Caracterização da qualidade e interpretação das propriedades físico-químicas de gasolinas C brasileiras através de cromatografia gasosa e métodos quimiométricos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Utilização de melaço, manipueira e soro de queijo como substratos para produção de biossurfactante por Bacillus Pumilus e sua aplicação em biorremediação de solo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Microencapsulation of turmeric oleoresin in binary and ternary blends of gum arabic, maltodextrin and modified starch

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

Physical properties of edible films based on bovine myofibril proteins

Myofibril proteins have excellent filmogenic properties. The objective of this article was to study the effect of the thermal treatment, of the pH and of the plasticizer concentration (Cp) of the filmogenic solution (FS), using over some physical properties of edible films, using a surface and response methodology (SRM). Films were made of lyophilized myofibril proteins (LMP) extracted from bovine muscle, employing the technique of solubility obtained from diluted saline solutions. The films were elaborated from FS containing 1 g of LMP/100g of FS and from Cp of 50 g to 79 g of glycerin/100 g of LMP. The LMP was dispersed in water under moderate agitation, and the pH was kept at 2.5-3.5 with the use of acetic acid. The FS were submitted to thermal treatment at different temperatures for 45 minutes. Films were dried in ventilated oven at 37 degrees C/18hr, conditioned at 75% of relative humidity at 25 degrees C/48 hr before analysis of: mechanical properties by puncture test; apparent opacity by spectrophotometer; solubility by immersion in water; and water vapor permeability by the gravimetric method. In general, films showed good appearance, translucent, easily handled and touchable, except for the films formed with pH 2.5 and at a low temperature (35 degrees C), with a medium thickness of 0.400 +/- 0.005 mm. The pH of the FS significantly affected all the physical properties under study. The temperature of the thermal treatment of the FS greatly affected the force at the rupture, solubility and water vapor permeability. This treatment can promote intermolecular interactions through the formation of disulphide bonds; however a very intense treatment can reverse this effect by irreversible structural alterations in the proteins. The glycerol concentration affected considerably all the properties under study, with the exception of the apparent opacity. Plasticizer increases the mobility of macromolecules with consequences in all physical properties.

Simulated temperature changes as a result of Antarctic ice sheet growth and CO2 reduction

During the Middle Miocene climate transition about 14 million years ago, the Antarctic ice sheet expanded to near-modern volume. Surprisingly, this ice sheet growth was accompanied by a warming in the surface waters of the Southern Ocean, whereas a slight deep-water temperature increase was delayed by more than 200 thousand years. Here we use a coupled atmosphere-ocean model to assess the relative effects of changes in atmospheric CO2 concentration and ice sheet growth on regional and global temperatures. In the simulations, changes in the wind field associated with the growth of the ice sheet induce changes in ocean circulation, deep-water formation and sea-ice cover that result in sea surface warming and deep-water cooling in large swaths of the Atlantic and Indian ocean sectors of the Southern Ocean. We interpret these changes as the dominant ocean surface response to a 100-thousand-year phase of massive ice growth in Antarctica. A rise in global annual mean temperatures is also seen in response to increased Antarctic ice surface elevation. In contrast, the longer-term surface and deep-water temperature trends are dominated by changes in atmospheric CO2 concentration. We therefore conclude that the climatic and oceanographic impacts of the Miocene expansion of the Antarctic ice sheet are governed by a complex interplay between wind field, ocean circulation and the sea-ice system.

A ferrous oxalate mediated photo-Fenton system: Toward an increased biodegradability of indigo dyed wastewaters

This study assessed the applicability of a ferrous oxalate mediated photo-Fenton pretreatment for indigo-dyed wastewaters as to produce a biodegradable enough effluent, likely of being derived to conventional biological processes. The photochemical treatment was performed with ferrous oxalate and hydrogen peroxide in a Compound Parabolic Concentrator (CPC) under batch operation conditions. The reaction was studied at natural pH conditions (5–6) with indigo concentrations in the range of 6.67–33.33 mg L−1, using a fixed oxalate-to-iron mass ratio (C2O42−/Fe2+ = 35) and assessing the system's biodegradability at low (257 mg L−1) and high (1280 mg L−1) H2O2 concentrations. In order to seek the optimal conditions for the treatment of indigo dyed wastewaters, an experimental design consisting in a statistical surface response approach was carried out. This analysis revealed that the best removal efficiencies for Total Organic Carbon (TOC) were obtained for low peroxide doses. In general it was observed that after 20 kJ L−1, almost every treated effluent increased its biodegradability from a BOD5/COD value of 0.4. This increase in the biodegradability was confirmed by the presence of short chain carboxylic acids as intermediate products and by the mineralization of organic nitrogen into nitrate. Finally, an overall decrease in the LC50 for Artemia salina indicated a successful detoxification of the effluent.

