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

Síntese e caracterização de membranas zeolíticas tipo mfi e aplicação em separação de aromáticos

The synthesis of MFI-type zeolite membranes was carried by the process in situ or hydrothermal crystallization. We studied the homogenization time of the room temperature and gel filtration just before the crystallization step performed out in an oven, thus obtaining a more uniform zeolite film. The powder synthesized zeolite (structure type MFI, Silicalite) was characterized by several complementary techniques such as Xray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis, temperature programmed desorption (TPD), Fourier Transform infrared spectroscopy (FTIR) and textural analysis by nitrogen adsorption (specific surface area). For the purpose of evaluating the quality of the layer supported on the ceramic support, N2 permeation tests were carried starting from room temperature to 600 °C, where values were observed values more appropriate permeation from 200 °C. With the data obtained, it was made into a graph of temperature versus permeation function, the curve of surface diffusion was found. For scanning electron microscopy, we observed the formation of homogeneous crystals and the zeolite film showed no fissures or cracks, indicating that the process of synthesis and subsequent treatments not damaged the zeolite layer on the support. Carried permeation studies were found values ranging from 3.64x10-6 to 3.78x10-6, 4.71x10-6 to 5.02x10-6, to pressures 20 and 25 psi, respectively. And the mixture xylenes/N2 values were between 5.39x10-6 to 5.67x10-6 and 8.13x10-6 to 8.36x10-6, also for pressures of 20 and 25 psi. The values found for the separation factor were 15.22 at 400 °C in the first experiment and 1.64 for the second experiment at a temperature of 150 °C. It is concluded that the Silicalite membrane was successfully synthesized and that it is effective in the separation of binary mixtures of xylenes

Estudo comparativo entre a pirólise do polietileno de baixa densidade, utilizando vermiculita modificada e SBA-15

Catalytic processes are widely present in everyday life. This results in large number of studies seeking materials that may combine the low cost catalytic efficiency. Based on this assumption, the clays have long been used as catalysts, with its huge availability, diversity and possibility of improving their properties from structural changes, primarily responsible for this great use. Among the natural clays, vermiculite due to their characteristic properties (high cation exchange capacity and expansion), is suitable for various applications including as catalysts and catalyst supports. In this work, the acid leaching of clay vermiculite was performed, coming from Santa Luzia-PB, with nitric acid (2, 3 and 4 mol / L) and subsequent calcination of the materials obtained. The materials were named as Vx/400, where x is the acid concentration employed and 400 used in calcination temperature. The effectiveness of changes made was determined by XRD techniques, FT-IR, EDS, TG/DTG, nitrogen physisorption and DTP of n-butylamine. Acid leaching has improved some properties of the clay - specific area and acidity - but the control of the acid concentration used is of vital importance, since the highest concentration caused the partial destruction of vermiculite entailing a decline in their properties. For analysis of the catalytic activity of the modified clay was made a comparative study with the SBA -15 mesoporous materials, synthesized via hydrothermal method, using the pyrolysis of low density polyethylene (LDPE). The results showed that the acid plays a fundamental role in the conversion of the polymer into smaller molecules, the material V3/400 was more selective for the source monomer (ethylene) due to their increased acidity, which promotes more breaks bonds in the polymeric chain, while materials and V0/400 V2/400, lower acidity, showed higher selectivity to light hydrocarbons, the range of fuel (41.96 and 41.23%, respectively), due to less breakage and secondary condensation reactions chains; already V4/400 SBA-15/550 and resulted in lower percentages of light hydrocarbons and the partial destruction of the structure and low acidity, respectively, responsible for the inefficiency of materials

Degradação eletroquímica de benzeno, tolueno e xileno via oxidação eletroquímica utilizando eletrodo Ti/Pt

