963 resultados para PHYSICO-CHEMICAL PROPERTIES


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El biochar es un material rico en carbono que se obtiene tras la pirólisis de la biomasa. Este material ha despertado en los últimos años un gran interés en la comunidad científica principalmente por su capacidad para mejorar la productividad de los suelos, influenciando las propiedades fisicoquímicas de los mismos y como medio de fijación de carbono, reduciendo, por tanto, las emisiones de CO2 a la atmósfera. Sin embargo, lo cierto es que hasta la fecha, no existen conclusiones claras o avances definitivos que permitan crear una estandarización para la comercialización del biochar, debido a la variabilidad de sus propiedades (considerando la materia prima de origen y las condiciones de reacción en la pirólisis). En este estudio, partiendo de un análisis exhaustivo de las distintas publicaciones existentes sobre la materia, se trata de dar respuesta a la pregunta sobre cuál sería el verdadero potencial de producción de biochar en España, al tiempo que se trata de cuantificar cuál sería la reducción de las emisiones de CO2 a la atmósfera que conllevaría gestionar los residuos (industria papelera, lodos de EDAR, RSU y residuos ganaderos) a través de la pirólisis. En particular, se ha cuantificado la reducción de las emisiones de CO2 a la atmósfera y se ha evaluado cuánto biochar se debería producir a partir de residuos papeleros, lodos de EDAR o residuos ganaderos para aumentar en un 1% la cantidad de materia orgánica en un suelo y para llevar el contenido en materia orgánica de los suelos agrícolas españoles a un 3,5%. En primer lugar, sobre la cuantificación de la reducción de las emisiones, cabe concluir que, en todos los residuos estudiados, y bajo todas las condiciones de reacción consideradas, la reducción de las emisiones de CO2 a la atmósfera sería realmente notable, oscilando entre un 22,53% y un 96,12 %. En segundo lugar, para aumentar en un 1% el contenido medio en materia orgánica de la superficie agrícola española, sería necesario un aporte de 2,03816*108 t de materia orgánica, que supondría una demanda mínima de biochar de 255.408.361 t en el caso de la aplicación de biochar de estiércol de vacuno a Por otro lado, para llevar la materia orgánica de los suelos agrícolas a un 3,5%, la demanda de biochar variaría entre un mínimo de 158.937 t en el (Comunidad Autónoma con menor necesidad de aporte de materia orgánica) illa la Mancha (Comunidad Autónoma que, por el contrario, necesitaría mayor aporte). ABSTRACT Biochar is a carbon-rich material obtained after a biomass pyrolysis procedure. This material has aroused in recent years a great interest in the scientific community, mainly for its ability to improve the productivity of soils, influencing the physico-chemical properties of soils and as means of carbon storage, reducing emissions of CO2 into the atmosphere). Despite the interest that may raise this matter, the fact is that to date, no clear conclusions or definitive progress have been done to create a standardization for the commercialization of biochar, due to the variability of its properties (considering the raw material and the reaction conditions in the pyrolysis). This study, based on a thorough analysis of the various existing literature on the subject and, leaving other approaches that could have been taken of the interest of the subject in question, attempts to provide answers to the question about what would be the true potential production of biochar in Spain and what would be the reduction of CO2 emissions into the atmosphere, which would entail waste management through pyrolysis. In particular, this study has identified the reduction of CO2 emissions into the atmosphere and has analyzed whether the production of biochar could increase the organic matter content of Spanish agricultural soils. Firstly, regarding the quantification of emissions reductions, by referring to the values contained in the work, it can be concluded that the reduction of CO2 emissions to the atmosphere would be really remarkable, ranging from 22.53% to 96.12%. Secondly, to increase by 1% the average content of organic matter in the spanish agricultural area would require a contribution of 2.03816*108 t of organic matter, which would demand a minimum of 255.408.361 t of cattle manure biochar and a maximum demand of 1.746.494.190 t of deinking sludge pyrolyzed at 500C. On the other hand, to reach a 3.5%, the demand for biochar would vary from a minimum of 158.937 t, in case of cattle manure biochar at C applied to the Canary Islands (Autonomous Community with less need for input of organic matter), and a maximum of 694.695.081 in case of applying deinking sludge biochar at C to Castilla la Mancha (Autonomous Region, which needs the highest contribution).

