Structural modifications in silica sonogels prepared with additions of poly(vinyl alcohol)

Silica wet gels were prepared from acid sonohydrolysis of tetraethoxysilane (TEOS) and additions of poly(vinyl alcohol) (PVA)-water solution. Aerogels were obtained from supercritical CO(2) extraction. The samples were studied by thermal gravimetric (TG) analysis, small-angle X-ray scattering (SAXS), and nitrogen adsorption. The structure of wet gels can be described as a mass fractal with dimension D equal to 2.0 on the whole length scale experimentally probed by SAXS, from similar to 0.3 to similar to 15 nm. Pure and low-PVA-addition wet gels exhibit an upper cutoff accounting for a finite characteristic length xi of the mass fractal structure. Additions , of PVA increase without modifying D, which was attributed to a steric effect of the polymer in the structure. The pore volume fraction of the aerogels diminishes typically about 11% with respect to that of the wet gels, although nitrogen adsorption could be underestimating some porosity. The pore size distribution of the aerogels is shifted toward the mesopore region with the additions of PVA, in a straight relationship with the increase of xi in the wet gels. The thermal stability of the pore size distribution of the aerogels was studied up to 1000 degrees C.

Hydro(radio)chemical relationships in the giant Guarani aquifer, Brazil

This investigation was carried out within the Parana sedimentary basin and involved the sampling of 78 pumped tubular wells for evaluating the hydrochemistry and radioactivity due to the nuclides (238)U, (234)U, (222)Ra, (226)Ra, and (228)Ra in the Brazilian part of Guarani aquifer. Several significant correlations were found involving the geostatic pressure, for instance, specific flow rate, CO(3)(2-), SO(4)(2-) temperature, dissolved O(2), free CO(2), pH, redox potential Eh, conductivity, Na, HCO(3)-, CO(3)(2-) , SI(calcite), Cl(-), F(-), SO(4)(2-), and B. Carbonates precipitation was evidenced by inverse correlation between CO(3)(2-) and Ca, Mg, Sr, and Ba, whereas Na exhibited an opposite trend, dissolving rather than precipitating with increasing CO(3)(2-) concentration. An inverse correlation between 3 and K was found, possibly related to the increasing tendency of K to recombine with the thickness of the clayey layers. HCO(3)-played an important role on Na, Ca, Mg, and Sr dissolution. The dissolved U content and (234)U/(238)U activity ratio data were plotted on a two-dimensional diagram that was successfully utilized on identifying an unreported zone of U accumulation, though not necessarily of economic size and grade. The variability in chemical and radionuclides data indicated an important influence of the underlying Paleozoic sediments in the composition of waters from Guarani aquifer. The available data allowed estimate the groundwater residence time by two U-isotopes disequilibrium methods. Values of 45-61 ka were initially calculated, depending on the adopted porosity (15-20%), but a longer residence time (- 640 ka) was also estimated, which is more compatible with the hydraulic conductivity data in Guarani aquifer and groundwater flow velocity occurring at Milk River aquifer, Alberta, Canada. Such time range agrees with previously reported (14)C ages exceeding 30 ka BP at the more central parts of the Parana sedimentary basin. (c) 2005 Elsevier B.V. All rights reserved.

Black and green pigments based on chromium-cobalt spinels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Changes in optical properties caused by UV-irradiation of aquatic humic substances from the amazon river basin: Seasonal variability evaluation

Aquatic humic substances (AHS) isolated from two characteristic seasons of the Negro river, winter and summer corresponding to floody and dry periods, were structurally characterized by (13)C nuclear magnetic ressonance. Subsequently, AHS aqueous solutions were irradiated with a polychromatic lamp (290-475 nm) and monitored by its total organic carbon (TOC) content, ultraviolet-visible (UV-vis) absorbance, fluorescence and Fourier transformed infrared spectroscopy (FTIR). As a result, a photobleaching upto 80% after irradiation of 48 h was observed. Conformational rearrangements and formation of low molecular complexity structures were formed during the irradiation, as deduced from the pH decrement and the fluorescence shifting to lower wavelengths. Additionally a significant mineralization with the formation of CO(2), CO, and inorganic carbon compounds was registered, as assumed by TOC losses of up to 70%. The differences in photodegradation between samples expressed by photobleaching efficiency were enhanced in the summer sample and related to its elevated aromatic content. Aromatic structures are assumed to have high autosensitization capacity effects mediated by the free radical generation from quinone and phenolic moieties.

