Desenvolvimento de membranas de poli(éter imida) sultonada para a permeacão de gases

A busca por membranas com propriedades adequadas a separação de gases em escala industrial tem levado a modificação e sIntese de polImeros de engenharia, com objetivo de obter membranas com propriedades adequadas. Uma das modificaçoes que tem se apresentado promissora é a inserção de grupos sulfônicos em polImeros comerciais. Espera-se que o polImero sulfonado apresente um aumento na permeação de gases polares, em relação a gases apolares, devido a sua estrutura mais polar e flexIvel. Neste contexto, o objetivo do presente trabalho é a sIntese e caracterização de membranas de poli(éter imida) sulfonada para a permeação de gases. Um planejamento experimental foi desenvolvido, em diferentes condiçoes reacionais de temperatura, tempo e excesso de um dos reagentes (ácido acético), para a sIntese de poli(éter imida) sulfonada (SPEI). Através deste planejamento, constatou-se que as variáveis que mais influenciam o grau de sulfonação são a temperatura e o tempo. O polImero com o maior grau de sulfonação, determinado por capacidade de troca iônica (IEC= 92 mEq H+/g), foi utilizado para o preparo da membrana de SPEI, obtida pela técnica de inversão de fase por evaporação do solvente, utilizando-se clorofórmio como solvente. Este filme foi caracterizado a partir das seguintes análises: espectroscopia de infravermelho (FTIR), calorimetria diferencial de varredura (DSC), análise termogravimétrica (TGA) e microscopia eletrônica de varredura (MEV), a fim de avaliar a influência da inserção do grupo sulfônico na matriz polimérica. O espectro de infravermelho de SPEI apresentou bandas relacionadas as vibraçoes assimétricas em 1240 cm-1 (ligação O=S=O), ligação simétrica em 1171 cm-1 (O=S=O) e ligação S-O entre 1010-1024 cm-1. Isto indica a presença de grupos sulfônicos. A análise de DSC foi realizada entre 150-250C. Nesta faixa, não foram observadas alteraçoes na temperatura de transição vItrea (Tg) do polImero modificado (217C). Acredita-se que a decomposição do grupo sulfona aconteça antes da temperatura atingir o Tg do polImero. Esta suposição é confirmada na análise de TGA. As imagens de MEV mostraram que foram obtidos filmes livres de poros e defeitos. A membrana da SPEI foi utilizada no ensaio de permeaçao dos gases 02, N2 e C02, a fim de determinar a permeabilidade e seletividade da membrana. As permeabilidades encontradas para o gas oxigênio foram de 0,76 barrer para a PEI e 0,46 barrer para a SPEI. A seletividade do dióxido de carbono em relaçao ao oxigênio aumentou de 3,5, na membrana de PEI, para 4,83, na membrana de SPEI. Em relaçao ao nitrogênio, as permeabilidades medidas foram 0,064 barrer e 0,043 barrer, para a PEI e para a SPEI, respectivamente, enquanto a seletividade em relaçao ao C02 aumentou de 41,1 para 55,5. Estes resultados indicam que o efeito de sorçao predominou devido ao aumento das interaçöes moleculares, reduzindo assim o volume livre, o que tornou a membrana sulfonada mais compacta, com permeabilidade menor e maior seletividade. Estes resultados corroboram com a premissa de que a sulfonaçao é um processo promissor para o desenvolvimento de membranas mais eficientes.

Oxygen relationships in intermittent sand filtration of wastewaters

A model for some of the many physical-chemical and biological processes in intermittent sand filtration of wastewaters is described and an expression for oxygen transfer is formulated.

The model assumes that aerobic bacterial activity within the sand or soil matrix is limited, mostly by oxygen deficiency, while the surface is ponded with wastewater. Atmospheric oxygen reenters into the soil after infiltration ends. Aerobic activity is resumed, but the extent of penetration of oxygen is limited and some depths may be always anaerobic. These assumptions lead to the conclusion that the percolate shows large variations with respect to the concentration of certain contaminants, with some portions showing little change in a specific contaminant. Analyses of soil moisture in field studies and of effluent from laboratory sand columns substantiated the model.

