931 resultados para Thermodynamic and Chemical Phenomena.


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Analyses of sediments from Leg 64 sites reveal a diverse and in one case unique geochemistry. Sites are characterized by high heat flow along an active, divergent plate boundary, or rapid accumulation of diatom muds, or both. The geochemical trends of Sites 474-476 at the tip of Baja California reflect changes4n the percentages of sedimentary components - particularly biogenous matter and mineralogy - that support interpretations of sedimentary environments inferred to be present since the commencement of subsidence along this young, passive continental margin. The sediments below dolerite sills in Holes 477, 477A, 478, and 481 show major mineralogic and chemical deviations from "average" hemipelagic sediments. The sills appear to have two functions: (1) they allow hydrothermal circulation and metamorphism in a partially closed system by trapping heat and fluids emanating from below, and (2) they expel heated interstitial fluids at the moment of intrusion and mobilize elements, most likely leading to the formation of metalliferous deposits along the surface traces of normal faults in the basin. The hydrothermal system as a whole appears to be localized and ephemeral, as is indicated by the lack of similar geochemical trends and high heat flow at Sites 478 and 481. Site 479 illustrates sedimentation in an oxygen-minimum zone with anoxic sediments and concomitant geochemical trends, especially for MnO. With few exceptions, geochemical trends are remarkably constant with depth, suggesting that Site 479 can serve as an "internal" standard or average sediment against which the magnitude of hydrothermal alteration at the basinal Sites 477, 478, and 481 can be measured.

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Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.

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Cryosols are permafrost-affected soils whose genesis is dominated by cryogenic processes, resulting in unique macromorphologies, micromorphologies, thermal characteristics, and physical and chemical properties. In addition, these soils are carbon sinks, storing high amounts of organic carbon collected for thousands of years. In the Canadian soil classification, the Cryosolic Order includes mineral and organic soils that have both cryogenic properties and permafrost within 1 or 2 m of the soil surface. This soil order is divided into Turbic, Static and Organic great groups on the basis of the soil materials (mineral or organic), cryogenic properties and depth to permafrost. The great groups are subdivided into subgroups on the basis of soil development and the resulting diagnostic soil horizons. Cryosols are commonly associated with the presence of ground ice in the subsoil. This causes serious problems when areas containing these soils are used for agriculture and construction projects (such as roads, town sites and airstrips). Therefore, where Cryosols have high ice content, it is especially important either to avoid these activities or to use farming and construction methods that maintain the negative thermal balance.

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Mineral and chemical alterations of basalts were studied in the upper part of the ocean crust using data of deep-sea drilling from D/S Glomar Challenger in the main structures of the Pacific floor. Extraction of majority of chemical elements (including heavy metals) from basalts results mainly from their interaction with heated sea water. As a result mineralized hydrothermal solutions are formed. On entering the ocean they influence greatly on ocean sedimentation and ore formation.

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Results of petrographic studies of ultrabasites and gabbro from rift zones of the Indian Ocean are discussed using materials of Cruise 36 of R/V Vityaz. Rocks sampled from two sites 2700 km apart are close to each other in their composition. Petrographically ultrabasic rocks are divided into four subgroups: I - dunite; II - harzburgite, serpentinite; III - plagioclase lherzolite; and IV - metamorphically altered rocks. Petrographic description and chemical composition of basic rock varieties are presented as well as description of rock-forming minerals and their optical properties. Formation of pyroxene and plagioclase is shown to be related to autometasomatosis. Formation of ultrabasite in rift zones is related to complicated processes.

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Results of petrographic studies of ultrabasite and gabbro from the rift zones of the Indian Ocean ridges are discussed using materials of R/V Vityaz Cruise 36. Rocks sampled from two sites 2700 km apart are close to each other in their composition. Petrographically ultrabasic rocks are divided into four subgroups: I - dunite; II - harzburgite, serpentinite; III - plagioclase lherzolite; and IV - metamorphically altered rocks. Petrographic description and chemical composition of basic rock varieties are presented as well as description of rock-forming minerals and their optical properties. Formation of pyroxene and plagioclase is shown to be related to autometasomatosis, which concludes the magmatic phase proper in rock mass formation accompanied by activity of residual intragranular liquid. Formation of ultrabasite in the rift zones is related to complicated processes.