This work is directed to the treatment of organic compounds present in produced water from oil using electrochemical technology. The water produced is a residue of the petroleum industry are difficult to treat , since this corresponds to 98 % effluent from the effluent generated in the exploration of oil and contains various compounds such as volatile hydrocarbons (benzene, toluene, ethylbenzene and xylene), polycyclic aromatic hydrocarbons (PAHs), phenols, carboxylic acids and inorganic compounds. There are several types of treatment methodologies that residue being studied, among which are the biological processes, advanced oxidation processes (AOPs), such as electrochemical treatments electrooxidation, electrocoagulation, electrocoagulation and eletroredution. The electrochemical method is a method of little environmental impact because instead of chemical reagents uses electron through reactions of oxide-reducing transforms toxic substances into substances with less environmental impact. Thus, this paper aims to study the electrochemical behavior and elimination of the BTX (benzene, toluene and xylene) using electrode of Ti/Pt. For the experiment an electrochemical batch system consists of a continuous source, anode Ti/Pt was used, applying three densities of current (1 mA/cm2, 2,5 mA/cm2 and 5 mA/cm2). The synthetic wastewater was prepared by a solution of benzene, toluene and xylene with a concentration of 5 ppm, to evaluate the electrochemical behavior by cyclic voltammetry and polarization curves, even before assessing the removal of these compounds in solution by electrochemical oxidation. The behavior of each of the compounds was evaluated by the use of electrochemical techniques indicate that each of the compounds when evaluated by cyclic voltammetry showed partial oxidation behavior via adsorption to the surface of the Ti/Pt electrode. The adsorption of each of the present compounds depends on the solution concentration but there is the strong adsorption of xylene. However, the removal was confirmed by UV-Vis, and analysis of total organic carbon (TOC), which showed a percentage of partial oxidation (19,8 % - 99,1 % TOC removed), confirming the electrochemical behavior already observed in voltammetry and cyclic polarization curves

Síntese e caracterização de zeólita beta hierarquizada e materiais híbridos micro-mesoporosos aplicados no craqueamento de PEAD

A catalyst of great interest to the scientific community tries to unite the structure of ordered pore diameter from mesoporous materials with the properties of stability and acid activity to microporous zeolites. Thus a large number of materials was developed in the past decades, which although being reported as zeolites intrinsically they fail to comply with some relevant characteristics to zeolites, and recently were named zeolitic materials of high accessibility. Among the various synthesis strategies employed, the present research approaches the synthesis methods of crystallization of silanized protozeolitic units and the method of protozeolitic units molded around surfactant micelles, in order for get materials defined as hierarchical zeolites and micro-mesoporous hybrid materials, respectively. As goal BEA/MCM-41 hybrid catalysts with bimodal pore structure formed by nuclei of zeolite Beta and cationic surfactant cetyltrimethylammonium were developed. As also was successfully synthesized the hierarchical Beta zeolite having a secondary porosity, in addition to the typical and uniform zeolite micropores. Both catalysts were applied in reactions of catalytic cracking of high density polyethylene (HDPE), to evaluate its properties in catalytic activity, aiming at the recycling of waste plastics to obtain high value-added raw materials and fuels. The BEA/MCM-41 hybrid materials with 0 days of pre-crystallization did not show enough properties for use in catalytic cracking reactions, but they showed superior catalytic properties compared to those ordered mesoporous materials of Al-MCM-41 type. The structure of Beta zeolite with hierarchical porosity leads the accessibility of HDPE bulky molecules to active centers, due to high external area. And provides higher conversion to hydrocarbons in the gasoline range, especially olefins which have great interest in the petrochemical industry

Revitalização do Rio Golandim (RN/Brasil) após décadas de contaminação por efluentes industriais e domésticos: este rio está recuperado?