The oxygen content of the system at sufficiently long times after addition of wastes can be described by a quasi-steady-state diffusion equation including a term for an oxygen sink. Measurements of oxygen content during laboratory and field studies show that the oxygen profile changes only slightly up to two days after the quasi-steady state is attained.

Results of these hypotheses and experimental verification can be applied in the operation of existing facilities and in the interpretation of data from pilot plant-studies.

Oxygen flux through salmonid spawning gravels

Laboratory and field studies have shown that the survival of salmonid fish eggs and alevins is dependent upon the supply rate or flux of dissolved oxygen through gravel beds used for spawning. Although there have been a number of studies concerned with North American species there are few data for Atlantic salmon (Salmo salar) and the brown trout (S. trutta). For this study intragravel seepage velocities and dissolved oxygen concentrations have been measured throughout the incubation period in spawning gravels utilized by brown trout (Salmo trutta). Variation in the hatching success of batches of trout and salmon (Salmo salar) can, in part, be attributed to a critical threshold of oxygen flux through the gravels.

The effects of a sand layer upon swim-up success in UK salmonids

There are two main ways in which gravel composition and changes therein arising from siltation, can influence the survival of young salmonids. First, the composition of the gravel will affect its permeability and, hence, may influence the survival of eggs and alevins through its effect upon the rate of supply of oxygen and the rate of removal of metabolic products. Second, the composition of the gravel may affect the ease, or otherwise, of emergence at the time of swim-up and alevins may become trapped in the gravel and perish. This aspect is the main concern of the present report. Experiments were conducted to examine the effects upon fry emergence of a sand layer deposited on the gravel surface. The study concludes that fry of brown trout and Atlantic salmon emerged through layers of sand up to 8 cm thick but the percentage emergence, even from the controls with no sand, was relatively low (5 - 68%). There was no firm evidence that the experimental treatments influenced percentage emergence, timing of emergence or weight of fry at the time of emergence.

I. Phosphorescence and the true lifetime of triplet states in fluid solutions. II. Why is condensed oxygen blue?

I. PHOSPHORESCENCE AND THE TRUE LIFETIME OF TRIPLET STATES IN FLUID SOLUTIONS

Phosphorescence has been observed in a highly purified fluid solution of naphthalene in 3-methylpentane (3-MP). The phosphorescence lifetime of C₁₀H₈ in 3-MP at -45 °C was found to be 0.49 ± 0.07 sec, while that of C₁₀D₈ under identical conditions is 0.64 ± 0.07 sec. At this temperature 3-MP has the same viscosity (0.65 centipoise) as that of benzene at room temperature. It is believed that even these long lifetimes are dominated by impurity quenching mechanisms. Therefore it seems that the radiationless decay times of the lowest triplet states of simple aromatic hydrocarbons in liquid solutions are sensibly the same as those in the solid phase. A slight dependence of the phosphorescence lifetime on solvent viscosity was observed in the temperature region, -60° to -18°C. This has been attributed to the diffusion-controlled quenching of the triplet state by residual impurity, perhaps oxygen. Bimolecular depopulation of the triplet state was found to be of major importance over a large part of the triplet decay.

The lifetime of triplet C₁₀H₈ at room temperature was also measured in highly purified benzene by means of both phosphorescence and triplet-triplet absorption. The lifetime was estimated to be at least ten times shorter than that in 3-MP. This is believed to be due not only to residual impurities in the solvent but also to small amounts of impurities produced through unavoidable irradiation by the excitation source. In agreement with this idea, lifetime shortening caused by intense flashes of light is readily observed. This latter result suggests that experiments employing flash lamp techniques are not suitable for these kinds of studies.

The theory of radiationless transitions, based on Robinson's theory, is briefly outlined. A simple theoretical model which is derived from Fano's autoionization gives identical result.

Il. WHY IS CONDENSED OXYGEN BLUE?

