Organic and mineral matter changes due to oil generation, saturation and expulsion processes based on artificial maturation experiments

Hydrous pyrolysis experiments were conducted on immature organic-rich rock with type-I kerogen to evaluate petroleum generation, saturation and expulsion processes. The experiments were carried out under isothermal conditions at ten different temperatures (280° through 360°C) for nine different time spans between 18 and 144h. Rock samples recovered from the experiments were analyzed for total organic carbon (TOC-weight%), Rock-Eval pyrolysis, vitrinite reflectance (Ro%), spectral fluorescence and visual characterization of organic matter under the microscopy. TOC, S2 and HI tend to decrease with increasing temperature and duration of the experiments as expected. The Ro% values reach up to 1.14% in the most severe experiment (i.e. 360°C/96h). The Ro% is believed to be suppressed due to hydrogen incorporation from bitumen. The bitumen production was observed with the increase of transformation index (TI) and two types of bitumen were differentiated by fluorescence color. The bitumen with yellow fluorescence was mainly composed of saturate and aromatic hydrocarbons that were probably generated earlier than the bitumen with brown fluorescence which is rich in NSO compounds. The greatest bitumen saturation occurs at TI around of 41% to 45%, when the S1 reaches its highest values. The decrease of bitumen saturation and consequent oil expulsion is marked by a reduction in S1 values and fluorescence color. This phenomenon occurs simultaneously with the development of fractures and voids in the mineral matrix which reduces the oil retention capability and facilitates the expulsion process. These observations enhanced the understanding of oil generation and saturation processes, as well as primary migration, expulsion and type of generated bitumen

Organic and mineral matter changes due to oil generation, saturation and expulsion processes based on artificial maturation experiments

Hydrous pyrolysis experiments were conducted on immature organic-rich rock with type-I kerogen to evaluate petroleum generation, saturation and expulsion processes. The experiments were carried out under isothermal conditions at ten different temperatures (280° through 360°C) for nine different time spans between 18 and 144h. Rock samples recovered from the experiments were analyzed for total organic carbon (TOC-weight%), Rock-Eval pyrolysis, vitrinite reflectance (Ro%), spectral fluorescence and visual characterization of organic matter under the microscopy. TOC, S2 and HI tend to decrease with increasing temperature and duration of the experiments as expected. The Ro% values reach up to 1.14% in the most severe experiment (i.e. 360°C/96h). The Ro% is believed to be suppressed due to hydrogen incorporation from bitumen. The bitumen production was observed with the increase of transformation index (TI) and two types of bitumen were differentiated by fluorescence color. The bitumen with yellow fluorescence was mainly composed of saturate and aromatic hydrocarbons that were probably generated earlier than the bitumen with brown fluorescence which is rich in NSO compounds. The greatest bitumen saturation occurs at TI around of 41% to 45%, when the S1 reaches its highest values. The decrease of bitumen saturation and consequent oil expulsion is marked by a reduction in S1 values and fluorescence color. This phenomenon occurs simultaneously with the development of fractures and voids in the mineral matrix which reduces the oil retention capability and facilitates the expulsion process. These observations enhanced the understanding of oil generation and saturation processes, as well as primary migration, expulsion and type of generated bitumen

