Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium

Hidrocarbonetos policíclicos aromáticos no meio ambiente: diferenciação de fontes em sedimentos e metabólitos em bile de peixes

Many studies on environmental ecosystems quality related to polycyclic aromatic hydrocarbons (PAH) have been carried out routinely due to their ubiquotus presence worldwide and to their potential toxicity after its biotransformation. PAH may be introduced into the environmet by natural and anthropogenic processes from direct runoff and discharges and indirect atmospheric deposition. Sources of naturally occurring PAHs include natural fires, natural oil seepage and recent biological or diagenetic processes. Anthropogenic sources of PAHs, acute or chronic, are combustion of organic matter (petroleum, coal, wood), waste and releases/spills of petroleum and derivatives (river runoff, sewage outfalls, maritime transport, pipelines). Besides the co-existence of multiples sources of PAH in the environmental samples, these compounds are subject to many processes that lead to geochemical fates (physical-chemical transformation, biodegradation and photo-oxidation), which leads to an alteration of their composition. All these facts make the identification of the hydrocarbons sources, if petrogenic, pyrolytic or natural, a challenge. One of the objectives of this study is to establish tools to identify the origin of hydrocarbons in environmental samples. PAH diagnostic ratios and PAH principal component analysis were tested on a critical area: Guanabara Bay sediments. Guanabara Bay is located in a complex urban area of Rio de Janeiro with a high anthropogenic influence, being an endpoint of chronic pollution from the Greater Rio and it was the scenario of an acute event of oil release in January 2000. It were quantified 38 compounds, parental and alkylated PAH, in 21 sediment samples collected in two surveys: 2000 and 2003. The PAH levels varied from 400 to 58439 ng g-1. Both tested techniques for origin identification of hydrocarbons have shown their applicability, being able to discriminate the PAH sources for the majority of the samples analysed. The bay sediments were separated into two big clusters: sediments with a clear pattern of petrogenic introduction of hydrocarbons (from intertidal area) and sediments with combustion characteristics (from subtidal region). Only a minority of the samples could not display a clear contribution of petrogenic or pyrolytic input. The diagnostic ratios that have exhibited high ability to distinguish combustion- and petroleum-derived PAH inputs for Guanabara Bay sediments were Phenanthrene+Anthracene/(Phenanthrene+Anthracene+C1Phenanthrene); Fluorantene/(Fluorantene+Pyrene); Σ (other 3-6 ring PAHs)/ Σ (5 alkylated PAH series). The PCA results prooved to be a useful tool for PAH source identification in the environment, corroborating the diagnostic indexes. In relation to the temporal evaluation carried out in this study, it was not verified significant changes on the class of predominant source of the samples. This result indicates that the hydrocarbons present in the Guanabara Bay sediments are mainly related to the long-term anthropogenic input and not directly related to acute events such as the oil spill of January 2000. This findings were similar to various international estuarine sites. Finally, this work had a complementary objective of evaluating the level of hydrocarbons exposure of the aquatic organisms of Guanabara Bay. It was a preliminary study in which a quantification of 12 individual biliar metabolites of PAH was performed in four demersal fish representing three different families. The analysed metabolites were 1-hydroxynaphtalene, 2-hidroxinaphtalene, 1hydroxyphenanthrene, 9-hydroxyphenanthrene, 2-hydroxyphenanthrene, 1hydroxypyrene, 3-hidroxibiphenil, 3- hydroxyphenanthrene, 1-hydroxychrysene, 9hydroxyfluorene, 4-hydroxyphenanthrene, 3-hydroxybenz(a)pyrene. The metabolites concentrations were found to be high, ranging from 13 to 177 µg g-1, however they were similar to worldwide regions under high anthropogenic input. Besides the metabolites established by the used protocol, it was possible to verified high concentrations of three other compounds not yet reported in the literature. They were related to pyrolytic PAH contribution to Guanabara Bay aquatic biota: 1-hydroxypyrine and 3-hydroxybenz(a)pyrine isomers

Inter-relação da produtividade de madeira do pinus com atributos físico-químicos de um latossolo do cerrado brasileiro