The blue color of oxygen is mostly derived from double transitions. This paper presents a theoretical calculation of the intensity of the double transition (a ¹Δ_g) (a ¹Δ_g)←(X ³Σ_g^-) (X ³Σ_g^-), using a model based on a pair of oxygen molecules at a fixed separation of 3.81 Å. The intensity enhancement is assumed to be derived from the mixing (a ¹Δ_g) (a ¹Δ_g) _~~~ (X ³Σ_g^-) (X ³Σ_u^-) and (a ¹Δ_g) (¹Δ_u) _~~~ (X ³Σ_g^-) (X ³Σ_g^-). Matrix elements for these interactions are calculated using a π-electron approximation for the pair system. Good molecular wavefunctions are used for all but the perturbing (B ³Σ_u^-) state, which is approximated in terms of ground state orbitals. The largest contribution to the matrix elements arises from large intramolecular terms multiplied by intermolecular overlap integrals. The strength of interaction depends not only on the intermolecular separation of the two oxygen molecules, but also as expected on the relative orientation. Matrix elements are calculated for different orientations, and the angular dependence is fit to an analytical expression. The theory therefore not only predicts an intensity dependence on density but also one on phase at constant density. Agreement between theory and available experimental results is satisfactory considering the nature of the approximation, and indicates the essential validity of the overall approach to this interesting intensity enhancement problem.

Biodegradação dos óleos e sua relação com as fácies sedimentares da região do Anhembi

Este trabalho consistiu em aprimorar o entendimento da rota de migração do óleo no reservatório e verificar a possibilidade de variação da intensidade da biodegradação com as heterogeneidades existentes. Foram utilizadas como base para a dissertação sete amostras coletadas na bacia sedimentar do Paraná, no arenito asfáltico do Anhembi, afloramento da Fazenda Betumita. A Fazenda Betumita é considerada a ocorrência mais expressiva de óleo na região do alto estrutural do Anhembi, apresentando a maior acumulação de arenito asfáltico na borda leste da Bacia do Paraná. A ocorrência dos arenitos asfálticos na área de estudo é predominantemente por arenitos da Formação Pirambóia. Estes arenitos foram preenchidos por hidrocarbonetos relacionados ao sistema Irati-Pirambóia e são caracterizados como imaturo, devido ausência de n-alcanos e abundância de esteranos e terpanos. As amostras coletadas foram analisadas através da cromatografia líquida e gasosa e correlacionadas com a descrição das fácies do afloramento. A biodegradação do óleo apresentou a tendência de aumentar do topo para a base do afloramento, local caracterizado por fácies subaquosas, onde se encontra o contato óleo/água, propício para o crescimento dos microorganismos degradadoras de óleo. Na fácie de interduna, a biodegradação foi menor, pois este ambiente é caracterizado por partículas argilo-minerais e menores permo-porosidade, não propício para o crescimento de microorganismos capazes de degradar o óleo. Foi observada a presença de diasteranos e 25-norhopanos nas amostras coletadas, indicando que o óleo do afloramento está severamente biodegradado. Os esteranos apresentaram maior biodegradação na base do afloramento onde está o contato óleo/água e maior reposição de oxigênio pela infiltração de água meteórica, tornando-se ambiente propício para crescimento das bactérias aeróbicas tendendo a degradar preferencialmente os esteranos. Entretanto os hopanos apresentaram maior biodegradação no topo do afloramento, local com condições propícias para o crescimento das bactérias anaeróbicas, que tenderam a degradar preferencialmente os hopanos. As informações adquiridas nesta pesquisa são de grande relevância para o conhecimento na exploração do petróleo, pois geralmente esses conhecimentos não estão disponíveis nos dados de subsuperfície. Este trabalho servirá de parâmetro para o planejamento da produção e recuperação secundária e terciária de reservatórios com fácies sedimentares semelhantes da área estudada.