Environmental pollution causes the loss of the quality of aquatic resources and also affects the health of human beings. The Golandim River is located in São Gonçalo do Amarante (RN Brazil) and had its water recovered seven years ago by measurements of parameters of the water s quality analyses physicochemistry, microbiological and heavy metals. However, it is not well established if this river is truly recovered, so this study provides a wide knowledge about the quality of these waters. Therefore, this investigation was accomplished by assays of ecotoxicology utilizing Ceriodaphnia dubia and of genotoxicity of the river s water using a biomarker Tradescantia Pallida (Trad-MCN). In set, it carried through a study of environmental perception through questionnaires that approached questions related to the profile of the interviewed one, knowledge on the environment and of the river Golandim with the community that lives in the neighborhoods of the river to diagnosis as they perceive the environment where live and its problems. The assays of the water had been carried out by collecting samples in three different sites of the Golandim River. They were collected between the periods of December 2010 (dry season in the northeast of Brazil) and July 2011 (rainy season in the northeast of). The analysis of the data allowed observing that the majority of the inhabitants are adult and presents a global vision of what it is part of the environment, the majority mentions the pollution of the river as one of the problems of the city, considering it serious. The ecotoxicology assay showed that there was not acute toxicity in all three samples collected. Meanwhile, all these three samples demonstrated significant chronic toxicity. The results from the Trad-MCN assay presented an increase in the frequency of micronucleus in one of the sites analyzed (S3) (p<0.01), in both seasons collected. On the other hand, the sites S1 and S2 did not presented a significant increase of micronucleus using this bioassay. The analyses of chemicals detected an increase in the levels of some metals, in different seasons and samples, which can be associates with some compounds found in urban and industrial areas. On the other hand, the physicochemistries parameters demonstrated that the Golandim River is recouped, when compared with the values presented at the CONAMA s legislation. However, these results indicate the presence of compounds capable of inducing chromosomal mutation in plants. On the other hand, the parameters physicistchemistries demonstrate that the river Golandim is if recouping, since when compares the values observed with the legislation of the CONAMA. All these results point to the fact that the Trad-MCN assay was sensitive and efficient biomarker for chromosomal instability and the C. dubia ecotoxicology assay was as though an efficient biomarker of toxicity of water s quality. The results from Trad-MCN associated with the ecotoxicology demonstrates that these analyses are important for environmental monitoring, once the first bioassay described above indicates alterations at the standards of cells and the other one indicates alterations at the standards of organisms. This study alerts for the necessity to carry out biological assays for the analyses of the water s quality

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

Estudo do potencial da técnica de nanossísmica para o monitoramento de hidrofraturamento em reservatórios de hidrocarbonetos

Hydraulic fracturing is an operation in which pressurised fluid is injected in the geological formation surrounding the producing well to create new permeable paths for hydrocarbons. The injection of such fluids in the reservoir induces seismic events. The measurement of this reservoir stimulation can be made by location these induced microseismic events. However, microseismic monitoring is an expensive operation because the acquisition and data interpretation system using in this monitoring rely on high signal-to-noise ratios (SNR). In general, the sensors are deployed in a monitoring well near the treated well and can make a microseismic monitoring quite an expensive operation. In this dissertation we propose the application of a new method for recording and location of microseismic events called nanoseismic monitoring (Joswig, 2006). In this new method, a continuous recording is performed and the interpreter can separate events from noise using sonograms. This new method also allows the location of seismic sources even when P and S phases onsets are not clear like in situations of 0 dB SNR. The clear technical advantage of this new method is also economically advantageous since the sensors can potentially be installed on the surface rather than in observation well. In this dissertation field tests with controlled sources were made. In the first test small explosives using fire works at 28 m (slant distances) were detected yealding magnitudes between -2.4 ≤ ML ≤ -1.6.. In a second test, we monitored perforation shots in a producing oil field. In this second test, one perforation shot was located with slant distances of 861 m and magnitude 2.4 ML. Data from the tests allow us to say that the method has potential to be used in the oil industry to monitor hydrofracture