Inspection of parts with complex geometry and welds with structural health monitoring techniques

Structural Health Monitoring (SHM) systems were developed to evaluate the integrity of a system during operation, and to quickly identify the maintenance problems. They will be used in future aerospace vehicles to improve safety, reduce cost and minimize the maintenance time of a system. Many SHM systems were already developed to evaluate the integrity of plates and used in marine structures. Their implementation in manufacturing processes is still expected. The application of SHM methods for complex geometries and welds are two important challenges in this area of research. This research work started by studying the characteristics of piezoelectric actuators, and a small energy harvester was designed. The output voltages at different frequencies of vibration were acquired to determine the nonlinear characteristics of the piezoelectric stripe actuators. The frequency response was evaluated experimentally. AA battery size energy harvesting devices were developed by using these actuators. When the round and square cross section devices were excited at 50 Hz frequency, they generated 16 V and 25 V respectively. The Surface Response to Excitation (SuRE) and Lamb wave methods were used to estimate the condition of parts with complex geometries. Cutting tools and welded plates were considered. Both approaches used piezoelectric elements that were attached to the surfaces of considered parts. The variation of the magnitude of the frequency response was evaluated when the SuRE method was used. The sum of the square of the differences was calculated. The envelope of the received signal was used for the analysis of wave propagation. Bi-orthogonal wavelet (Binlet) analysis was also used for the evaluation of the data obtained during Lamb wave technique. Both the Lamb wave and SuRE approaches along with the three methods for data analysis worked effectively to detect increasing tool wear. Similarly, they detected defects on the plate, on the weld, and on a separate plate without any sensor as long as it was welded to the test plate.

Development of New Structural Health Monitoring Techniques

During the past two decades, many researchers have developed methods for the detection of structural defects at the early stages to operate the aerospace vehicles safely and to reduce the operating costs. The Surface Response to Excitation (SuRE) method is one of these approaches developed at FIU to reduce the cost and size of the equipment. The SuRE method excites the surface at a series of frequencies and monitors the propagation characteristics of the generated waves. The amplitude of the waves reaching to any point on the surface varies with frequency; however, it remains consistent as long as the integrity and strain distribution on the part is consistent. These spectral characteristics change when cracks develop or the strain distribution changes. The SHM methods may be used for many applications, from the detection of loose screws to the monitoring of manufacturing operations. A scanning laser vibrometer was used in this study to investigate the characteristics of the spectral changes at different points on the parts. The study started with detecting a load on a plate and estimating its location. The modifications on the part with manufacturing operations were detected and the Part-Based Manufacturing Process Performance Monitoring (PbPPM) method was developed. Hardware was prepared to demonstrate the feasibility of the proposed methods in real time. Using low-cost piezoelectric elements and the non-contact scanning laser vibrometer successfully, the data was collected for the SuRE and PbPPM methods. Locational force, loose bolts and material loss could be easily detected by comparing the spectral characteristics of the arriving waves. On-line methods used fast computational methods for estimating the spectrum and detecting the changing operational conditions from sum of the squares of the variations. Neural networks classified the spectrums when the desktop – DSP combination was used. The results demonstrated the feasibility of the SuRE and PbPPM methods.

Development of New Structural Health Monitoring Techniques

During the past two decades, many researchers have developed methods for the detection of structural defects at the early stages to operate the aerospace vehicles safely and to reduce the operating costs. The Surface Response to Excitation (SuRE) method is one of these approaches developed at FIU to reduce the cost and size of the equipment. The SuRE method excites the surface at a series of frequencies and monitors the propagation characteristics of the generated waves. The amplitude of the waves reaching to any point on the surface varies with frequency; however, it remains consistent as long as the integrity and strain distribution on the part is consistent. These spectral characteristics change when cracks develop or the strain distribution changes. The SHM methods may be used for many applications, from the detection of loose screws to the monitoring of manufacturing operations. A scanning laser vibrometer was used in this study to investigate the characteristics of the spectral changes at different points on the parts. The study started with detecting a load on a plate and estimating its location. The modifications on the part with manufacturing operations were detected and the Part-Based Manufacturing Process Performance Monitoring (PbPPM) method was developed. Hardware was prepared to demonstrate the feasibility of the proposed methods in real time. Using low-cost piezoelectric elements and the non-contact scanning laser vibrometer successfully, the data was collected for the SuRE and PbPPM methods. Locational force, loose bolts and material loss could be easily detected by comparing the spectral characteristics of the arriving waves. On-line methods used fast computational methods for estimating the spectrum and detecting the changing operational conditions from sum of the squares of the variations. Neural networks classified the spectrums when the desktop – DSP combination was used. The results demonstrated the feasibility of the SuRE and PbPPM methods.

