. New (40)Ar/(39)Ar ages gave an average of 5.12 +/- 0.04 Ma. Plateau fission-track ages determined using the IRMM-540 certified glass and U and Th thin films for neutron fluence measurements agree better with these new (40)Ar/(39)Ar ages than the previously published ages. Roccastrada glass (Italy) - a new (40)Ar/(39)Ar age, 2.45 +/- 0.04 Ma, is consistent with previous determinations. The Quiron obsidian (Argentina) is a recently discovered glass that has been proposed as an additional reference material for its high spontaneous track density (around 100 000 cm(-2)). Defects that might produce spurious tracks are virtually absent. An independent (40)Ar/(39)Ar age of 8.77 +/- 0.09 Ma was determined and is recommended for this glass. We believe that these materials, which will be distributed upon request to fission-track groups, will be very useful for testing system calibrations and experimental procedures.

Sugarcane bagasse ash as a potential quartz replacement in red ceramic

Sugarcane bagasse ash (SCBA) is an industrial waste that contains silicon and aluminum oxides as the major components and iron, calcium, magnesium, and potassium oxides as the main minor components. In this paper, SCBA from one Brazilian factory was characterized and tested for its influence on the ceramic properties of clay/ash ceramic probes. Prismatic probes were pressed (18 MPa) using a ceramic mass mixed with 0%, 5%, 8%, and 10% ash. The probes were fired at temperatures between 800 degrees and 1200 degrees C. X-ray diffraction, X-ray fluorescence, thermal analysis (differential thermal analysis, thermo-gravimetric analysis/differential thermogravimetric analysis), and tests for texture (particle-size analysis), flexural strength, and linear shrinkage were carried out to characterize the samples. The results showed that the amount of ash to be incorporated will depend on mainly the composition of clay but also ash, and indicated that the clay used in this work can incorporate up to 10% weight of ash to produce solid bricks. The results also showed an improvement in ceramic/ash properties up to sintering temperatures higher than 1000 degrees C.

Fission track and U-Pb in situ dating applied to detrital zircon from the Vale do Rio do Peixe Formation, Bauru Group, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Micro-Raman spectroscopy and SEM/EDX applied to improve the zircon fission track method used for dating geological formations

The zircon mineral is widely studied in geochronology. In the case of the fission track method (FTM), the age is determined by the density of fission tracks at the zircon surface, which can be observed with an optical microscope after an appropriate chemical treatment (etching). The etching must be isotropic at the zircon grain surface to be used in the FTM, which leads those zircon grains whose etching is anisotropic to be discarded. The only reason for this discarding is the nonuniform morphology of the surface grain seen by optical microscopy, that is, no further physicochemical analysis is performed. In this work, combining micro-Raman and scanning electron microscopy (SEM) to study the etching anisotropy, it was shown that zircon grains that present at least one area at the surface where the density of fission track is uniform can be used in the FTM. The micro-Raman showed characteristic spectra of the standard zircon sample either from the areas where there are tracks or from where there are not. The only difference found was in the Raman bandwidths, which were broader for the areas with higher density of fission tracks. This suggests simply a decrease in the relative percentage of the crystalline/amorphous phases at these areas. The SEM/energy dispersive spectrometry (EDX) showed that there were no significant differences in the principal chemical composition at the areas with and without fission tracks. Copyright (c) 2008 John Wiley & Sons, Ltd.

Zircon fission track and U-Th-Pb in situ dating of Rio Parana Formation, Parana Basin, Brazil

Ages of zircon from sedimentary samples of Rio Parana Formation, belonging of Bauru Group, north of Parana Basin, Brazil, has been determined by zircon Fission Track and U-Th-Pb in situ dating methods. The obtained ages are from same zircon grain that provided information on the source areas for the sediments and the morphotectonic events.

ESR dating of a subfossil shell from Couve Island, Ubatuba, Brazil

The occurrence of subfossil material in bottom sediments of Couve Island, Ubatuba region, São Paulo State, is confirmed. The analyzed material consists of a bivalve shell that was dated by the electron spin resonance technique. By the additive irradiation method an archaeological absorbed dose of (25 +/- 5) Gy was obtained and calibration with other dating works in the same area allows the inference of an age of (25 +/- 5) x 10(2) years. The importance of this finding and its paleoecological implications could contribute to elucidating the nature of short-term environmental changes in the Brazilian coastline during the Holocene, as well as becoming an important tool to the understanding of the distribution and biological aspects of the bivalve fauna. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Interfacial fracture of dentin adhesively bonded to quartz-fiber reinforced composite

The paper presents the results of an experimental study of interfacial failure in a multilayered structure consisting of a dentin/resin cement/quartz-fiber reinforced composite (FRC). Slices of dentin close to the pulp chamber were sandwiched by two half-circle discs made of a quartz-fiber reinforced composite, bonded with bonding agent (All-bond 2, BISCO, Schaumburg) and resin cement (Duo-link. BISCO, Schaumburg) to make Brazil-nut sandwich specimens for interfacial toughness testing. Interfacial fracture toughness (strain energy release rate, G) was measured as a function of mode mixity by changing loading angles from 0 degrees to 15 degrees. The interfacial fracture surfaces were then examined using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) to determine the failure modes when loading angles changed. A computational model was also developed to calculate the driving forces, stress intensity factors and mode mixities. Interfacial toughness increased from approximate to 1.5 to 3.2 J/m(2) when the loading angle increases from approximate to 0, 0 to 15 degrees. The hybridized dentin/cement interface appeared to be tougher than the resin cement/quartz-fiber reinforced epoxy. The Brazil-nut sandwich specimen was a suitable method to investigate the mechanical integrity of dentin/cement/FRC interfaces. (C) 2011 Elsevier B.V. All rights reserved.