Investigação por espectroscopia Mössbauer de compostos de ferro(0) contendo dissulfeto de carbono

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Caracterização e biodigestão anaeróbia dos dejetos de caprinos

Quantificar e caracterizar os dejetos gerados por cabras Saanen em quatro categorias de idade e alimentadas com três dietas e na seqüência, e promover a biodigestão anaeróbia dos dejetos constituíram os objetivos deste trabalho. Para a produção de dejetos, foram utilizadas 36 cabras Saanen, com idades entre 2 e 4 (C1), 4 e 8 (C2), 8 e 12 (C3) e acima de 12 meses (C4), alimentadas com as dietas 1 (D1: 80% volumoso (Vol) e 20% concentrado (Con)); 2 (D2: 60% Vol e 40% Con) e 3 (D3: 40% Vol e 20% Con). Foram quantificadas as produções diárias de fezes e urina e seus teores em N, P, K, Ca, Mg, Na, Fe, Cu, Zn e Mn. Com a mistura das fezes e urina de todas as categorias, separadas segundo as dietas, foram abastecidos biodigestores batelada, com capacidade para 4 L de substrato em fermentação. A C1 apresentou menor (P<0,05) excreção de fezes (164,1 g de MS (massa seca)/animal por dia) e o menor consumo de alimento (362,2g MS (massa seca)/animal por dia). As maiores concentrações de N, P, K, Ca, Mg e K ocorreram nas fezes e urina geradas por cabras da C4 e alimentadas pela D3. O substrato preparado com dejetos oriundos da D3 apresentou 45% de redução nos teores de sólidos voláteis (SV). Os substratos preparados com dejetos obtidos de animais alimentados com a D3 produziram mais biogás (P<0,01) por kg de sólidos totais e SV adicionados.

A SIMPLE NUMERICAL-METHOD FOR HYDROSTATIC INCOMPRESSIBLE MODELS WITH RIGID LIDS

A simple and easily implemented method is developed to keep the vertical velocity equal to zero at the bottom and top of hydrostatic incompressible numerical models. The pressure is computed at the top by correcting its value given in the previous time step so that the vertical integral of the horizontal divergence is zero at each column. Numerical experiments that exhibit small time variations of pressure at the top are able to simplify the algorithm and save computer time. Numerical simulations illustrate the method effectiveness for a horizontal deformation-induced frontogenesis.

Allometric growth in the fiddler crab Uca thayeri (Brachyura, Ocypodidae) from a subtropical mangrove

The relative growth of U. thayeri was studied for a subtropical mangrove population in the estuary of the Comprido and Escuro rivers, Ubatuba, São Paulo State, Brazil. The evaluation of the morphological sexual maturity of U. thayeri was performed using the allometric technique. Remarkable ontogenetic changes were observed in the allometric growth of the male major cheliped and the female abdomen, indicating that these structures are closely connected to the timing of sexual maturity. For males, the relative-growth analysis of cheliped propodus length rendered an estimate of 13.8 mm of carapace width for the size at onset of sexual maturity. A distinct growth pattern was observed for the abdomen of U. thayeri females. It has a wide puberty size range (from 10.7 to 16.8 mm of CW) compared to other brachyurans previously studied. Thus, the females' abdominal growth can be represented by three growth phases: immature, transitional, and mature. The major cheliped is the fight one in 50% of males. The median length of the male major cheliped did not differ between right- and left-handed crabs.

Colonization of a 'Lost World': Encrustation patterns in modern subtropical brachiopod assemblages.