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Sediments from near the basement of a number of Deep Sea Drilling Project (DSDP) sites, from the Bauer Deep, and from the East Pacific Rise have unusually high transition metal-to-aluminum ratios. Similarities in the chemical, isotopic, and mineralogical compositions of these deposits point to a common origin. All the sediments studied have rare-earth-element (REE) patterns strongly resembling the pattern of sea water, implying either that the REE's were coprecipitated with ferromanganese hydroxyoxides (hydroxyoxides denote a mixture of unspecified hydrated oxides and hydroxides), or that they are incorporated in small concentrations of phosphatic fish debris found in all samples. Oxygen isotopic data indicate that the metalliferous sediments are in isotopic equilibrium with sea water and are composed of varying mixtures of two end-member phases with different oxygen isotopic compositions: an iron-manganese hydroxyoxide and an iron-rich montmorillonite. A low-temperature origin for the sediments is supported by mineralogical analyses by x-ray diffraction which show that goethite, iron-rich montmorillonite, and various manganese hydroxyoxides are the dominant phases present. Sr87/Sr86 ratios for the DSDP sediments are indistinguishable from the Sr87/Sr86 ratio in modern sea water. Since these sediments were formed 30 to 90 m.y. ago, when sea water had a lower Sr87/Sr86 value, the strontium in the poorly crystalline hydroxyoxides must be exchanging with interstitial water in open contact with sea water. In contrast, uranium isotopic data indicate that the metalliferous sediments have formed a closed system for this element. The sulfur isotopic compositions suggest that sea-water sulfur dominates these sediments with little or no contribution of magmatic or bacteriologically reduced sulfur. In contrast, ratios of lead isotopes in the metalliferous deposits resemble values for oceanic tholeiite basalt, but are quite different from ratios found in authigenic marine manganese nodules. Thus, lead in the metalliferous sediments appears to be of magmatic origin. The combined mineralogical, isotopic, and chemical data for these sediments suggest that they formed from hydrothermal solutions generated by the interaction of sea water with newly formed basalt crust at mid-ocean ridges. The crystallization of solid phases took place at low temperatures and was strongly influenced by sea water, which was the source for some of the elements found in the sediments.

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Diffusion controls the gaseous transport process in soils when advective transport is almost null. Knowledge of the soil structure and pore connectivity are critical issues to understand and modelling soil aeration, sequestration or emission of greenhouse gasses, volatilization of volatile organic chemicals among other phenomena. In the last decades these issues increased our attention as scientist have realize that soil is one of the most complex materials on the earth, within which many biological, physical and chemical processes that support life and affect climate change take place. A quantitative and explicit characterization of soil structure is difficult because of the complexity of the pore space. This is the main reason why most theoretical approaches to soil porosity are idealizations to simplify this system. In this work, we proposed a more realistic attempt to capture the complexity of the system developing a model that considers the size and location of pores in order to relate them into a network. In the model we interpret porous soils as heterogeneous networks where pores are represented by nodes, characterized by their size and spatial location, and the links representing flows between them. In this work we perform an analysis of the community structure of porous media of soils represented as networks. For different real soils samples, modelled as heterogeneous complex networks, spatial communities of pores have been detected depending on the values of the parameters of the porous soil model used. These types of models are named as Heterogeneous Preferential Attachment (HPA). Developing an exhaustive analysis of the model, analytical solutions are obtained for the degree densities and degree distribution of the pore networks generated by the model in the thermodynamic limit and shown that the networks exhibit similar properties to those observed in other complex networks. With the aim to study in more detail topological properties of these networks, the presence of soil pore community structures is studied. The detection of communities of pores, as groups densely connected with only sparser connections between groups, could contribute to understand the mechanisms of the diffusion phenomena in soils.

