Determinação de dados de equilíbrio de fases para sistemas aquosos com eletrólitos

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer s ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Avaliação de diferentes processos oxidativos avançados no tratamento de resíduos de petróleo

The petroleum industry deals with problems which are difficult to solve because of their relation to environmental issues. This is because amounts of residue are generated which vary in type and danger level. The soil contamination by non aqueous liquid phase mixtures, specifically hydrocarbon petroleum has been a reason for great concern, mainly the aromatic and polycyclic aromatic, which present risk to human health due to its carcinogenic and mutagenic character. The Advanced Oxidative Processes (AOP) are efficient technologies for destruction of organic compounds of difficult degradation and, often, they are present in low concentrations. They can be considered clean technologies, because there is no formation of solid by-products or the transfer of pollutor phases. This work focuses on the study of the degradation of petroleum industrial waste, by Advanced Oxidation Processes. Treatments tackling petroleum residues, contaminated soil, and water occurring in the production of petroleum reached the following Polycyclic Aromatic Hydrocarbons (PAH) degradation levels: solid residues 100% in 96 treatment hours; water residue - 100% in 6 treatment hours; soil contamination (COT degradation) - 50.3% in 12 treatment hours. AOP were effective in dealing with petroleum residues thus revealing themselves to be a promising treatment alternative

Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Study of the interaction between cardiolipin bilayers and methylene blue in polymer-based Layer-by-Layer and Langmuir films applied as membrane mimetic systems

An increase of the reports involving mimetic systems has been observed. Briefly, these systems use biological phospholipids to exploit specific interactions between membrane-models and drugs. Here, the Layer-by-Layer (LbL) and Langmuir techniques were used to investigate the interaction between cardiolipin (CLP-negative phospholipid) and a cationic-like drug methylene blue (MB). Supported by a cationic polyelectrolyte (PAH), LbL films containing PAH/(CLP + MB) and PAH/(CLP + MB + AgNP) were grown up to 14 bilayers. The optical microscopy analysis revealed a decrease of the CLP vesicle sizes in the presence of MB as a possible consequence of the MB action onto the mechanical properties of the CLP membrane. From FTIR spectra, changes mainly related to peak position and band intensity and shape were observed in the spectra from PAH/CLP when in the presence of MB. The latter supports that the interactions between the phosphate and amine charged groups from CLP and PAH, respectively, established during the LbL film fabrication, besides the CLP hydrocarbon environment, are influenced by the presence of MB. Using the micro-Raman technique, a chemical mapping was build based on MB spectrum by resonance Raman scattering (RRS) and surface-enhanced resonance Raman scattering (SERRS). The later phenomenon was activated by Ag nanoparticles (AgNPs) trapped within the LbL film allowing collecting spectra for a single bilayer of PAH/(CLP + MB + AgNP). A rough estimation showed a SERRS amplification of 10(3) in comparison to RRS spectra. As a complementary approach, Langmuir films of CLP in the presence of co-spread MB were investigated through surface pressure vs mean molecular area (pi-A) isotherms. The results showed that for concentrations of MB below 100 mol%, the drug is expelled to water subphase for high values of surface pressure (condensed phase). For concentration at 100% and higher, the MB keeps bound to CLP floating monolayer. (C) 2010 Elsevier B.V. All rights reserved.

The reactivity of oytho-methoxy-substituted catechol radicals with sulfhydryl groups: Contribution for the comprehension of the mechanism of inhibition of NADPH oxidase by apocynin