The encrustation of Paleozoic rhynchonelliform brachiopods has been studied for decades, but modern brachiopods have not received similar scrutiny. The discovery of abundant subtropical brachiopods from the Southeast Brazilian Bight provides an unprecedented opportunity to assess epibiont abundance, diversity, and encrustation patterns in modern brachiopod assemblages. Across the outer shelf, encrustation frequencies vary among taxa, from mean values of 0.45% for Platidia to 9.3% for Argyrotheca. Encrustation frequencies for Bouchardia increase from 1.6% on the outer shelf to 84% on the inner shelf Larger valves are encrusted more frequently, and epibionts preferentially colonize valve interiors. Increased encrustation on the inner shelf may reflect the greater surface area of larger hosts, longer exposure of dead shells, water-mass characteristics, sedimentation rates, productivity, or other factors that vary with depth. Inner-shelf brachiopods exhibit encrustation frequencies comparable to those reported for epifaunal bivalves. The epibiont fauna is dominated by bryozoans and serpulids, with minor roles played by spirorbids, bivalves, barnacles, foraminifera, algae, and other taxa. Epibiont abundance at each site is highly variable, but sites are similar in rank importance of epibiont taxa. A different suite of epibionts colonized Paleozoic brachiopods, but similar patterns of encrustation have been observed, including preferential settlement according to valve morphology. These results provide a baseline for evaluating the encrustation of modern bivalves and ancient brachiopods, and may elucidate the macroevolutionary history of epibionts and their relationship to their hosts.

The amphibian tree of life

The evidentiary basis of the currently accepted classification of living amphibians is discussed and shown not to warrant the degree of authority conferred on it by use and tradition. A new taxonomy of living amphibians is proposed to correct the deficiencies of the old one. This new taxonomy is based on the largest phylogenetic analysis of living Amphibia so far accomplished. We combined the comparative anatomical character evidence of Haas (2003) with DNA sequences from the mitochondrial transcription unit HI (12S and 16S ribosomal RNA and tRNA(Valine) genes, 2,400 bp of mitochondrial sequences) and the nuclear genes histone H3, rhodopsin, tyrosinase, and seven in absentia, and the large ribosomal subunit 28S (approximate to 2,300 bp of nuclear sequences; ca. 1.8 million base pairs; x ($) over bar = 3.7 kb/terminal). The dataset includes 532 terminals sampled from 522 species representative of the global diversity of amphibians as well as seven of the closest living relatives of amphibians for outgroup comparisons.

Bromeliad-living spiders improve host plant nutrition and growth

Although bromeliads are believed to obtain nutrients from debris deposited by animals in their rosettes, there is little evidence to support this assumption. Using stable isotope methods, we found that the Neotropical jumping spider Psecas chapoda (Salticidae), which lives strictly associated with the terrestrial bromeliad Bromelia balansae, contributed 18% of the total nitrogen of its host plant in a greenhouse experiment. In a one-year field experiment, plants with spiders produced leaves 15% longer than plants from which the spiders were excluded. This is the first study to show nutrient provisioning in a spider-plant system. Because several animal species live strictly associated with bromeliad rosettes, this type of facultative mutualism involving the Bromeliaceac may be more common than previously thought.

Biotic interactions recorded in shells of recent rhynchonelliform brachiopods from San Juan Island, USA

Biotic interactions between brachiopods and spionid polychaete worms, collected around San Juan Islands (USA), were documented using observations from live-collected individuals and traces of bioerosion found in dead brachiopod shells. Specimens of Terebratalia tranversa (Sowerby), Terebratulina unguicula (Carpenter), Laqueus californianus (Koch), and Hemithiris psittacea (Gmelin) were collected from rocky and muddy substrates, from sites ranging from 14.7-93.3 m in depth. Out of 1,131 specimens, 91 shells showed traces of bioerosion represented by horizontal tubes. Tubes are U-shaped, straight or slightly curved, sometimes branched, with both tube openings communicating externally. on internal surfaces of infested shells, blisters are observed. All brachiopod species yielded tubes, except for H. psittacea. Tubes are significantly more frequent on live specimens, and occur preferentially on larger, ventral valves. This pattern suggests selectivity by the infester rather than a taphonomic bias. Given the mode of life of studied brachiopods (epifaunal, sessile, attached to the substrate, lying on dorsal valve), ventral valves of living specimens should offer the most advantageous location for suspension-feeding infesters. Frequent infestation of brachiopods by parasitic spionids is ecologically and commercially noteworthy because farmed molluscs are also commonly infested by parasitic polychaetes. In addition, brachiopod shells are among the most common marine macroscopic fossils found in the Phanerozoic fossil record. From a paleontological perspective, spionid-infested brachiopod shells may be a prime target for studying parasite-host interactions over evolutionary time scales.

