Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Desenvolvimento de dobras e falhas em ambiente distensional: Aplicação da modelagem física

The geological modeling allows, at laboratory scaling, the simulation of the geometric and kinematic evolution of geological structures. The importance of the knowledge of these structures grows when we consider their role in the creation of traps or conduits to oil and water. In the present work we simulated the formation of folds and faults in extensional environment, through physical and numerical modeling, using a sandbox apparatus and MOVE2010 software. The physical modeling of structures developed in the hangingwall of a listric fault, showed the formation of active and inactive axial zones. In consonance with the literature, we verified the formation of a rollover between these two axial zones. The crestal collapse of the anticline formed grabens, limited by secondary faults, perpendicular to the extension, with a curvilinear aspect. Adjacent to these faults we registered the formation of transversal folds, parallel to the extension, characterized by a syncline in the fault hangingwall. We also observed drag folds near the faults surfaces, these faults are parallel to the fault surface and presented an anticline in the footwall and a syncline hangingwall. To observe the influence of geometrical variations (dip and width) in the flat of a flat-ramp fault, we made two experimental series, being the first with the flat varying in dip and width and the second maintaining the flat variation in width but horizontal. These experiments developed secondary faults, perpendicular to the extension, that were grouped in three sets: i) antithetic faults with a curvilinear geometry and synthetic faults, with a more rectilinear geometry, both nucleated in the base of sedimentary pile. The normal antithetic faults can rotate, during the extension, presenting a pseudo-inverse kinematics. ii) Faults nucleated at the top of the sedimentary pile. The propagation of these faults is made through coalescence of segments, originating, sometimes, the formation of relay ramps. iii) Reverse faults, are nucleated in the flat-ramp interface. Comparing the two models we verified that the dip of the flat favors a differentiated nucleation of the faults at the two extremities of the mater fault. V These two flat-ramp models also generated an anticline-syncline pair, drag and transversal folds. The anticline was formed above the flat being sub-parallel to the master fault plane, while the syncline was formed in more distal areas of the fault. Due the geometrical variation of these two folds we can define three structural domains. Using the physical experiments as a template, we also made numerical modeling experiments, with flat-ramp faults presenting variation in the flat. Secondary antithetic, synthetic and reverse faults were generated in both models. The numerical modeling formed two folds, and anticline above the flat and a syncline further away of the master fault. The geometric variation of these two folds allowed the definition of three structural domains parallel to the extension. These data reinforce the physical models. The comparisons between natural data of a flat-ramp fault in the Potiguar basin with the data of physical and numerical simulations, showed that, in both cases, the variation of the geometry of the flat produces, variation in the hangingwall geometry

Comparação de desempenho da deconvolução preditiva multicanal e da filtragem f-k na atenuação de múltiplas do fundo do mar

The seismic reflection is used on a large scale in oil exploration. In case of marine acquisition the presence of high impedance contrast at the interfaces water/air generates multiple reflections events. Such multiple events can mask primary events; thus from the interpretational viewpoint it is necessary to mitigate the multiples. In this manuscript we compare two methods of multiple attenuation: the predictive multichannel deconvolution (DPM) and the F-K filtering (FKF). DPM is based in the periodicity of the multiples while FKF is based in multiples and primaries splitting in F-K domain. DPM and FKF were applied in common-offset and CDP gathers, respectively. DPM is quite sensible to the correct identification of the period and size of the filter while FKF is quite sensible to an adequate choice of the velocity in order to split multiples and primaries events in the F-K domain. DPM is a method that is designed to act over a specific event. So, when the parameters are well selected, DPM is very efficient in removing the specified multiple. Then DPM can be optimized by applying it several times, each time with a different parameterization. A deficiency of DPM occurs when a multiple is superposed to a primary event: in this situation, DPM can attenuate also the primary event. On the other hand, FKF presents almost the same performance to all multiples that are localized in the same sector of the F-K domain. The two methods can be combined in order to take advantage of their associated potentials. In this situation, DPM is firstly applied, with a focus in the sea bed multiples. Then FKF is applied in order to attenuate the remaining multiples