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Lactose, in particular α-lactose monohydrate, is the most used carrier for inhalation. Its surface and solid-state properties are of paramount importance in determining drug aerosolization performance. However, these properties may be altered by processing, such as micronization, thus affecting the product performance and stability. The present research project focused on the study of the effect of lactose solid-state on the aerosolization performance of drug-carrier mixtures, giving particular attention to the impact of micronization on lactose physico-chemical properties. The formation of a fraction of hygroscopic anhydrous α-lactose, rather than amorphous lactose, as a consequence of the mechanical stress stemming from micronization was evidenced by 1H NMR, XRPD and DSC analyses performed on samples of micronized lactose. The development of a new DVS method capable to identify and quantify different forms of α-lactose (hygroscopic anhydrous, stable anhydrous and amorphous), even simultaneously present in the same sample, confirmed the results obtained with the above-mentioned techniques. The influence of lactose solid-state on drug respirability was then evaluated through the preparation and in vitro aerodynamic assessment of ternary and binary mixtures containing two different drugs. In particular, the use, as carriers, of anhydrous forms of α-lactose in place of the conventional α-lactose monohydrate resulted in significantly improved respirability in the case of salbutamol sulphate and poorer performance in the case of budesonide. In an attempt to rationalize the obtained results, IGC was selected as a tool to investigate possible variations in the surface energy of the studied lactose carriers and APIs. A direct correlation between the total surface free energy of lactose carriers and drug respirability was not found. However, salbutamol sulphate and budesonide exhibited different specific surface free energy, to which the difference in the aerosolization performance may be, at least in part, ascribed.

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Nos últimos anos tem havido um aumento significativo da procura de frutos vermelhos. Os mirtilos são considerados frutos de boa qualidade, dado o seu elevado teor em compostos fitoquímicos biologicamente ativos, associados a efeitos benéficos para a saúde e bem-estar do Homem. A produção em modo biológico é reconhecida pelo consumidor como um processo que melhora a qualidade do produto. No presente trabalho pretendeu-se avaliar o efeito do modo de produção (biológico versus convencional) de três cultivares de mirtilo (Duke, Bluecrop, Ozarkblue) nas suas propriedades físico-químicas, e em particular na sua composição fenólica e atividade antioxidante. Foi ainda estudado o efeito da temperatura de armazenamento (± 5ºC e ± 15-25ºC) sobre essas propriedades. Para tal, as amostras foram analisadas à colheita e após 7 e 14 dias de armazenamento. A atividade antioxidante medida pelos métodos ABTS e DPPH mostrou que não há diferenças significativas entre as cultivares estudadas, sendo elevada em todos os casos. Os resultados obtidos confirmam, por isso, que o mirtilo é uma importante fonte de compostos fenólicos com elevada atividade antioxidante. Foi ainda verificado existirem algumas diferenças significativas em algumas propriedades em função da variedade (nomeadamente teor em matéria seca, cor ou textura). Também se verificara diferenças significativas em função do modo de produção, o qual influencia em particular a acidez e a doçura, o teor em taninos, a cor e a elasticidade dos frutos. Por fim, a temperatura de armazenamento mostrou ter uma influência significativa apenas no que respeita às propriedades físicas, nomeadamente cor e textura.