Study of ion movements in isolated chicken retinas during spreading depression

Spreading depression (SD) is a phenomenon observed in several sections of vertebrate central nervous system. It can occur spontaneously or be evoked by a variety of stimuli, and consists of a wave of depression of the normal electrical activity of the nervous tissue which spreads slowly in all directions in the tissue. This wave of depression is accompanied by several concomitants including ion movements. All the concomitants of SD can be explained by an increase in the sodium permeability of the plasma membranes of cellular elements involved in this phenomenon.

In the chicken retina, SD is accompanied by a transparency change which can be detected with the naked eye. The isolated retina is a thin (0.1 mm) membrane in which the extracellular fluid quickly and completely equilibrates with the incubation solutions. This preparation was therefore used to study the ion movements during SD by measuring and comparing the ion contents and the extracellular space (ECS) of retinas incubated in various solutions of which some inhibited SD, whereas others allowed this phenomenon to occur.

The present study has shown that during SD there is a shift of extracellular sodium into the intracellular compartment of the retina, a release of intracellular K and a decrease in the magnitude of ECS. These results are in agreement with previous postulates about SD, although the in vitro experimental condition makes the ion movements appear larger and the loss of ECS smaller than observed in the intact cortical tissue. The movements of Na and K, in opposite directions, are reversible. The development and magnitudes of SD is very little affected by deprivation of the oxygen supply.

It was established that the inward sodium shift is not a consequence of an arrest of the Na-pump. It can be prevented, together with SD by the membrane stabilizers, magnesium and procaine. Spreading depression and the ion movements are incompletely inhibited by tetrodotoxin, which blocks the sodium influx into nerve fibers during the action potential. The replacement of Na in the bathing solution by Li does not prevent SD, which is accompanied by Li accumulation in the intracellular compartment. From these experiments and others it was concluded that the mechanism underlying SD and the ion shifts is an increase in the sodium permeability of cell membranes.

Characterization of a dissolved oxygen sensor made of plastic optical fiber coated with ruthenium-incorporated solgel

A dissolved oxygen sensor made of plastic optical fiber as the substrate and dichlorotris (1, 10-phenanthroline) ruthenium as a fluorescence indicator is studied. Oxygen quenching characteristics of both intensity and phase were measured; the obtained characteristics showed deviation from the linear relation described by the Stern-Volmer equation. A two-layer model is proposed to explain the deviation, and main parameters can be deduced with the model. (C) 2009 Optical Society of America

Final Evaluation Memorandum: Strategies for Resolving Low Dissolved Oxygen and Methylmercury Events in Northern Suisun Marsh

The purpose of the project is to improve our understanding about best management practices that can be utilized on diked managed wetlands in Suisun Marsh for reducing the occurrence of low dissolved oxygen (DO) and high methylmercury (MeHg) events associated primarily with fall flood-up practices. Low DO events are of concern because they can lead to undue stress and even mortality of sensitive aquatic organisms. Elevated MeHg levels are of concern because MeHg is a neurotoxin that bio-magnifies up the food chain and can cause deleterious effects to higher trophic level consumers such as piscivorous fish, birds, and mammals (including humans). This study involved two years (2007-2008) of intensive field data collection at two managed wetland sites in northwest Suisun Marsh and their surrounding tidal sloughs, an area with prior documented low DO events. In addition, the study collected limited soils and water quality field data and mapped vegetation for three managed wetland sites in the central interior of Suisun Marsh, for the purpose of examining whether wetlands at other locations exhibit characteristics that could indicate potential for similar concerns. In Year 1 of the study, the objective was to identify the baseline conditions in the managed wetlands and determine which physical management conditions could be modified for Year 2 to reduce low DO and MeHg production issues most effectively. The objective of Year 2 was to evaluate the effectiveness of these modified management actions at reducing production of low DO and elevated MeHg conditions within the managed wetlands and to continue improving understanding of the underlying biogeochemical processes at play. This Final Evaluation Memorandum examined a total of 19 BMPs, 14 involving modified water management operations and the remaining five involving modified soil and vegetation management practices. Some of these BMPs were previously employed and others have not yet been tested. For each BMP this report assesses its efficacy in improving water quality conditions and potential conflicts with wetland management. It makes recommendations for further study (either feasibility assessments or field testing) and whether to consider for future use. Certain previously used BMPs were found to be important contributors to poor water quality conditions and their continued use is not recommended. Some BMPs that could improve water quality conditions appear difficult to implement in regards to compatibility with wetland management; these BMPs require further elaboration and feasibility assessment to determine whether they should be field tested. In practice for any given wetland, there is likely a combination of BMPs that would together have the greatest potential to address the low DO and high MeHg water quality concerns. Consequently, this report makes no sweeping recommendations applicable to large groups of wetlands but instead promotes a careful consideration of factors at each wetland or small groups of wetlands and from that assessment to apply the most effective suite of BMPs. This report also identifies a number of recommended future actions and studies. These recommendations are geared toward improving the process understanding of factors that promote low DO and high MeHg conditions, the extent of these problems in Suisun Marsh, the regulatory basis for the DO standards for a large estuarine marsh, the economics of BMPs, and alternative approaches to BMPs on diked managed wetlands that may address the water quality issues. The most important of these recommendations is that future BMP implementation should be carried out within the context of rigorous scientific evaluation so as to gain the maximum improvement in how to manage these water quality issues in the diked managed wetlands of Suisun Marsh.