Os efeitos das queimadas na Amazônia em nível celular e molecular

The Amazon holds over half of the planet's remaining tropical forests and comprises the largest biodiversity in the world, accounting for approximately 60 % of the Brazilian territory. However, deforestation fires in the region causes serious problems to exposed human. The aim of this study was to evaluate the chemical compounds as well as the cellular and molecular effects after exposure to organic material extracted from particulate matter less than 10 µm (PM10) in the Amazon region. As for the chemical composition, n-alkanes analysis showed a prevalence of anthropogenic influence during the fires in the region. In addition, there was a predominance of monosaccharides from biomass burning markers. Also, the Polycyclic Aromatic Hydrocarbons (PAH) and their derivatives have also been identified in samples collected in the Amazon. By using the PAH concentrations was possible to calculate the BaP-equivalent and it was found that the dibenz(a) anthracene contributes with 83% to potential carcinogenic risk. As for the potential mutagenic risk, the benzo (a) pyrene is the HPA that has a major contribution in this analysis. It may be noted that the retene was the most abundant PAH. This compound was genotoxic and cause death by necrosis in the human lung cells. In biological tests, the data showed that organic PM10 is capable of causing genetic damage in both plant cells and in human lung cells. This damage cause an arrest in the G1 phase of the cell cycle exposed, increasing the expression of p53 and p21. Additionally, the PM10 caused cell death by apoptosis, increasing the foci of histone - H2AX. Given these results, it is important to emphasize the reduction and better control of biomass burning in the Amazon region thus improving the quality of health of the population being exposed. As clearly stated recently by the World Health Organization, the reduction of air pollution could save millions of lives annually.

Aplicação da destilação simulada por cromatografia gasosa e da termogravimetria para a avaliação da influência da redução do teor de enxofre sobre as propriedades físico-químicas do óleo diesel

One of the main problems related to the use of diesel as fuel is the presence of sulfur (S) which causes environmental pollution and corrosion of engines. In order to minimize the consequences of the release of this pollutant, Brazilian law established maximum sulfur content that diesel fuel may have. To meet these requirements, diesel with a maximum sulfur concentration equal to 10 mg/kg (S10) has been widely marketed in the country. However, the reduction of sulfur can lead to changes in the physicochemical properties of the fuel, which are essential for the performance of road vehicles. This work aims to identify the main changes in the physicochemical properties of diesel fuel and how they are related to reduction of sulfur content. Samples of diesel types S10, S500 and S1800 were tested according with the methods of the American Society for Testing and Materials (ASTM). The fuels were also characterized by thermogravimetric analysis (TG) and subjected to physical distillation (ASTM D86) and simulated distillation gas chromatography (ASTM D2887). The results showed that the reduction of sulfur turned the fuel lighter and fluid, allowing a greater applicability to low temperature environments and safer for transportation and storage. Through the simulated distillation data was observed that decreasing sulfur content resulted in higher initial boiling point temperatures and the decreasing of the boiling temperature of the medium and heavy fractions. Thermogravimetric analysis showed a loss event mass attributed to volatilization or distillation of light and medium hydrocarbons. Based on these data, the kinetic behavior of the samples was investigated and it was observed that the activation energies (Ea) did not show significant changes throughout conversion. Considering the average of these energies, the S1800 had the highest Ea during the conversion and the S10 the lowest values