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As defined by the European Union, “ ’Nanomaterial’ (NM) means a natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or agglomerate, where, for 50 % or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm-100 nm ” (2011/696/UE). Given their peculiar physico-chemical features, nanostructured materials are largely used in many industrial fields (e.g. cosmetics, electronics, agriculture, biomedical) and their applications have astonishingly increased in the last fifteen years. Nanostructured materials are endowed with very large specific surface area that, besides making them very useful in many industrial processes, renders them very reactive towards the biological systems and, hence, potentially endowed with significant hazard for human health. For these reasons, in recent years, many studies have been focused on the identification of toxic properties of nanostructured materials, investigating, in particular, the mechanisms behind their toxic effects as well as their determinants of toxicity. This thesis investigates two types of nanostructured TiO2 materials, TiO2 nanoparticles (NP), which are yearly produced in tonnage quantities, and TiO2 nanofibres (NF), a relatively novel nanomaterial. Moreover, several preparations of MultiWalled Carbon Nanotubes (MWCNT), another nanomaterial widely present in many products, are also investigated.- Although many in vitro and in vivo studies have characterized the toxic properties of these materials, the identification of their determinants of toxicity is still incomplete. The aim of this thesis is to identify the structural determinants of toxicity, using several in vitro models. Specific fields of investigation have been a) the role of shape and the aspect ratio in the determination of biological effects of TiO2 nanofibres of different length; b) the synergistic effect of LPS and TiO2 NP on the expression of inflammatory markers and the role played therein by TLR-4; c) the role of functionalization and agglomeration in the biological effects of MWCNT. As far as biological effects elicited by TiO2 NF are concerned, the first part of the thesis demonstrates that long TiO2 nanofibres caused frustrated phagocytosis, cytotoxicity, hemolysis, oxidative stress and epithelial barrier perturbation. All these effects were mitigated by fibre shortening through ball-milling. However, short TiO2 NF exhibited enhanced ability to activate acute pro-inflammatory effects in macrophages, an effect dependent on phagocytosis. Therefore, aspect ratio reduction mitigated toxic effects, while enhanced macrophage activation, likely rendering the NF more prone to phagocytosis. These results suggest that, under in vivo conditions, short NF will be associated with acute inflammatory reaction, but will undergo a relatively rapid clearance, while long NF, although associated with a relatively smaller acute activation of innate immunity cells, are not expected to be removed efficiently and, therefore, may be associated to chronic inflammatory responses. As far as the relationship between the effects of TiO2 NP and LPS, investigated in the second part of the thesis, are concerned, TiO2 NP markedly enhanced macrophage activation by LPS through a TLR-4-dependent intracellular pathway. The adsorption of LPS onto the surface of TiO2 NP led to the formation of a specific bio-corona, suggesting that, when bound to TiO2 NP, LPS exerts a much more powerful pro-inflammatory effect. These data suggest that the inflammatory changes observed upon exposure to TiO2 NP may be due, at least in part, to their capability to bind LPS and, possibly, other TLR agonists, thus enhancing their biological activities. Finally, the last part of the thesis demonstrates that surface functionalization of MWCNT with amino or carboxylic groups mitigates the toxic effects of MWCNT in terms of macrophage activation and capability to perturb epithelial barriers. Interestingly, surface chemistry (in particular surface charge) influenced the protein adsorption onto the MWCNT surface, allowing to the formation of different protein coronae and the tendency to form agglomerates of different size. In particular functionalization a) changed the amount and the type of proteins adsorbed to MWCNT and b) enhanced the tendency of MWCNT to form large agglomerates. These data suggest that the different biological behavior of functionalized and pristine MWCNT may be due, at least in part, to the different tendency to form large agglomerates, which is significantly influenced by their different capability to interact with proteins contained in biological fluids. All together, these data demonstrate that the interaction between physico-chemical properties of nanostructured materials and the environment (cells + biological fluids) in which these materials are present is of pivotal importance for the understanding of the biological effects of NM. In particular, bio-persistence and the capability to elicit an effective inflammatory response are attributable to the interaction between NM and macrophages. However, the interaction NM-cells is heavily influenced by the formation at the nano-bio interface of specific bio-coronae that confer a novel biological identity to the nanostructured materials, setting the basis for their specific biological activities.

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1. Structure-activity relationships for the binding of human α-calcitonin gene-related peptide 8-37 (hαCGRP8-37) have been investigated at the CGRP receptors expressed by human SK-N-MC (neuroblastoma) and Col 29 (colonic epithelia) cells by radioligand binding assays and functional assays (hαCGRP stimulation of adenylate cyclase). 2. On SK-N-MC cells the potency order was hαCGRP8-37 > hαCGRP19-37 = AC187 > rat amylin8-37 > hα[Tyr0]-CGRP28-37 (apparent pKBS of 7.49 ± 0.25, 5.89 ± 0.20, 6.18 ± 0.19, 5.85 ± 0.19 and 5.25 ± 0.07). The SK-N-MC receptor appeared CGRP1-like. 3. On Col 29 cells, only hαCGRP8-37 of the above compounds was able to antagonize the actions of hαCGRP (apparent pKB = 6.48 ± 0.28). Its receptor appeared CGRP2-like. 4. hα[Ala11,18]-CGRP8-37, where the amphipathic nature of the N-terminal α-helix has been reduced, bound to SK-N-MC cells a 100 fold less strongly than hαCGRP8-37. 5. On SK-N-MC cells, hαCGRP(8-18, 28-37) (M433) and mastoparan-hαCGRP28-37 (M432) had apparent pKBS of 6.64 ± 0.16 and 6.42 ± 0.26, suggesting that residues 19-27 play a minor role in binding. The physico-chemical properties of residues 8-18 may be more important than any specific side-chain interactions. 6. M433 was almost as potent as hαCGRP8-37 on Col 29 cells (apparent pKB = 6.17 ± 0.20). Other antagonists were inactive.