Hypoxic and low pH water in the nearshore marine environments of Monterey Bay, California: characterizing a decade of oxygen and pH, and drivers of variability.

A decade-long time series recorded in southern Monterey Bay, California demonstrates that the shallow, near-shore environment (17 m depth) is regularly inundated with pulses of cold, hypoxic and low pH water. During these episodes, oxygen can drop to biologically threatening levels, and pH levels were lower than expected. Weekly water chemistry monitoring revealed that the saturation state of aragonite (the more soluble form of calcium carbonate) was often below saturation and had a moderate positive relationship with pH, however, analytical and human error could be high. Pulses of hypoxia and low pH water with the greatest intensity arise at the onset of the spring upwelling season, and fluctuations are strongly semidurnal (tidal) and diurnal. Arrival of cold, hypoxic water on the inner shelf typically occurs 3 days after the arrival of a strong upwelling event and appears to be driven by upwelling modulated by internal tidal fluctuations. I found no relationship between the timing of low-oxygen events and the diel solar cycle nor with terrestrial nutrient input. These observations are consistent with advection of hypoxic water from the deep, offshore environment where water masses experience a general decline of temperature, oxygen and pH with depth, and inconsistent with biochemical forcing. Comparisons with concurrent temperature and oxygen time series taken ~20 km away at the head of the Monterey Canyon show similar patterns but even more intense hypoxic events due to stronger semidiurnal forcing there. Analysis of the durations of exposure to low oxygen levels establishes a framework for assessing the ecological relevance of these events. Increasing oceanic hypoxia and acidification of both surface and deep waters may increase the number, intensity, duration and spatial extent of future intrusions along the Pacific coast. Evaluation of the resiliency of nearshore ecosystems such as kelp forests, rocky reefs and sandy habitats, will require consideration of these events.

Low-loss planar and stripe waveguides in Nd3+-doped silicate glass produced by oxygen-ion implantation

We report on the fabrication and characterization of low-loss planar and stripe waveguides in a Nd3+-doped glass by 6 MeV oxygen-ion implantation at a dose of 1x10(15) ions/cm(2). The dark mode spectroscopy of the planar waveguide was measured using a prism coupling arrangement. The refractive index profile of the planar waveguide was reconstructed from a code based on the reflectivity calculation method. The results indicate that a refractive index enhanced region as well as an optical barrier have been created after the ion beam processing. The near-field mode profiles of the stripe waveguide were obtained by an end-fire coupling arrangement, by which three quasitransverse electric modes were observed. After annealing, the propagation losses of the planar and stripe waveguides were reduced to be similar to 0.5 and similar to 1.8 dB/cm, respectively. (c) 2007 American Institute of Physics.