Redox processes are involved in the mechanism of action of NADPH oxidase inhibitors such as diphenyleneiodonium and apocynin. Here, we studied the structure-activity relationship for apocynin and analogous ortho-methoxy-substituted catechols as inhibitors of the NADPH oxidase in neutrophils and their reactivity with peroxidase. Aiming to alter the reduction potential, the ortho-methoxy-catechol moiety was kept constant and the substituents at para position related to the hydroxyl group were varied. Two series of compounds were employed: methoxy-catechols bearing electron-withdrawing groups (MC-W) such as apocynin, vanillin, 4-nitroguaiacol, 4-cyanoguaiacol, and methoxy-catechol bearing electron-donating groups (MC-D) such as 4-methylguaiacol and 4-ethylguaiacol. We found that MC-D were weaker inhibitors compared to MD-W. Furthermore, the radicals generated by oxidation of MC-W via MPO/H(2)O(2), but not for MC-D, were able to oxidize glutathione (GSH) as verified by the formation of thiyl radicals, depletion of GSH, and recycling of the ortho-methoxy-catechols during their oxidations. The capacity of oxidizing sulfhydryl (SH) groups was also verified when ovalbumin was incubated with MC-W, but not for MC-D. Since the effect of apocynin has been correlated with inactivation of the cytosolic fractions of the NADPH oxidase complex and its oxidation during the inhibitory process develops a special role in this process, we suggest that the close relationship between the reactivity of the radicals of MC-W compounds with thiol groups and their efficacy as NADPH oxidase inhibitor could be the chemical pathway behind the mechanism of action of apocynin and should be taken into account in the design of new and specific NADPH oxidase inhibitors. (c) 2007 Elsevier B.V. All rights reserved.

Prospecção de genes de interesse biotecnológico : uma abordagem metagenômica

The total number of prokaryotic cells on Earth has been estimated at 4 to 6x1030 and only about 1% of microorganisms present in the environment can be cultivated by standard techniques of cultivation and plating. Therefore, it is a huge biological and genetic pool that can be exploited, for the identification and characterization of genes with biotechnological potential. Within this perspective, the metagenomics approach was applied in this work. Functional screening methods were performed aiming to identify new genes related to DNA repair and / or oxidative stress resistance, hydrocarbon degradation and hydrolytic activities (lipase, amylase and protease). Metagenomic libraries were built utilizing DNA extracted from soil samples collected in João Câmara RN. The libraries were analyzed functionally using specific substrate containing solid medium (hydrolytic activity), supplemented with H2O2 (DNA repair and / or resistance to oxidative stress) and liquid medium supplemented with light Arabian oil (activity, degradation of hydrocarbons). After confirmation of activity and exclusion of false-positive results, 49 clones were obtained, being 2 positive for amylase activity, 22 resistant to oxidative stress generated by H2O2 and 25 clones active for hydrocarbons degradation. Analysis of the sequences showed hypothetical proteins, dienelactona hydrolase, DNA polymerase, acetyltransferase, phosphotransferase, methyltransferase, endonucleases, among other proteins. The sequence data obtained matched with the functions tested, highlighting the success of metagenomics approaches combined with functional screening methods, leading to very promising results

Bark and ambrosia beetle (Coleoptera : Scolytidae) responses to volatiles from aging loblolly pine billets

Many species of bark and ambrosia beetles use host volatiles as cues for breeding site location. In a study where the objectives were to identify the different volatiles released by Pinus taeda L. billets as they age, to determine the arrival sequence of scolytids (Colcoptera: Scolytidae), and to correlate volatile emission by the billets with beetle catches, 25 species of scolytids were trapped. Bark beetles were more attracted to the billets in the beginning of the period. whereas ambrosia beetles arrived later. Among the bark beetles, Dendroctonus terebrans (Olivier) was significantly more attracted during the Ist 3 wk after tree felling, Hylastes tenuis Eichhoff in the Ist 2 wk. Pityophtorus pulicarius (Zimmermann) in weeks 2 and 3, and Ips grandicollis (Eichhoff) was more attracted on weeks 3 and 4. Among the ambrosia beetles, Xyleborinus saxeseni (Ratzeburg) was more attracted to billets during weeks 4-6, whereas Xyleborus pubescens Zimmermann and Xyleborus californicus Wood were more attracted during week 6. The billets showed marked decline in attractiveness to all scolytids after 8 wk. Volatiles collected during the beetle trapping periods included 15 hydrocarbon monoterpenes, 18 oxygenated monoterpenes, 4-allylanisole, and ethanol. The hydrocarbon monoterpenes and 4-allylanisole decreased sharply over time, but oxygenated monoterpenes and ethanol increased up to weeks 4-6, after which they also decreased. Good correlations between certain billet volatiles and catches for some beetle species were obtained, but their biological significance could not be determined.