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The objectives of this study were to investigate: (1) whether foliose lichen thalli could be transplanted from one substrate to another and (2) whether such transplants could be used to study the influence of the substrate on growth. Hence, six saxicolous lichens, with contrasting distributions on lime-rich and lime-poor substrates in South Gwynedd, Wales, were transplanted onto slate, granite, asbestos and cement. Fragments of the perimeters of thalli were glued to the different substrates using Bostic adhesive. Parmelia conspersa (Ehrh. Ex Ach.)Ach. and Parmelia saxatilis (L.)Ach., fragments increased in area over 15 months on slate and granite but decreased in area or did not survive on asbestos and cement. Fragments of Xanthoria parietina (L.)Th.Fr. and Physcia tenella (Scop.)DC. em Bitt. did not survive on slate and granite while some fragments survived but grew poorly on asbestos and cement. Parmelia glabratula ssp. fuliginosa (Fr. ex Duby)Laund. fragments decreased in area on all substrates and especially on cement and asbestos while Physcia orbicularis (Neck.)Poetsch fragments increased in area on granite and cement, decreased on asbestos and did not change significantly on slate. The results suggested that the distribution of P. conspersa and P. saxatilis was determined primarily by physico-chemical properties of the substrate. By contrast, P. glabratula ssp. fuliginosa may have responded to the transplant procedure while X. parietina, Ph. tenella and Ph. orbicularis may require nutrient enrichment to grow successfully on a substrate.

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Tear component deposition onto contact lenses is termed `spoilation' and occurs due to the interaction of synthetic polymers with their biological fluid environment. Spoilation phenomena alter the physico-chemical properties of hydrophilic contact lenses, diminishing the optical properties of the lens; causing discomfort and complications for the wearer. Eventually these alterations render the lens unwearable. The primary aim of this interdisciplinary study was to develop analytical techniques capable of analysing the minute quantities of biological deposition involved, in particular the lipid fraction. Prior to this work such techniques were unavailable for single contact lenses. It is envisaged that these investigations will further the understanding of this biological interfacial conversion. Two main analytical techniques were developed: a high performance liquid chromatography (HPLC) technique and fluorescence spectrofluorimetry. The HPLC method allows analysis of a single contact lens and provided previously unavailable valuable information about variations in the lipid profiles of deposited contact lenses and patient tear films. Fluorescence spectrophotofluorimetry is a sensitive non-destructive technique for observing changes in the fluorescence intensity of biological components on contact lenses. The progression and deposition of tear materials can be monitored and assessed for both in vivo and in vitro spoiled lenses using this technique. An improved in vitro model which is comparable to tears and chemically mimics ocular spoilation was also developed. This model allows the controlled study of extrinsic factors and hydrogel compositions. These studies show that unsaturated tear lipids, probably unsaturated fatty acids, are involved in the interfacial conversion of hydrogel lenses, rendering them incompatible with the ocular microenvironment. Lipid interaction with the lens surface then facilitates secondary deposition of other tear components. Interaction, exchange and immobilisation (by polymerisation) of the lipid layer appears to occur before the final and rapid growth of more complex, insoluble discrete deposits, sometimes called `white spots'.