Com relação aos atributos do solo, a produtividade de madeira do pinus varia substancialmente em função do pH, do teor de matéria orgânica e da resistência à penetração. No ano de 2007, no Município de Selvíria (MS) foi analisada a produtividade de madeira do Pinus caribaea var. hondurensis, em função de alguns atributos físico-químicos de um Latossolo Vermelho Distrófico estabelecido num maciço florestal com 21 anos de idade. O objetivo foi selecionar, entre os atributos pesquisados do solo, aquele que melhor se apresentasse para explicar a variabilidade da produtividade de madeira. Para tanto, foi instalado um grid geoestatístico, para a coleta dos dados do solo e da planta, contendo 121 pontos amostrais, numa área de 3 ha do referido maciço. A produtividade de madeira variou diretamente com o pH do solo, tanto linear quanto espacialmente, com valores de 27,0-32,6 m³ ha-1 ano-1 e 3,9-4,4, respectivamente. Nos maiores, 32,6-36,9 m³ ha-1 ano-1 e 4,4-4,9. Dessa forma, o pH revelou ser um apreciável indicador da qualidade química do solo quando o objetivo foi estimar, linear e espacialmente, a produtividade de madeira da essência florestal pesquisada nas condições do Cerrado brasileiro do Sudeste do Estado do Mato Grosso do Sul.

Características produtivas, físicas e químicas de frutos de cultivares de pessegueiros sobre dois porta-enxertos no oeste do Estado de São Paulo

Objetivou-se avaliar as características físicas e químicas de seis cultivares de pessegueiros sobre os porta-enxertos Okinawa e Umê. O trabalho foi desenvolvido no Pólo Regional Alta Sorocabana-APTA, Presidente Prudente-SP, em 2004/2006. Foram avaliados a massa, comprimento, diâmetros sutural dos frutos, produção por planta, teor de sólidos solúveis (SS) e acidez titulável (AT). As avaliações permitiram concluir que os porta-enxertos influenciaram na massa dos frutos, tendo sobressaído o Umê, com frutos de maior massa média. em 2006, ocorreu aumento significativo na produtividade de todas as cultivares, sobressaindo-se as cvs. Talismã e Doçura 2, com valores acima da média. A cv. Doçura 2 sobre 'Okinawa' destacou-se por reunir melhores características físicas dos frutos e produção por planta. As cvs. Talismã e Dourado 2 produziram frutos com maiores valores de massa, comprimento e diâmetro sutural, sobre os porta-enxertos 'Okinawa' e Umê. A cv. Tropical destacou-se pelos atributos de qualidade, independentemente do porta-enxerto.

Produtividade do milho em sucessão a adubos verdes no sistema de plantio direto e convencional

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Efeito da adubação verde e época de semeadura de cultivares de feijão, sob sistema plantio direto, em região de cerrado

Cover crops are used for the purpose of land cover in order to improve the physical, chemical and biological properties of cultivated soils and improve the sustainability of grain production. The objective of this study was to evaluate the effect of different cover crops and the sowing of beans on the characteristics of three cultivars of commom bean in no tillage sistem. The research was develop in Fazenda de Ensino Pesquisa da Faculdade de Engenharia-UNESP-Campus de Ilha Solteira. The experimental design was completely randomized blocks and treatments were arranged in bands in 5x2x3 factorial design with four replications. The treatments consisted of cover crops (millet, jack bean, sunn hemp, velvet bean and fallow), sowing of beans (Perola, IAC Tuna, Carioca Precoce) grown in two years. Were evaluated: the final stand of plants, number of pods per plant, number of seeds per pod and per plant, weight of 100 seeds and seed yield. The cover crops sunn hemp and millet showed higher amount of fresh biomass in both years of cultivation, being recommended for our region. Occurring variations in the productivity of seeds depending on the years of cultivation, but the IAC Tuna was more stable in the variables analyzed.