Síntese, caracterização e aplicação do MCM-41 e A1-MCM-41 na pirólise do resíduo atmosférico de petróleo

In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamaré- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products

Comparação entre metodologias de extração de HPAs em água utilizando um planejamento fatorial com quantificação no CG/EM

PAHs (Polycyclic Aromatic Hydrocarbons) are a group of organic substances which receive considerable attention because of the carcinogenic and mutagenic properties of some of them. It is therefore important to determine the PAHs in different environmental matrices. Several studies have shown the use of gas chromatography coupled to mass spectrometry as a technique for quantification of PAHs by presenting excellent detection limits. This study aimed to develop an analytical methodology for the determination of 16 PAHs listed by the USEPA, test two methods for extraction of PAHs in water from a 23 factorial design, quantify them through the analytical technique coupled to gas chromatography mass spectrometry (GC/MS) using the method developed, and finally apply the results in chemometrics. The sample was synthesized and subjected to tests of the 23 factorial design, which has the factors: the type of extraction technique (ultrasound and digester), the ratio solvent / sample (1:1 and 1:3) and the type of solvent (dichloromethane / hexane and acetone / dichloromethane). The responses of eight combinations of the factorial design were obtained from the quantification by external calibration in GC/MS. The quantification method was developed from an optimized adaptation of the USEPA Method 8270. We used the full scan mode as a way of acquiring the mass spectra of 16 PAHs. The time in which the samples were subjected to ultrasound was fixed at 10 min and held an investigation to establish the conditions of power and time in the digester. We had the best response in the investigation of the digester power of 100 watts and the time of six minutes. The factorial design of liquid-liquid extraction showed that the most representative factors were: the use of the digester as extraction technique, the ratio solvent / sample 1:1 and the use of a 1:1 mixture of dichloromethane / hexane as a solvent more suitable. These results showed that the 1:1 mixture of dichloromethane / hexane is an excellent mixture to recover the extraction of PAHs an aqueous sample using the microwave digester. The optimization of the method of separation, identification and quantification of PAHs in the GC/MS was valid for 16 PAHs present in each chromatogram of the samples

Dessulfurização oxidativa em diesel utilizando catalisadores à base de vanádio ou manganês

The oxidative desulfurization process (ODS) of a commercial diesel fuel was performed under mild conditions in the presence of catalysts based on vanadium or manganese, supported on alumina, clays (commercial, natural and pillared) and zeolites (NaX, NaY, beta, mordenite and ZSM-5). The catalysts were synthesized by wet impregnation and characterized by X-ray diffraction, textural analysis by N2 adsorption and scanning electron microscopy. The dibenzothiophene (DBT) was used as sulfur compound in catalytic evaluation. The reactions were performed using acetonitrile as solvent and the hydrogen peroxide as oxidant at 55°C. The reaction products were analized by gas chromatography (GC-FID). In the studied conditions, the process was efficient due to the DBT was converted to its corresponding sulfone. Both DBT and corresponding sulfone were extracted by the solvent. Removals and oxidations up to 100% of sulfur compound were achieved. The catalysts supported on ZSM-5 zeolite showed are more effective for oxidation reaction of sulfur compound, presenting the best results. It was observed for oxidation reaction, that vanadium catalysts were more effective and manganese catalysts showed best results for removal of sulfur compounds

Evolução tectono-estrutural do Campo de Xaréu (Sub-bacia de Mundaú, Bacia do Ceará - NE do Brasil: abordagem multiescala e pluriferramental