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The advent of DNA vaccines has heralded a new technology allowing the design and elicitation of immune responses more adequate for a wider range of pathogens. The formulation of these vaccines into the desired dosage forms extends their capability in terms of stability, routes of administration and efficacy. This thesis describes an investigation into the fabrication of plasmid DNA, the active principle of DNA vaccines, into microspheres, based on the tenet of an increased cellular uptake of microparticulate matter by phagocytic cells. The formulation of plasmid DNA into microspheres using two methods, is presented. Formulation of microspheric plasmid DNA using the double emulsion solvent evaporation method and a spray-drying method was explored. The former approach involves formation of a double emulsion, by homogenisation. This method produced microspheres of uniform size and smooth morphology, but had a detrimental effect on the formulated DNA. The spray-drying method resulted in microspheres with an improved preservation of DNA stability. The use of polyethylenimine (PEI) and stearylamine (SA) as agents in the microspheric formulation of plasmid DNA is a novel approach to DNA vaccine design. Using these molecules as model positively-charged agents, their influence on the characteristics of the microspheric formulations was investigated. PEI improved the entrapment efficiency of the plasmid DNA in microspheres, and has minimal effect on either the surface charge, morphology or size distribution of the formulations. Stearylamine effected an increase in the entrapment efficiency and stability of the plasmid DNA and its effect on the micropshere morphology was dependent on the method of preparation. The differences in the effects of the two molecules on microsphere formulations may be attributable to their dissimilar physico-chemical properties. PEI is water-soluble and highly-branched, while SA is hydrophobic and amphipathic. The positive charge of both molecules is imparted by amine functional groups. Preliminary data on the in vivo application of formulated DNA vaccine, using hepatitis B plasmid, showed superior humoral responses to the formulated antigen, compared with free (unformulated) antigen.

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Azidoprofen {2-(4-azidophenyl)propionic acid; AZP}, an azido-substituted arylalkanoic acid, was investigated as a model soft drug candidate for a potential topical non-steroidal anti-inflammatory agent (NSAIA). Reversed-phase high performance liquid chromatography (HPLC) methods were developed for the assay of AZP, a series of ester analogues and their· degradation products. 1H-NMR spectroscopy was also employed as an analytical method in selected cases. Reduction of the azido-group to the corresponding amine has been proposed as a potential detoxification mechanism for compounds bearing this substituent. An in vitro assay to measure the susceptibility of azides towards reduction was developed using dithiothreitol as a model reducing agent. The rate of reduction of AZP was found to be base-dependent, hence supporting the postulated mechanism of thiol-mediated reduction via nucleophilic attack by the thiolate anion. Prodrugs may enhance topical bioavailability through the manipulation of physico-chemical properties of the parent drug. A series of ester derivatives of AZP were investigated for their susceptibility to chemical and enzymatic hydrolysis, which regenerates the parent acid. Use of alcoholic cosolvents with differing alkyl functions to that of the ester resulted in transesterification reactions, which were found to be enzyme-mediated. The skin penetration of AZP was assessed using an in vitro hairless mouse skin model, and silastic membrane in some cases. The rate of permeation of AZP was found to be a similar magnitude to that of the well established NSAIA ibuprofen. Penetration rates were dependent on the vehicle pH and drug concentration when solutions were employed. In contrast, flux was independent of pH when suspension formulations were used. Pretreatment of the skin with various enhancer regimes, including oleic acid and azone in propylene glycol, promoted the penetration of AZP. An intense IR absorption due to the azide group serves as a highly diagnostic marker, enabling azido compounds to be detected in the outer layers of the· stratum corneum following their application to skin, using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). This novel application enabled a non-invasive examination of the percutaneous penetration enhancement of a model azido compound in vivo in man, in the presence of the enhancer oleic acid.

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This present study compares the efficacy of microsphere formulations, and their method of antigen presentation, for the delivery of the TB sub-unit vaccine antigen, Ag85B-ESAT-6. Microspheres based on poly(lactide-co-glycolide) (PLGA) and chitosan incorporating dimethyldioctadecylammonium bromide (DDA) were prepared by either the w/o/w double emulsion method (entrapped antigen) or the o/w single emulsion method (surface bound antigen), and characterised for their physico-chemical properties and their ability to promote an immune response to Ag85B-ESAT-6. The method of preparation, and hence method of antigen association, had a pronounced effect on the type of immune response achieved from the microsphere formulations, with surface bound antigen favouring a humoural response, whereas entrapped antigen favoured a cellular response.