Composição tecidual e qualidade da gordura na carne de cordeiros castrados e não castrados confinados sob dois fotoperíodos

Avaliaram-se os efeitos do fotoperíodo e da castração sobre a composição dos tecidos da paleta e características de qualidade da gordura do lombo e da paleta, de 20 cordeiros mestiços Ideal, distribuídos em esquema fatorial 2 x 2 (dois fotoperíodos - curto (FC), com 12 horas de luz, e longo (FL), com 18 horas de luz, e duas condições sexuais - não castrados (NC) e castrados (C)), com cinco repetições. Os animais foram abatidos aos 37kg de peso corporal. Maior quantidade de gordura total ocorreu nos cordeiros C e mais tecido conjuntivo nos animais NC. A castração influenciou o resíduo mineral fixo (RMF), o extrato etéreo (EE) e a proteína da gordura subcutânea. O efeito da interação entre fotoperíodo longo e castração resultou em aumento do teor de umidade na gordura intermuscular da paleta. A castração elevou o teor de EE e diminuiu o percentual de RMF. Não foi evidenciado efeito do fotoperíodo no EE dos músculos da paleta, e os animais castrados apresentaram gordura intramuscular mais elevada. Os níveis de colesterol da paleta foram mais elevados que os do lombo. Na carne de animais C, verificou-se maior quantidade de ácidos graxos saturados.

Qualidade da carne de cordeiros castrados e não-castrados confinados sob dois fotoperíodos

Objetivou-se avaliar a qualidade da carne por meio da determinação da composição centesimal e das características físicas da paleta e do lombo de 20 cordeiros mestiços Ideal, não-castrados (NC) e castrados (C), submetidos a fotoperíodos curto, de 12 horas (FC), e longo, de 18 horas (FL). Os animais foram divididos ao acaso em esquema fatorial 2 x 2 (condição sexual x fotoperíodo), em quatro tratamentos (NC em FC; C em FC; NC em FL; e C em FL), com cinco repetições, sendo terminados em confinamento individual até que atingissem 37 kg de PV. A qualidade da carne foi determinada em amostras da paleta e do músculo Longissimus lumborum (LL). Os mais baixos teores de umidade e os mais altos de EE, tanto na paleta como no lombo, foram determinados na carne dos animais castrados. O fotoperíodo longo influenciou significativamente os teores de EE e proteína total do músculo LL. A capacidade de retenção de água foi afetada pelo FL, no qual foram encontrados percentuais mais baixos. Não houve efeito do fotoperíodo nem da condição sexual sobre a capacidade de absorção de água e a perda de peso por cozimento do músculo LL. Os valores de força de cisalhamento (FoCi) na carne de cordeiros NC e dos submetidos ao FL foram superiores aos da carne dos animais castrados ou expostos ao FC.

Características e potencial tecnológico da carne da capivara

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Uso de bioestimulante na videira 'Niagara Rosada'

O experimento foi realizado no período de agosto a dezembro de 2004, em vinhedo de 'Niagara Rosada' localizado em Pratânea-SP. O objetivo foi avaliar o efeito de bioestimulante nas características morfológicas e físico-químicas dos cachos de uva 'Niagara Rosada'. Os tratamentos consistiram na pulverização dos cachos com o bioestimulante nas doses de 0, 5, 10, 15 e 20 mg L-1, 25 dias após o pleno florescimento. O delineamento estatístico utilizado foi em blocos ao acaso com cinco repetições, e parcelas constituídas por 3 cachos. Analisou-se a massa fresca, comprimento e largura dos cachos e bagos, massa fresca do engaço, número de bagos por cacho, diâmetro do pedicelo, teor de sólidos solúveis totais, acidez titulável e o pH. Concluiu-se que o bioestimulante promoveu aumento linear no comprimento do cacho, aumento quadrático no diâmetro do pedicelo e um decréscimo linear no teor de sólidos solúveis totais.