Novos adsorventes para aplicação na remoção de enxofre de combustíveis

Currently the market requires increasingly pure oil derivatives and, with that, comes the need for new methods for obtaining those products that are more efficient and economically viable. Considering the removal of sulfur from diesel, most refineries uses catalytic hydrogenation process, the hydrodesulfurization. These processes needs high energy content and high cost of production and has low efficiency in removing sulfur at low concentrations (below 500 ppm). The adsorption presents itself as an efficient and economically viable alternative in relation to the techniques currently used. With that, the main purpose of this work is to develop and optimize the obtaining of new adsorbents based on diatomite, modified with two non ionic surfactants microemulsions, adding efficiency to the material, to its application on removal of sulfur present in commercial diesel. Analyses were undertaken of scanning electron microscopy (SEM), x-ray diffraction (XRD), x-ray fluorescence (XRF), thermogravimetry (TG) and N2 adsorption (BET) for characterization of new materials obtained. The variables used for diatomite modification were: microemulsion points for each surfactant (RNX 95 and UNTL 90), microemulsion aqueous phase through the use or non-use of salts (CaCl2 and BaCl2), the contact time during the modification and the contact form. The study of adsorption capacity of materials obtained was performed using a statistical modeling to evaluate the influence of salt concentration in the aqueous phase (20 ppm to 1500 ppm), finite bath temperature (25 to 60° C) and the concentration of sulphur in diesel. It was observed that the temperature and the concentration of sulphur (300 to 1100 ppm) were the most significant parameters, in which increasing their values increase the ability of modified clay to adsorb the sulphur in diesel fuel. Adsorption capacity increased from 0.43 to mg/g 1.34 mg/g with microemulsion point optimization and with the addition of salts.

Avaliação do potencial das fibras de Ceiba Pentandra (Kapok) e Calotropis Procera como adsorventes de petróleo

On the basis of human evolution and the population increase was necessary, the emergence of new sources of energy, the development of new products and technologies. One such product, object of the industry revolution and of great importance to the development of humanity is the oil, a substance composed primarily of hydrocarbons which give rise to several other products as fuels, lubricants, polymers, solvents, cooking gas, asphalt for roads, fertilizers, medicines, paints, among other. However, mishandling this product may cause leaks and spills that generate huge damages to the environment and the economy. Soon, with the purpose of contributing to decrease is problematic, in this master's work was carried out an intensive search of the possible potential of the fibers of Ceiba pentandra (L.) "Kapok" and Calotropis Procera as bioadsorbents of petroleum in water. The choice of these fibers is due to surface properties such as oleophylics and hydrophobic, their buoyancy and yet, being biodegradable natural polymers derived from the Brazilian Northeast. This research was used experimental planning with response surface methodology (RSM) with the software Design Expert. The results were statistically efficient, obtaining a R2= 0.9995 for Calotropis Procera and a R2= 0.9993 for Kapok. And that, both fibers showed adsorption efficiency, removing more than 80% petroleum in water static and dynamic state.

A regulação da exploração e produção de hidrocarbonetos não convencionais no Brasil

The global energy crisis triggered the possibility of unconventional hydrocarbons exploration and production, culminating in the US energy revolution as well as making other countries interested in the development of these natural resources. The justification for this research comes from Brazil's interest in the use of hydraulic fracturing techniques in unconventional resources since the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP) organized the 12th acquisition process and published the Resolution no. 21 of April 10, 2014. The conflict between economic viability and the social and environmental damage from exploration and production of unconventional hydrocarbons in Brazil resulted in the search for a legal solution that would consider the economic, social and environmental interests. The main purpose here is to analyze the regulation of unconventional oil exploration and production in Brazil in order to show lack of regulatory instruments so far. The specific objectives are to investigate how the lack of effective regulation may ultimately prevent the development itself, analyze the importance of systematization of a new regulatory tool for ensuring legal security and energy, identify the key negative environmental and social impacts, and suggest possibilities approaches within the new regulatory framework. The research methodology stands out the hypothetico-deductive model as approach, and the comparative model as procedural method. Moreover, the research techniques used here are performance of a theoretical and descriptive questioning over literature search, analysis of Brazilian standardization and case laws, and a brief comparative study, in order to provide suggested approaches for a new regulatory framework.