The Xaréu Oil Field, located in the center-southern portion of the Mundaú Sub-Basin (eastern portion of the Ceará Basin), is characterized by a main Iramework of NW-trending and NE-dipping faults. The faults in the Xaréu Oil Field, among which the Xaréu Fautt stands out, are arranged according to an extensional-listriclan, rooted on a detachment surface corresponding to the Mundaú Fault, the border fautt of Mundaú Sub-Basin. During the tectonic-structural evolution of the Xaréu Oil Field and the Mundaú Sub-Basin, the Mundaú Fault played a crucial role on the control of the geometry of both compartments. The main carbonatic unit in the Xaréu Oil Field, named the Trairí Member(Paracuru Formation of Late Aptian to Early Albian age), contains the largest oil volume in the field, concentrated in structurally-controlled accumulations. The Trairí Member is composed by a variety of carbonatic rocks (massive, bedded or laminated calcilutites, ostracodites, calcarenites and carbonatic rudites, all of them presenting variable degrees of dolomitization). The carbonatic rocks are interbedded into thick packages of black shales and marls, besides local beds of siliciclastic conglomerates, sandstones, siltnes and argillites. From the spatial association and the genetic relationships between the carbonatic and siliciclastic units, it is possible to group them in three lithofacies associations (Marginal Plain, Ramp and Lacustrine Interior) that, together, were developed in a lacustrine system associated to a marginal sabkha. Structural studies based on drill coresthat sample the Trairí Member in the Xaréu Oil Field allowed to characterize two generations of meso- to microscale structures: the D1 group presents a typical hydroplastic character, being characterized by intra/interstratal to oblique-bedding shear zones. The hydroplastic character related to these structures allowed to infer their development at an early-lithilication stage of the Trairí Member, leading to infer an Early Cretaceous age to them. The second group of structures identified in the drill cores, nominated D2 and ascribed to a Neogene age, presents a strictly brttle character, being typilied by normal faults and slickenfibers of re-crystallized clayminerals, ali olthem displaying variable orientations. Although the present faults in the Xaréu Oil Field (and, consequently, in the Mundaú Sub-Basin) were classically relerred as struetures of essentially normal displacement, the kinematics analysis of the meso-to microscaie D1 struetures in the drill cores led to deline oblique displacements (normal with a clockwise strike-slip component) to these faults, indicating a main tectonic transport to ENE. These oblique movements would be responsible for the installation of a transtensive context in the Mundaú Sub-Basin, as part of the transcurrent to translormant opening of the Atlantic Equatorial Margin. The balancing of four struetural cross-sections ofthe Xaréu Oil Field indicates that the Mundaú Fault was responsible for more than 50% of the total stretching (ß factor) registered during the Early Aptian. At the initial stages of the "rifting", during Early Aptianuntil the Holocene, the Mundaú Sub-Basin (and consequently the Xaréu Oil Fleld) accumulated a total stretching between 1.21 and 1.23; in other words, the crust in this segment of the Atlantic Equatorial Margin was subjeeted to an elongation of about 20%. From estimates of oblique displacements related to the faults, it ws possible to construct diagrams that allow the determination of stretching factors related to these displacements. Using these diagrams and assuming the sense 01 dominant teetonictransport towards ENE, it was possible to calculate the real stretching lactors related to the oblique movement 0 of the faults in the Mundaú Sub-Basin. which reached actual values between 1.28 and 1.42. ln addnion to the tectonic-structural studies in the Xaréu Oil Field, the interpretation of remote sensing products, coupled wnh characterization of terrain analogues in seleeted areas along the northern Ceará State (continental margins of the Ceará and Potiguar basins), provided addnional data and constraints about the teetonic-structural evolution of the oil lield. The work at the analogue sites was particularly effective in the recognition and mapping, in semidetail scale, several generations of struetures originated under a brittle regime. Ali the obtained information (from the Xaréu Oil Field, the remote sensor data and the terrain analogues) were jointly interpreted, culminating with the proposnion of an evolutionary model lor this segment of the Atlantic Equatorial Margin; this model that can be applied to the whole Margin, as well. This segmentof the Atlantic Equatorial Margin was delormedin an early E-W (when considered lhe present-day position of the South American Plate) transcurrent to transform regime with dextral kinematics, started Irom, at least, the Early Aptian, which left its record in several outcrops along the continental margin of the Ceará State and specilically in the Xaréu off Field. The continuous operation of the regime, through the Albian and later periods, led to the definitive separation between the South American and African plates, with the formation of oceanic lithosphere between the two continental blocks, due to the emplacement off spreading centers. This process involved the subsequent transition of the transcurrent to a translorm dextral regime, creating lhe Equatorial Atlantic Oceano With the separation between the South American and African plates already completed and the increasing separation between lhe continental masses, other tecton ic mechanisms began to act during the Cenozoic (even though the Cretaceous tectonic regime lasted until the Neogene), like an E-W compressive stress líeld (related to the spreading olthe oceanic floor along lhe M id-Atlantic Ridge and to the compression of the Andean Chain) effective Irom the Late Cretaceous, and a state of general extension olthe horizontal surface (due to the thermal uplift ofthe central portion of Borborema Province), effective during the Neogene. The overlap of these mechanisms during the Cenozoic led to the imprint of a complex tectonic framework, which apparently influenced the migration and entrapment 01 hydrocarbon in the Ceará Basin