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Solid tumours display a complex drug resistance phenotype that involves inherent and acquired mechanisms. Multicellular resistance is an inherent feature of solid tumours and is known to present significant barriers to drug permeation in tumours. Given this barrier, do acquired resistance mechanisms such as P-glycoprotein (P-gp) contribute significantly to resistance? To address this question, the multicellular tumour spheroid (MCTS) model was used to examine the influence of P-gp on drug distribution in solid tissue. Tumour spheroids (TS) were generated from either drug-sensitive MCF7WT cells or a drug-resistant, P-gp-expressing derivative MCF7Adr. Confocal microscopy was used to measure time courses and distribution patterns of three fluorescent compounds; calcein-AM, rhodamine123 and BODIPY-taxol. These compounds were chosen because they are all substrates for P-gp-mediated transport, exhibit high fluorescence and are chemically dissimilar. For example, BODIPY-taxol and rhodamine 123 showed high accumulation and distributed extensively throughout the TSWT, whereas calcein-AM accumulation was restricted to the outermost layers. The presence of P-gp in TSAdr resulted in negligible accumulation, regardless of the compound. Moreover, the inhibition of P-gp by nicardipine restored intracellular accumulation and distribution patterns to levels observed in TSWT. The results demonstrate the effectiveness of P-gp in modulating drug distribution in solid tumour models. However, the penetration of agents throughout the tissue is strongly determined by the physico-chemical properties of the individual compounds.

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This present study compares the efficacy of microsphere formulations, and their method of antigen presentation, for the delivery of the TB sub-unit vaccine antigen, Ag85B-ESAT-6. Microspheres based on poly(lactide-co-glycolide) (PLGA) and chitosan incorporating dimethyldioctadecylammonium bromide (DDA) were prepared by either the w/o/w double emulsion method (entrapped antigen) or the o/w single emulsion method (surface bound antigen), and characterised for their physico-chemical properties and their ability to promote an immune response to Ag85B-ESAT-6. The method of preparation, and hence method of antigen association, had a pronounced effect on the type of immune response achieved from the microsphere formulations, with surface bound antigen favouring a humoural response, whereas entrapped antigen favoured a cellular response.

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Tree islands are an important structural component of many graminoid-dominated wetlands because they increase ecological complexity in the landscape. Tree island area has been drastically reduced with hydrologic modifications within the Everglades ecosystem, yet still little is known about the ecosystem ecology of Everglades tree islands. As part of an ongoing study to investigate the effects of hydrologic restoration on short hydroperiod marshes of the southern Everglades, we report an ecosystem characterization of seasonally flooded tree islands relative to locations described by variation in freshwater flow (i.e. locally enhanced freshwater flow by levee removal). We quantified: (1) forest structure, litterfall production, nutrient utilization, soil dynamics, and hydrologic properties of six tree islands and (2) soil and surface water physico-chemical properties of adjacent marshes. Tree islands efficiently utilized both phosphorus and nitrogen, but indices of nutrient-use efficiency indicated stronger P than N limitation. Tree islands were distinct in structure and biogeochemical properties from the surrounding marsh, maintaining higher organically bound P and N, but lower inorganic N. Annual variation resulting in increased hydroperiod and lower wet season water levels not only increased nitrogen use by tree species and decreased N:P values of the dominant plant species (Chrysobalanus icaco), but also increased soil pH and decreased soil temperature. When compared with other forested wetlands, these Everglades tree islands were among the most nutrient efficient, likely a function of nutrient immobilization in soils and the calcium carbonate bedrock. Tree islands of our study area are defined by: (1) unique biogeochemical properties when compared with adjacent short hydroperiod marshes and other forested wetlands and (2) an intricate relationship with marsh hydrology. As such, they may play an important and disproportionate role in nutrient and carbon cycling in Everglades wetlands. With the loss of tree islands that has occurred with the degradation of the Everglades system, these landscape processes may have been altered. With this baseline dataset, we have established a long-term ecosystem-scale experiment to follow the ecosystem trajectory of seasonally flooded tree islands in response to hydrologic restoration of the southern Everglades.

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SILVA, J. S. P. Estudo das características físico-químicas e biológicas pela adesão de osteoblastos em superfícies de titânio modificadas pela nitretação em plasma. 2008. 119 f. Tese (Doutorado) - Faculdade de Medicina, Universidade de São Paulo. São Paulo, 2008.