Effects of Annona squamosa extract on early pregnancy in rats

Annona squamosa Linn., family Annonaceae, is said to show varied medicinal effects, including insecticide, antiovulatory and abortifacient. The purpose of present study was to investigate if A. squamosa seed aqueous extract, in doses higher than that popularly used to provoke abortion, interferes with reproductive performance, and to correlate the ingestion of this extract with possible alterations in rat embryonic implantation. Doses of 300 mg/kg (Treated Group I, n = 17) and 600 mg/kg (Treated Group II, n = 12) body wt. were administered by gavage, during days 1 to 5 of pregnancy (preimplantation period). The control group (n = 13) received water in the same manner, during the same period for comparison with experimental groups. The animals were euthanized on day 10 of pregnancy. Treatment of dams during the preimplantation period showed no signs of toxicity, and no alteration in the corpora lutea, implantations and embryo in terms of development numbers. The percentage of preimplantation and postimplantation losses in treated groups I and II did not differ from those of control. Treatment with aqueous extract of A. squamosa seeds caused no morphological change in the endometrium. The absence of morphological alterations in uterine epithelial cells in treated groups I and II permitted a viable embryonic implantation, as verified by the number of embryos in development at day 10 of pregnancy. Thus, A. squamosa seed aqueous extract did not interfere with the reproductive performance of pregnant rats.

Determination of lead in the absence of supporting electrolyte using carbon fiber ultramicroelectrode without mercury film

The determination of lead ions directly in water, for application in analysis of samples of environmental interest, was studied by electroanalytical techniques. Linear sweep anodic stripping voltammetry with a carbon fiber disk ultramicroelectrode (7.0 mu m in diameter), without mercury film, has been used for lead determination, by standard addition, in purified water in the absence of supporting electrolyte. The response was linear in the range from 10.0 to 50.0 mu g L-1, with a detection limit of 0.8 mu g L-1, for 300 s preconcentration time, at -1.2 V and 1.0 V s(-1) scan rate. The reliability of the analytical procedure was evaluated by precision using relative standard deviations (5.6%, for three repetitive stripping current measurements of solution with 10.0 mu g L-1 lead ions) and by the accuracy with recovery experiments (mean of 110.8%) for the same concentration.

Fine-scale microhabitat selection in a bromeliad-dwelling jumping spider (Salticidae)

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

Optimal and sub-optimal control in Dengue epidemics

This work concerns the application of the optimal control theory to Dengue epidemics. The dynamics of this insect-borne disease is modelled as a set of non-linear ordinary differential equations including the effect of educational campaigns organized to motivate the population to break the reproduction cycle of the mosquitoes by avoiding the accumulation of still water in open-air recipients. The cost functional is such that it reflects a compromise between actual financial spending (in insecticides and educational campaigns) and the population health (which can be objectively measured in terms of, for instance, treatment costs and loss of productivity). The optimal control problem is solved numerically using a multiple shooting method. However, the optimal control policy is difficult to implement by the health authorities because it is not practical to adjust the investment rate continuously in time. Therefore, a suboptimal control policy is computed assuming, as the admissible set, only those controls which are piecewise constant. The performance achieved by the optimal control and the sub-optimal control policies are compared with the cases of control using only insecticides when Breteau Index is greater or equal to 5 and the case of no-control. The results show that the sub-optimal policy yields a substantial reduction in the cost, in terms of the proposed functional, and is only slightly inferior to the optimal control policy. Copyright (C) 2001 John Wiley & Sons, Ltd.