Litoestratigrafia e deformação cenzóica na região de Icapuí, Ceará, e implicações para a estruturação de campos de petróleo na borda ocidental da bacia Potiguar(NE do Brasil)

This thesis deals with the sedimentological/stratigraphic and structural evolution of the sedimentary rocks that occur in the NW continental border of the Potiguar Basin. These rocks are well exposed along coastal cliffs between the localities of Lagoa do Mato and Icapuí, Ceará State (NE Brazil). The sedimentological/stratigraphic study involved, at the outcrop scale, detailed facies descriptions, profile mapping of the vertical succession of different beds, and columnar sections displaying inferred lateral relationships. The approach was complemented by granulometric and petrographic analyses, including the characterization of heavy mineral assemblages. The data set allowed to recognize two kinds of lithological units, a carbonate one of very restricted occurrence at the base of the cliffs, and three younger, distinct siliciclastic units, that predominate along the cliffs, in vertical and lateral extent. The carbonate rocks were correlated to the late Cretaceous Jandaíra Formation, which is covered by the siliciclastic Barreiras Formation. The Barreiras Formation occurs in two distinct structural settings, the usual one with nondeformed, subhorizontal strata, or as tilted beds, affected by strong deformation. Two lithofacies were recognized, vertically arranged or in fault contacts. The lower facies is characterized by silty-argillaceous sandstones with low-angle cross bedding; the upper facies comprises medium to coarse grained sandstones, with conglomeratic layers. The Tibau Formation (medium to coarse-grained sandstones with argillite intercalations) occurs at the NW side of the studied area, laterally interlayered with the Barreiras Formation. Eolic sediments correlated to the Potengi Formation overly the former units, either displaying an angular unconformity, or simply an erosional contact (stratigraphic unconformity). Outstanding structural features, identified in the Barreiras Formation, led to characterize a neocenozoic stress field, which generated faults and folds and/or reactivated older structures in the subjacent late cretaceous (to paleogene, in the offshore basin) section. The structures recognized in the Barreiras Formation comprise two distinct assemblages, namely a main extensional deformation between the localities of Ponta Grossa and Redonda, and a contractional style (succeeded by oblique extensional structures) at Vila Nova. In the first case, the structural assemblage is dominated by N-S (N±20°Az) steep to gently-dipping extensional faults, displaying a domino-style or listric geometry with associated roll-over structures. This deformation pattern is explained by an E-W/WNW extension, contemporaneous with deposition of the upper facies of the Barreiras Formation, during the time interval Miocene to Pleistocene. Strong rotation of blocks and faults generated low-angle distensional faults and, locally, subvertical bedding, allowing to estimate very high strain states, with extension estimates varying between 40% up to 200%. Numerous detachment zones, parallel to bedding, help to acommodate this intense deformation. The detachment surfaces and a large number of faults display mesoscopic features analoguous to the ones of ductile shear zones, with development of S-C fabrics, shear bands, sigmoidal clasts and others, pointing to a hydroplastic deformation regime in these cases. Local occurrences of the Jandaíra limestone are controled by extensional faults that exhume the pre-Barreiras section, including an earlier event with N-S extension. Finally, WNWtrending extensional shear zones and faults are compatible with the Holocene stress field along the present continental margin. In the Vila Nova region, close to Icapuí, gentle normal folds with fold hinges shallowly pluging to SSW affect the lower facies of the Barreiras Formation, displaying an incipient dissolution cleavage associated with an extension lineation at high rake (a S>L fabric). Deposition of the upper facies siliciclastics is controlled by pull-apart graben structures, bordered by N-NE-trending sinistral-normal shear zones and faults, characterizing an structural inversion. Microstructures are compatible with tectonic deformation of the sedimentary pile, burried at shallow depths. The observed features point to high pore fluid pressures during deformation of the sediments, producing hydroplastic structures through mechanisms of granular flow. Such structures are overprinted by microfractures and microfaults (an essentially brittle regime), tracking the change to microfracturing and frictional shear mechanisms accompanying progressive dewatering and sediment lithification. Correlation of the structures observed at the surface with those present at depth was tested through geophysical data (Ground Penetrating Radar, seismics and a magnetic map). EW and NE-trending lineaments are observed in the magnetic map. The seismic sections display several examples of positive flower structures which affect the base of the cretaceous sediments; at higher stratigraphic levels, normal components/slips are compatible with the negative structural inversion characterized at the surface. Such correlations assisted in proposing a structural model compatible with the regional tectonic framework. The strong neogenepleistocene deformation is necessarily propagated in the subsurface, affecting the late cretaceous section (Açu and Jandaíra formations), wich host the hydrocarbon reservoirs in this portion of the Potiguar Basin. The proposed structural model is related to the dextral transcurrent/transform deformation along the Equatorial Margin, associated with transpressive terminations of E-W fault zones, or at their intersections with NE-trending lineaments, such as the Ponta Grossa-Fazenda Belém one (the LPGFB, itself controlled by a Brasiliano-age strike-slip shear zone). In a first step (and possibly during the late Cretaceous to Paleogene), this lineament was activated under a sinistral transpressional regime (antithetic to the main dextral deformation in the E-W zones), giving way to the folds in the lower facies of the Barreiras Formation, as well as the positive flower structures mapped through the seismic sections, at depth. This stage was succeeded (or was penecontemporaneous) by the extensional structures related to a (also sinistral) transtensional movement stage, associated to volcanism (Macau, Messejana) and thermal doming processes during the Neogene-Pleistocene time interval. This structural model has direct implications to hydrocarbon exploration and exploitation activities at this sector of the Potiguar Basin and its offshore continuation. The structure of the reservoirs at depth (Açu Formation sandstones of the post-rift section) may be controlled (or at least, strongly influenced) by the deformation geometry and kinematics characterized at the surface. In addition, the deformation event recognized in the Barreiras Formation has an age close to the one postulated for the oil maturation and migration in the basin, between the Oligocene to the Miocene. In this way, the described structural cenario represents a valid model to understand the conditions of hydrocarbon transport and acummulation through space openings, trap formation and destruction. This model is potentially applicable to the NW region of the Potiguar Basin and other sectors with a similar structural setting, along the brazilian Equatorial Atlantic Margin