Periodically nanostructured hydrogels for ethanol vapors sensing

Chemical sensing using optics has been under extensive research all over the world during last decades and many optical chemical sensors are nowadays finding increasing applications in industry, environmental monitoring, medicine, biomedicine and chemical analysis. These optical sensors can be based on various optical principles, such as absorbance, reflectance or transmittance, luminescence and fluorescence, covering different regions of the spectrum (UV, visible, IR, NIR). Optical chemical sensors have several advantages over conventional electricity-based sensors, in terms of selectivity, immunity to electromagnetic interference, higher sensitivity, and they are also relatively inexpensive and minimally invasive. A wide class of optical chemical sensors is based on Photonic Crystals (PCs), i.e. regular arrays of materials with different refractive indices. In particular, they are artificial structures with a periodic dielectric function. In this paper, we present the optical characterization of a polystyrene opal, infiltrated with a stimuli responsive hydrogel specifically formulated to be sensitive to ethanol (EtOH), also in the presence of water. Stimuli-responsive hydrogels are interesting materials for sensing applications due to thefact that they can change their volume significantly in response to small alterations of certain environmental parameters. In fact, hydrogels are increasingly considered as responsive materials to generate active inverse opals fortheir ability to exhibit significant reversible diffraction shifts as a response of a variety of stimuli, such astemperature, pH and ionic strength, single molecules binding and mechanical forces.The stimuliresponsiveness must be accompanied by adequate elasticity and chemical stability forthe inverse opal to be able to survive, without collapsing, to the template removal process byorganic solvents (for polymer colloids) during preparation and to withstand repeated swelling/deswelling cycles when in use, as well as erosion due to prolonged exposure to the swelling medium. While there are interesting studies which report diffraction shifts in a wide region of the visible spectral region when e.g. a crosslinked 2-hydroxyethyl methacrylate (HEMA) hydrogel is exposed either to pure liquid water or to concentrated ethanol/water liquid solutions, at the best of our knowledge there are no equivalent studies which report on the ability of hydrogel inverse opals tospecifically respond to ethanol vapors when already swollen by water.The hydrogel network should be designed so that it can uptake and retain water, when exposed towater vapor-rich atmospheres, and further swell when the atmosphere which is exposed to isprogressively concentrated of ethanol vapors. For this purpose, 2-hydroxyethyl methacrylate (HEMA) was used as main building block for the network, for its known favorable Flory-Hugginsmixing parameter with ethanol; acrylic acid (AA) at two different ratios was also considered as co-monomerfor its affinity toward water and its contribution to hydrogel network mechanicalproperties, due to establishment of further crosslinking through strong secondary interactions;finally poly-ethylene glycol-200dimethacrylate (PEG200DMA) was used as crosslinking agent. The polymerization process combined a \u201ccold\u201d UV-photocrosslinking step and a thermal post-cure.Preliminary swelling studies in the presence of both liquid ethanol and ethanol vapors were carried out on the macrogel analogue as well as a dynamic mechanical thermal analysis to withdraw usefulinformation on the hydrogels mechanical spectra and validate both the formulation and curingprocess. The most promising of the two formulations was selected to infiltrate a polystyrene (PS)opal structure, which was generated onto pre-etched silica through self-assembly of PS nanoparticles. The periodically nanostructured hydrogel film (Fig.1) was then evaluated as active component of an ethanol vapor optical sensor by means of UV-Vis transmission measurements atthe variance of ethanol vapor concentration (Fig.2)

Pearson Correlation Coefficient Applied to Petroleum System Characterization: The Case Study of Potiguar and Reconcavo Basins, Brazil

This study applied the Pearson correlation coefficient and principal component analysis as tools for unsupervised qualitative petroleum system evaluation techniques. A total of 252 oil samples (32 features per sample) representative of two Brazilian sedimentary basins (Recôncavo and Potiguar) were used to classify them according to their respective degrees of maturation and origin. The large initial set of variables comprises data on δ13C composition, saturate, aromatic, polar compound fractions, and the techniques reduced biomarkers to the most important variables, maintaining the global pattern of variance. The results were efficient in discriminating different petroleum systems from lacustrine, marine, and mixing sources, as observed in the studied accumulations from the Lower Cretaceous sediments of the Recôncavo and Potiguar basins. The methodology proved to be very useful to vene better characterize the petroleum systems. This methodology can be applied to analyze a large amount of oil samples, using simple software and spending relatively less time

Position-specific distribution of hydrogen isotopes in natural propane: Effects of thermal cracking, equilibration and biodegradation

Intramolecular isotope distributions, including isotope clumping and position specific fractionation, can provide proxies for the formation temperature and formation and destruction pathways of molecules. In this study, we explore the position-specific hydrogen isotope distribution in propane. We analyzed propane samples from 10 different petroleum systems with high-resolution molecular mass spectrometry. Our results show that the hydrogen isotope fractionation between central and terminal positions of natural propanes ranges from −102‰ to +205‰, a much larger range than that expected for thermodynamic equilibrium at their source and reservoir temperatures (36–63‰). Based on these findings, we propose that the hydrogen isotope structure of catagenic propane is largely controlled by irreversible processes, expressing kinetic isotope effects (KIEs). Kinetic control on hydrogen isotope composition of the products of thermal cracking is supported by a hydrous pyrolysis experiment using the Woodford Shale as substrate, in which we observed isotopic disequilibrium in the early stage of pyrolysis. We make a more general prediction of KIE signatures associated with kerogen cracking by simulating this chemistry in a kinetic Monte Carlo model for different types of kerogens. In contrast, unconventional shale fluids or hot conventional reservoirs contain propane with an isotopic structure close to equilibrium, presumably reflecting internal and/or heterogeneous exchange during high temperature storage (ca. 100–150 °C). In relatively cold (<100 °C) conventional gas accumulations, propane can discharge from its source to a colder reservoir, rapidly enough to preserve disequilibrium signatures even if the source rock thermal maturity is high. These findings imply that long times at elevated temperatures are required to equilibrate the hydrogen isotopic structure of propane in natural gas host rocks and reservoirs. We further defined the kinetics of propane equilibration through hydrogen isotope exchange experiments under hydrous conditions; these experiments show that hydrogen in propane is exchangeable over laboratory timescales when exposed to clay minerals such as kaolinite. This implies rather rapid transfer of propane from sources to cold reservoirs in some of the conventional petroleum systems. Propane is also susceptible to microbial degradation in both oxic and anoxic environments. Biodegradation of propane in the Hadrian and Diana Hoover oil fields (Gulf of Mexico) results in strong increases in central-terminal hydrogen isotope fractionation. This reflects preferential attack on the central position, consistent with previous studies