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Background Most aerial plant parts are covered with a hydrophobic lipid-rich cuticle, which is the interface between the plant organs and the surrounding environment. Plant surfaces may have a high degree of hydrophobicity because of the combined effects of surface chemistry and roughness. The physical and chemical complexity of the plant cuticle limits the development of models that explain its internal structure and interactions with surface-applied agrochemicals. In this article we introduce a thermodynamic method for estimating the solubilities of model plant surface constituents and relating them to the effects of agrochemicals. Results Following the van Krevelen and Hoftyzer method, we calculated the solubility parameters of three model plant species and eight compounds that differ in hydrophobicity and polarity. In addition, intact tissues were examined by scanning electron microscopy and the surface free energy, polarity, solubility parameter and work of adhesion of each were calculated from contact angle measurements of three liquids with different polarities. By comparing the affinities between plant surface constituents and agrochemicals derived from (a) theoretical calculations and (b) contact angle measurements we were able to distinguish the physical effect of surface roughness from the effect of the chemical nature of the epicuticular waxes. A solubility parameter model for plant surfaces is proposed on the basis of an increasing gradient from the cuticular surface towards the underlying cell wall. Conclusions The procedure enabled us to predict the interactions among agrochemicals, plant surfaces, and cuticular and cell wall components, and promises to be a useful tool for improving our understanding of biological surface interactions.

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Background Most aerial plant parts are covered with a hydrophobic lipid-rich cuticle, which is the interface between the plant organs and the surrounding environment. Plant surfaces may have a high degree of hydrophobicity because of the combined effects of surface chemistry and roughness. The physical and chemical complexity of the plant cuticle limits the development of models that explain its internal structure and interactions with surface-applied agrochemicals. In this article we introduce a thermodynamic method for estimating the solubilities of model plant surface constituents and relating them to the effects of agrochemicals. Results Following the van Krevelen and Hoftyzer method, we calculated the solubility parameters of three model plant species and eight compounds that differ in hydrophobicity and polarity. In addition, intact tissues were examined by scanning electron microscopy and the surface free energy, polarity, solubility parameter and work of adhesion of each were calculated from contact angle measurements of three liquids with different polarities. By comparing the affinities between plant surface constituents and agrochemicals derived from (a) theoretical calculations and (b) contact angle measurements we were able to distinguish the physical effect of surface roughness from the effect of the chemical nature of the epicuticular waxes. A solubility parameter model for plant surfaces is proposed on the basis of an increasing gradient from the cuticular surface towards the underlying cell wall. Conclusions The procedure enabled us to predict the interactions among agrochemicals, plant surfaces, and cuticular and cell wall components, and promises to be a useful tool for improving our understanding of biological surface interactions.

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Physico-chemical and organoleptic characteristics of food depend largely on the microscopic level distribution of gases and water, and connectivity and mobility through the pores. Microstructural characterization of food can be accomplished by Magnetic Resonance Imaging (MRI) and Nuclear Magnetic Spectroscopy (NMR) combined with the application of methods of dissemination and multidimensional relaxometry. In this work, funded by the EC Project InsideFood, several artificial food models, based on foams and gels were studied using MRI and 2D relaxometry. Two different kinds of foams were used: a sugarless and a sugar foam. Then, a half of a syringe was filled with the sugarless foam and the other half with the sugar foam. Then, MRI and NMR experiments were performed and the sample evolution was observed along 3 days in order to quantify macrostructural changes through proton density images and microstructural ones using T1T2 maps, using an inversion CPMG sequence. On the proton density images it may be seen that after 16 hours it was possible to differentiate the macrostructural changes, as the apparition of free water due to a syneresis phenomenon. On the interface it can be seen a brighter area after 16 hours, due to the occurrence of free water. Moreover, thanks to the bidimensional relaxometry (T1-T2) it was possible to differentiate among microscopic changes. Differences between the pores size can be observed as well as the microstructure evolution after 30.5 hours, as a consequence differences are shown on free water redistribution through larger pores and capillarity phenomena between both foams.

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In this work the spectrally resolved, multigroup and mean radiative opacities of carbon plasmas are calculated for a wide range of plasma conditions which cover situations where corona, local thermodynamic and non-local thermodynamic equilibrium regimes are found. An analysis of the influence of the thermodynamic regime on these magnitudes is also carried out by means of comparisons of the results obtained from collisional-radiative, corona or Saha–Boltzmann equations. All the calculations presented in this work were performed using ABAKO/RAPCAL code.