Dobramentos distensionais e a geometria da falha de Baixa Grande, Graben de Umbuzeiro, Bacia Potiguar (RN)

In spite of significant study and exploration of Potiguar Basin, easternmost Brazilian equatorial margin, by the oil industry, its still provides an interesting discussion about its origin and the mechanisms of hydrocarbon trapping. The mapping and interpretation of 3D seismic reflection data of Baixa Grande Fault, SW portion of Umbuzeiro Graben, points as responsible for basin architecture configuration an extensional deformational process. The fault geometry is the most important deformation boundary condition of the rift stata. The development of flat-ramp geometries is responsible for the formation of important extensional anticline folds, many of then hydrocarbon traps in this basin segment. The dominant extensional deformation in the studied area, marked by the development of normal faults developments, associated with structures indicative of obliquity suggests variations on the former regime of Potiguar Basin through a multiphase process. The changes in structural trend permits the generation of local transpression and transtension zones, which results in a complex deformation pattern displayed by the Potiguar basin sin-rift strata. Sismostratigraphic and log analysis show that the Baixa Grande Fault acts as listric growing fault at the sedimentation onset. The generation of a relay ramp between Baixa Grande Fault and Carnaubais Fault was probably responsible for the balance between subsidence and sedimentary influx taxes, inhibiting its growing behaviour. The sismosequences analysis s indicates that the extensional folds generation its diachronic, and then the folds can be both syn- and post-depositional

Estudo comparativo de abordagens de inversão do fator de qualidade Q

Seismic wave dispersion and attenuation studies have become an important tool for lithology and fluid discrimination in hydrocarbon reservoirs. The processes associated to attenuation are complex and are encapsulated in a single quantitative description called quality factor (Q). The present dissertation has the objective of comparing different approaches of Q determination and is divided in two parts. Firstly, we made performance and robustness tests of three different approaches for Q determination in the frequency domain. They are: peak shift, centroid shift and spectral ratio. All these tests were performed in a three-layered model. In the suite of tests performed here, we varied the thickness, Q and inclination of the layers for propagation pulses with central frequency of 30, 40 and 60 Hz. We found that the centroid shift method is produces robust results for the entire suíte of tests. Secondly, we inverted for Q values using the peak and centroid shift methods using an sequential grid search algorithm. In this case, centroid shift method also produced more robust results than the peak shift method, despite being of slower convergence