Experimental aspects of biomass fuels in a bubbling fluidized bed combustor

This work presents experimental information relevant to the combustion of biomass in a bubbling fluidized bed. The biomass distribution in a fluidized bed was studied through tests performed in a cold bed, while the volatiles released in the biomass pyrolysis, the burning rate of the resulting charcoal, and the combustion control regime, were studied through tests performed in a high temperature bed.Visual examination of photographs taken from a transparent walls bed, with a rectangular cross-section, showed that the large fuel particles, typical of biomass processing, were distributed in the bubbles, in the splash zone, and in the emulsion phase. The occurrence of biomass in the emulsion phase was favored by burning biomass particles of greater density and smaller size-expetimentally determined in each case. Decreasing the fuel particle size improved the biomass distribution inside the bed. The same was accomplished by increasing the superficial gas velocity as high as possible, compatibly with the acceptable elutriation.Burning tests showed that the biomass fuels have the advantage of reaching the diffusional regime at temperatures that can be lower than 1000 K, which ensures that the biomass fuels burn in a stable regime. (C) 2007 Elsevier B.V. All rights reserved.

Microbiological and physicochemical treatments applied to metallurgic industry aiming water reuse

Estudou-se o reuso de água de um sistema composto por estação de tratamento de esgoto (ETE) com aeração prolongada e lodo ativado, e em uma estação compacta de tratamento de água (ECTA) de uma indústria metalúrgica. Os processos para obtenção da água de reuso foram: microbiológico e físico-químico. O esgoto doméstico foi bombeado para a ETE, onde houve formação de flocos biológicos e água clarificada. Avaliou-se a eficiência do processo microbiológico da ETE mediante a remoção de demanda bioquímica de oxigênio (DBO), demanda química de oxigênio (DQO) e sólidos sedimentáveis (SS). A eficiência do processo físico-químico de clarificação e desinfecção foi avaliada mediante análises de pH, turbidez, cor, contagem de bactérias heterotróficas aeróbias, cloro livre, dureza, alcalinidade, cloretos, sulfatos, sólidos totais dissolvidos (STD). Na água de reuso além desses parâmetros avaliou-se a toxicidade aguda ao microcrustáceo Daphnia similis.

Podzolization as a deferralitization process: dynamics and chemistry of ground and surface waters in an Acrisol-Podzol sequence of the upper Amazon Basin

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

Development of an HPLC-UV/Vis method for the determination of dyes in a gasoline sample employing different pre-treatments

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

Germination of Styrax camporum Pohl. seeds in response to substrate types, moisture contents and the seed morphology

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Application methods and dosages of thiamethoxam in thrips control on tomato plants

O tripes Frankliniella schultzei Trybom (Thysanoptera: Thripidae) é um dos mais importantes vetores de tomato spotted wilt tospovirus (TSWV) na cultura do tomate no Brasil. Dois métodos de aplicação do inseticida thiamethoxam foram comparados no controle de tripes em tomate. O experimento foi conduzido em delineamento de blocos ao acaso com sete tratamentos e quatro repetições. Utilizou-se um pulverizador costal manual com lança simples provida de ponta de pulverização com jato cônico vazio JD 14-2 ou modificada, com aplicador tipo esguicho, em substituição à ponta de pulverização. Dosagens de 150 e 200 g i.a. ha-1 foram usadas em única aplicação com esguicho e 50 g i.a. ha-1 em pulverizações semanais, iniciadas aos 48 dias após a semeadura. A eficiência do inseticida em teste foi comparada com diafenthiuron (400 g i.a. ha-1), profenofos + cypermethrin (320+32 g i.a. ha-1, respectivamente) e methamidophos (60 g i.a. 100 L-1 de água), aplicados em pulverização. Não houve diferença estatística entre os métodos de aplicação e doses com thiamethoxam no controle de F. schultzei aos 24 dias após a aplicação, sendo vantajosa a realização de uma única aplicação das maiores dosagens de thiamethoxam com esguicho em comparação às aplicações semanais da menor dosagem em pulverização. A eficiência de controle do tripes com o inseticida thiamethoxam variou de 93 a 95%, nos diferentes métodos e dosagens em teste. Diafenthiuron e profenofos + cypermethrin apresentaram eficiência menor (78 e 88%, respectivamente), porém foram superiores às obtidas com methamidophos (71%). Os produtos e doses utilizados não causaram fitotoxicidade às plantas de tomate.