Phylogenetic analysis of the neotropical pseudopolybia de saussure, 1863, with description of the male genitalia of pseudopolybia vespiceps (Hymenoptera : Vespidae, epiponini)

The male genitalia of Pseudopolybia vespiceps are described and compared to congeners. Characters of the male genitalia are combined with morphological characters of the females and nests and used in a phylogenetic analysis. The single cladogram resulting supports monophyly of the genus Pseudopolybia and interrelationships among the species as: P. langi + (P. difficilis + (P. compressa + P. vespiceps)). A new, illustrated identification key is presented.

Mass fractal characteristics of wet sonogels as determined by small-angle x-ray scattering and differential scanning calorimetry

Low density silica sonogels were prepared from acid sonohydrolysis of tetraethoxysilane. Wet gels were studied by small-angle x-ray scattering (SAXS) and differential scanning calorimetry (DSC). The DSC tests were carried out under a heating rate of 2 degrees C/min from -120 degrees C up to 30 degrees C. Aerogels were obtained by CO(2) supercritical extraction and characterized by nitrogen adsorption and SAXS. The DSC thermogram displays two distinct endothermic peaks. The first, a broad peak extending from about -80 degrees C up to practically 0 degrees C, was associated to the melting of ice nanocrystals with a crystal size distribution with pore diameter ranging from 1 or 2 nm up to about 60 nm, as estimated from Thomson's equation. The second, a sharp peak with onset temperature close to 0 degrees C, was attributed to the melting of macroscopic crystals. The DSC incremental nanopore volume distribution is in reasonable agreement with the incremental pore volume distribution of the aerogel as determined from nitrogen adsorption. No macroporosity was detected by nitrogen adsorption, probably because the adsorption method applies stress on the sample during measurement, leading to a underestimation of pore volume, or because often positive curvature of the solid surface is in aerogels, making the nitrogen condensation more difficult. According to the SAXS results, the solid network of the wet gels behaves as a mass fractal structure with mass fractal dimension D=2.20 +/- 0.01 in a characteristic length scale below xi=7.9 +/- 0.1 nm. The mass fractal characteristics of the wet gels have also been probed from DSC data by means of an earlier applied modeling for generation of a mass fractal from the incremental pore volume distribution curves. The results are shown to be in interesting agreement with the results from SAXS.

Drill holes in shells of Permian benthic invertebrates

Newly discovered benthic fossils and specimens illustrated in the paleontological literature indicate that drilling predators (or parasites) were present in the Permian. New field data from southern Brazil document the first drill holes ever reported for Permian bivalve mollusks. In addition, a literature review revealed drill holes in shells of articulate brachiopods from Russia, Greece, and West Texas. Holes range in size from 0.1 to 5.8 mm and are typically round, cylindrical, singular penetrations perpendicular to the valve surface. Incomplete, healed, and multiple holes are absent. Drilling frequency, a proxy for predation intensity, is very low: less than 1 percent (this estimate may be seriously affected by taphonomic and monographic biases). Literature data suggest that frequency of drilled specimens varied significantly among higher brachiopod taxa. The geography and stratigraphy of drilled specimens indicate that drilling organisms were worldwide in their occurrence and continuously present in marine ecosystems throughout the Permian. This report is consistent with other recent studies indicating that although drillers were continuously present throughout the Phanerozoic, drilling intensity was lower in the Late Paleozoic and early Mesozoic.