Desenvolvimento de método para determinação de espécies de mercúrio empregando MSPD e GC-MS

Neste trabalho é proposto pela primeira vez, o desenvolvimento e validação de um método analítico baseado no emprego da dispersão da matriz em fase sólida (MSPD) modificada, para extração das espécies CH3Hg+ e Hg2+ em amostras de peixe e determinação por cromatografia em fase gasosa acoplada à espectrometria de massas (GC-MS). O método de extração utilizando a MSPD combina o rompimento da estrutura física da amostra, através da maceração e do uso de SiO2 como suporte sólido, com o método da extração ácida, utilizando uma solução de HCl 4,2 mol L-1 e NaCl 0,5 mol L-1. Para otimização da MSPD, foram avaliados parâmetros como massa de amostra, massa de suporte sólido, concentração de HCl, concentração de NaCl, tipo de suporte sólido e o tempo de agitação, com auxílio da metodologia de superfície de resposta. Além disso, a etapa de derivatização e a separação cromatográfica também foram otimizadas na determinação de CH3Hg+ e Hg2+ por GC-MS. O método mostrouse adequado para extração e determinação de espécies de mercúrio através da aplicação em materiais de referência certificados de fígado de peixe (DOLT-3) e músculo de peixe (DORM-2), apresentando boas concordâncias com os valores certificados e desvio padrão relativo inferior a 9,5%. Os limites de detecção foram de 0,06 e 0,12 µg g-1 para CH3Hg+ e Hg2+, respectivamente. Além disso, foi observado um significativo efeito de matriz e, por isso, a calibração foi feita com curvas preparadas com o extrato da MSPD. O método mostrou boa concordância na comparação entre a soma da concentração das espécies e a concentração de mercúrio total determinada por espectrometria de massas com plasma indutivamente acoplado com geração de vapor frio (CVG-ICP-MS), após digestão assistida por micro-ondas (MAD) em peixes do tipo atum (Thunnus thynnus), cação anjo (Squatina squatina) e cação viola (Rhinobatos blochii.).

Optimization of extrusion process to obtain shrimp snacks with rice grits and polished rice grains.

This research studied the effect of thermoplastic extrusion on the expansion index (EI), water absorption index (WAI), water solubility index (WSI), and sensory acceptance (SA) of a snack from rice grits, polished rice grains, and shrimp. A 23 factorial design was used with independent variables, temperature in the third extruder zone (63.2?96.8°C), initial moisture (106.4?173.6 g/kg), and shrimp content (16?184 g/kg), whereas EI, WAI, WSI, and SA were the responses. Through the surface-response methodology, the formulation with 80 g/kg shrimp and 130 g/kg initial moisture processed at 85°C in the third extruder zone was considered optimal. The product had good EI, WAI, and SA, 65.6 g/kg moisture, 24.0 g/kg lipids, 89.5 g/kg proteins, 34.2 kg/kg ashes, 72.4 g/kg fibers, and 714.3 g/kg carbohydrates. The product is an alternative for using rice grit, which has low commercial value, while also fully using the regional shrimp.

Canopy-scale biophysical controls of transpiration and evaporation in the Amazon Basin.

Canopy and aerodynamic conductances (gC and gA) are two of the key land surface biophysical variables that control the land surface response of land surface schemes in climate models. Their representation is crucial for predicting transpiration (λET) and evaporation (λEE) flux components of the terrestrial latent heat flux (λE), which has important implications for global climate change and water resource management. By physical integration of radiometric surface temperature (TR) into an integrated framework of the Penman?Monteith and Shuttleworth?Wallace models, we present a novel approach to directly quantify the canopy-scale biophysical controls on λET and λEE over multiple plant functional types (PFTs) in the Amazon Basin. Combining data from six LBA (Large-scale Biosphere-Atmosphere Experiment in Amazonia) eddy covariance tower sites and a TR-driven physically based modeling approach, we identified the canopy-scale feedback-response mechanism between gC, λET, and atmospheric vapor pressure deficit (DA), without using any leaf-scale empirical parameterizations for the modeling. The TR-based model shows minor biophysical control on λET during the wet (rainy) seasons where λET becomes predominantly radiation driven and net radiation (RN) determines 75 to 80 % of the variances of λET. However, biophysical control on λET is dramatically increased during the dry seasons, and particularly the 2005 drought year, explaining 50 to 65 % of the variances of λET, and indicates λET to be substantially soil moisture driven during the rainfall deficit phase. Despite substantial differences in gA between forests and pastures, very similar canopy?atmosphere "coupling" was found in these two biomes due to soil moisture-induced decrease in gC in the pasture. This revealed the pragmatic aspect of the TR-driven model behavior that exhibits a high sensitivity of gC to per unit change in wetness as opposed to gA that is marginally sensitive to surface wetness variability. Our results reveal the occurrence of a significant hysteresis between λET and gC during the dry season for the pasture sites, which is attributed to relatively low soil water availability as compared to the rainforests, likely due to differences in rooting depth between the two systems. Evaporation was significantly influenced by gA for all the PFTs and across all wetness conditions. Our analytical framework logically captures the responses of gC and gA to changes in atmospheric radiation, DA, and surface radiometric temperature, and thus appears to be promising for the improvement of existing land?surface?atmosphere exchange parameterizations across a range of spatial scales.