A regulação da exploração e produção de hidrocarbonetos não convencionais no Brasil

The global energy crisis triggered the possibility of unconventional hydrocarbons exploration and production, culminating in the US energy revolution as well as making other countries interested in the development of these natural resources. The justification for this research comes from Brazil's interest in the use of hydraulic fracturing techniques in unconventional resources since the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP) organized the 12th acquisition process and published the Resolution no. 21 of April 10, 2014. The conflict between economic viability and the social and environmental damage from exploration and production of unconventional hydrocarbons in Brazil resulted in the search for a legal solution that would consider the economic, social and environmental interests. The main purpose here is to analyze the regulation of unconventional oil exploration and production in Brazil in order to show lack of regulatory instruments so far. The specific objectives are to investigate how the lack of effective regulation may ultimately prevent the development itself, analyze the importance of systematization of a new regulatory tool for ensuring legal security and energy, identify the key negative environmental and social impacts, and suggest possibilities approaches within the new regulatory framework. The research methodology stands out the hypothetico-deductive model as approach, and the comparative model as procedural method. Moreover, the research techniques used here are performance of a theoretical and descriptive questioning over literature search, analysis of Brazilian standardization and case laws, and a brief comparative study, in order to provide suggested approaches for a new regulatory framework.

Caracterização do material particulado e avaliação do risco ocupacional e mecanismos moleculares associados à queima artesanal da castanha de caju

Brazil is among the largest cashew nut producers of the world. However, the roasting process is still carried out artisanally, especially in the Brazilian semiarid region. In face of this occupational problem, the aim of this study was to perform a physical-chemical characterization of the particulate matter (PM) emitted by the roasting of cashew nuts, as well as to determine the occupational risk and molecular mechanisms associated. The most evident PM characteristics were the prevalence of fine particles, typical biomass burning morphologies such as tar ball and the presence of the elements K, Cl, S, Ca and Fe. In addition, atmospheric modeling analyses suggest that these particles can reach neighboring regions of the emission source. Polycyclic aromatic hydrocarbons (PAHs) with carcinogenic potential, such as benzo[a]pyrene, dibenz[a,h]anthracene, benzo[a]anthracene, benzo[b]fluoranthene, chrysene, benzo[k]fluoranthene, indeno[1,2,3-c,d]pyrene and benzo[j]fluoranthene were the most abundant PAHs found in the two air monitoring campaigns. Among the identified oxy-PAH the benzanthrone (7H-benz[d,e]anthracen-7-one) had the highest concentration and the evaluation of lifetime cancer risk showed an increase of 12 to 37 cases of cancer for every 10,000 exposed people. Chemical analysis of roasted cashew nuts identified the PAHs: phenanthrene, benzo[g,h,i]perylene, pyrene and benzo[a]pyrene, besides the 3-pentadecilfenol allergen (urushiol analogue) as prevalent. Occupational exposure to PAHs was confirmed by the increase of urinary 1-hydroxypyrene levels and genotoxic effects were evidenced by the increase on micronuclei and nuclear bud frequency in exfoliated buccal mucosa cells among the exposed workers. Other biomarkers of effects such as karyorrhexis, pyknotic, karyolytic, condensed chromatin and binucleated cells also have their frequencies increased when compared to an unexposed control group. The investigation of the molecular mechanisms associated with the PM organic extract showed cytotoxicity in human lung cell lines (A549) at concentrations ≥ 4 nM BaPeq. Using non-cytotoxic doses the extract was able to activate proteins involved in the DNA damage response pathway (Chk1 and p53). Moreover, the specific contribution of the four most representative PAHs in the cashew nut roasting sample showed that benzo[a]pyrene was the most efficient to activate Chk1 and p53. Finally, the organic extract was able to increase persistently the mRNA expression involved in the PAHs metabolism (CYP1A1 and CYP1B1), inflammatory response (IL-8 and TNF-α) and cell cycle arrest (CDKN1A) for DNA repair (DDB2). The high PM concentrations and its biological effects associated warn of the serious harmful effects of artisanal cashew nut roasting and urgent actions should be taken to the sustainable development of this activity.