Influence of atypical pluviosity on phytoplankton assemblages in a stretch of a large sub-tropical river (Brazil)

This study aimed to evaluate the influence of alterations in pluviosity and ecological variables on microphytoplankton (> 20 mu m) structure (composition, richness, diversity, and abundance) and its biomass (chlorophyll-a), comparing different regions in a stretch of the low Igua double dagger u River and in some tributaries. Phytoplankton was sampled in 10 stations (5 in Igua double dagger u River and 5 in tributaries) during a dry period (April/2004) and an atypical rainy period (June/2004). The conductivity showed significant difference among the sampling points. Temperature, dissolved oxygen, pH, silicate, and nitrate showed significant differences between the dry and wet periods. Phytoplankton was composed of 149 taxa, and the most representative class was Chlorophyceae (71 taxa), followed by Bacillariophyceae (35 taxa), and Cyanophyceae (25 taxa). During the rainy period, stations of Igua double dagger u River showed higher taxa number and total density compared to the tributaries, but the values were similar in the dry period. Tributaries presented higher diversity and equitability in both periods. Except by two stations in Igua double dagger u River, the higher taxa number, densities and biomass occurred in the dry period, associated to low levels of suspended matter. The canonical correspondence analysis indicated the dominance of Bacillariophyceae and Chrysophyceae in the rainy period related to nitrate and suspended matter. Two other groups were observed in the dry period: one formed by Cyanophyceae, Dinophyceae, and Rhodophyceae, related to temperature and nitrite and other by Euglenophyceae and Chlorophyceae related to total phosphorus and silicate. The groups suggest adequate conditions of the physical, chemical and climatic factors to the establishment of the algae classes. Phytoplanktonic assemblages responded quickly to the environmental regional variations under strong influence of pluviosity, while in the dry period, homogeneity among stations and environmental variables was observed. The importance of climatic events is relevant in ecological studies in a temporal scale.

Tunnelling behaviour of the Asian subterranean termite in heterogeneous soils: presence of cues in the foraging area

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Produção de geléia de jambolão (Syzygium cumini Lamarck): processamento, parâmetros físico - químicos e avaliação sensorial

A fruta jambolão (Syzygium cumini Lamarck) é uma fruta de coloração roxa intensa e sabor agradável. Dado que não há na literatura nenhum relato de seu aproveitamento industrial, a produção de geléia de jambolão tornou-se uma interessante atividade de pesquisa. Este trabalho objetivou a elaboração e a avaliação das características físico-químicas e sensoriais da geléia obtida do jambolão. A fruta apresentou a seguinte composição química: cinzas, 0,34%; lipídeos, 0,30%; proteínas, 0,67%; carboidratos, 10,07%; fibras, 0,28%; umidade, 87,75%; frutose, 0,4%; glicose, 0,6%; antocianinas totais, 0,276%; substâncias pécticas, 0,245%; acidez titulável, 5,91%; sólidos solúveis, 9,00%; e pH, 3,9. A geléia obtida apresentou a seguinte composição: açúcares redutores, 20,99%; não-redutores, 18,01%; açúcares totais, 39,00%; pH, 3,42; sólidos solúveis, 67ºBrix; acidez titulável, 5,47%; e umidade, 29,63%. A análise sensorial foi realizada por uma equipe de 50 provadores não treinados que avaliaram os atributos cor, aparência, odor, textura, sabor e avaliação global, pelo método de escala hedônica com nove pontos. Os resultados obtidos mostraram que o atributo cor foi o que mais agradou aos provadores, o atributo odor foi o menos apreciado. em conclusão, o estudo de análise sensorial revelou uma aceitação satisfatória da geléia de jambolão.

Produção, propriedades e aplicações de oligossacarídeos

Oligosaccharides participate in the formation of dietary fiber and are mainly used as prebiotic agents. This review presents ways of obtaining these sugars, which can be produced by synthesis (chemical or enzymatic), or through depolymerization of polysaccharides (physical, chemical or enzymatic). Oligosaccharides have also been used commercially as an ingredient in cosmetics, pharmaceuticals, agricultural products and especially in the food industry because of their physical properties. The potential applications of oligosaccharides in several areas such as food, animal feed, pharmaceuticals and cosmetics have contributed to the increase in scientific research on these carbohydrates. The use of oligosaccharides as immuno-modulatory agents and biological response modifiers has been recently described, and their effects as anti-inflammatory and in reducing cholesterol. An overview of the various nutraceutical and biological functions of these carbohydrates in order to benefit human health is also reported.

Biochemical biomarkers and metals in Perna perna mussels from mariculture zones of Santa Catarina, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)