Canopy-scale biophysical controls of transpiration and evaporation in the Amazon Basin.

Canopy and aerodynamic conductances (gC and gA) are two of the key land surface biophysical variables that control the land surface response of land surface schemes in climate models. Their representation is crucial for predicting transpiration (?ET) and evaporation (?EE) flux components of the terrestrial latent heat flux (?E), which has important implications for global climate change and water resource management. By physical integration of radiometric surface temperature (TR) into an integrated framework of the Penman?Monteith and Shuttleworth?Wallace models, we present a novel approach to directly quantify the canopy-scale biophysical controls on ?ET and ?EE over multiple plant functional types (PFTs) in the Amazon Basin. Combining data from six LBA (Large-scale Biosphere-Atmosphere Experiment in Amazonia) eddy covariance tower sites and a TR-driven physically based modeling approach, we identified the canopy-scale feedback-response mechanism between gC, ?ET, and atmospheric vapor pressure deficit (DA), without using any leaf-scale empirical parameterizations for the modeling. The TR-based model shows minor biophysical control on ?ET during the wet (rainy) seasons where ?ET becomes predominantly radiation driven and net radiation (RN) determines 75 to 80?% of the variances of ?ET. However, biophysical control on ?ET is dramatically increased during the dry seasons, and particularly the 2005 drought year, explaining 50 to 65?% of the variances of ?ET, and indicates ?ET to be substantially soil moisture driven during the rainfall deficit phase. Despite substantial differences in gA between forests and pastures, very similar canopy?atmosphere "coupling" was found in these two biomes due to soil moisture-induced decrease in gC in the pasture. This revealed the pragmatic aspect of the TR-driven model behavior that exhibits a high sensitivity of gC to per unit change in wetness as opposed to gA that is marginally sensitive to surface wetness variability. Our results reveal the occurrence of a significant hysteresis between ?ET and gC during the dry season for the pasture sites, which is attributed to relatively low soil water availability as compared to the rainforests, likely due to differences in rooting depth between the two systems. Evaporation was significantly influenced by gA for all the PFTs and across all wetness conditions. Our analytical framework logically captures the responses of gC and gA to changes in atmospheric radiation, DA, and surface radiometric temperature, and thus appears to be promising for the improvement of existing land?surface?atmosphere exchange parameterizations across a range of spatial scales.

A Trans-dimensional inversion algorithm to model deformation sources with unconstrained shape in finite element domains

Ground deformation provides valuable insights on subsurface processes with pattens reflecting the characteristics of the source at depth. In active volcanic sites displacements can be observed in unrest phases; therefore, a correct interpretation is essential to assess the hazard potential. Inverse modeling is employed to obtain quantitative estimates of parameters describing the source. However, despite the robustness of the available approaches, a realistic imaging of these reservoirs is still challenging. While analytical models return quick but simplistic results, assuming an isotropic and elastic crust, more sophisticated numerical models, accounting for the effects of topographic loads, crust inelasticity and structural discontinuities, require much higher computational effort and information about the crust rheology may be challenging to infer. All these approaches are based on a-priori source shape constraints, influencing the solution reliability. In this thesis, we present a new approach aimed at overcoming the aforementioned limitations, modeling sources free of a-priori shape constraints with the advantages of FEM simulations, but with a cost-efficient procedure. The source is represented as an assembly of elementary units, consisting in cubic elements of a regular FE mesh loaded with a unitary stress tensors. The surface response due to each of the six stress tensor components is computed and linearly combined to obtain the total displacement field. In this way, the source can assume potentially any shape. Our tests prove the equivalence of the deformation fields due to our assembly and that of corresponding cavities with uniform boundary pressure. Our ability to simulate pressurized cavities in a continuum domain permits to pre-compute surface responses, avoiding remeshing. A Bayesian trans-dimensional inversion algorithm implementing this strategy is developed. 3D Voronoi cells are used to sample the model domain, selecting the elementary units contributing to the source solution and those remaining inactive as part of the crust.

Electrochemical Oxidation Of Landfill Leachate In A Flow Reactor: Optimization Using Response Surface Methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99 % of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.