Geochemical Considerations from the Carboniferous Unconventional Petroleum System of SW Iberia

The Baixo Alentejo Flysch Group (BAFG) is an important stratigraphic unit that covers over half of the South Portuguese Zone (SPZ) depositional area, and it is composed by three main tectono-stratigraphic units: the Mértola, Mira, and Brejeira formations. All of these formations contain significant thicknesses of black shales and have several wide areas with 0.81 wt.%, 0.91 wt.%, and 0.72 wt.% average total organic carbon (TOC) (respectively) and thermal maturation values within gas zones (overmature). This paper is considering new data from classical methods of organic geochemistry characterization, such as TOC, Rock–Eval pyrolysis, and organic petrography, to evaluate the unconventional petroleum system from the SPZ. A total of 53 samples were collected. From the stratigraphical point of view, TOC values seem to have a random distribution. The Rock– Eval parameters point out high thermal maturation compatible with gas window (overmature zone). The samples are dominated by gas-prone extremely hydrogen-depleted type III/IV kerogen, which no longer has the potential to generate and expel hydrocarbons. The petrographic analyses positioned the thermal evolution of these samples into the end of catagenesis to metagenesis (wet to dry gas zone), with values predominantly higher than 2 %Ro (dry gas zone). The presence of thermogenic hydrocarbon fluids characterized by previous papers indicate that the BAFG from SPZ represents a senile unconventional petroleum system, working nowadays basically as a gas reservoir

Hsp60, amateur chaperone in amyloid-beta fibrillogenesis

BACKGROUND: Molecular chaperones are a very special class of proteins that play essential roles in many cellular processes like folding, targeting and transport of proteins. Moreover, recent evidence indicates that chaperones can act as potentially strong suppressor agents in Alzheimer's disease (AD). Indeed, in vitro experiments demonstrate that several chaperones are able to significantly slow down or suppress aggregation of Aβ peptide and in vivo studies reveal that treatment with specific chaperones or their overexpression can ameliorate some distinct pathological signs characterizing AD. METHODS: Here we investigate using a biophysical approach (fluorescence, circular dichroism (CD), transmission electron (TEM) and atomic force (AFM) microscopy, size exclusion chromatography (SEC)) the effect of the human chaperonin Hsp60 on Aβ fibrillogenesis. RESULTS: We found that Hsp60 powerfully inhibits Aβ amyloid aggregation, by closing molecular pathways leading to peptide fibrillogenesis. CONCLUSIONS: We observe that Hsp60 inhibits Aβ aggregation through a more complex mechanism than a simple folding chaperone action. The action is specifically directed toward the early oligomeric species behaving as aggregation seeds for on-pathway amyloid fibrillogenesis. GENERAL SIGNIFICANCE: Understanding the specificity of the molecular interactions of Hsp60 with amyloid Aβ peptide allowed us to emphasize the important aspects to be taken into consideration when considering the recent promising therapeutic strategies for neurodegeneration. Copyright © 2016 Elsevier B.V. All rights reserved

Utilização de uma ferramenta multimídia para identificação de Artrópodes: avaliação de estudantes do Ensino Fundamental

No presente artigo apresentamos um modelo de montagem e produção de um CD-ROM com recursos para identificação de 22 animais, que disponibiliza, para o aluno, uma chave multimídia para identificação de artrópodes. Tratamos de avaliar esta chave multimídia como ferramenta didática em quatro turmas (sétimo, oitavo e nono ano do Ensino Fundamental) de uma escola privada do município de Parnamirim, RN. A avaliação foi dividida em duas etapas: avaliação através de questionário imediatamente após o contato com a chave multimídia, e comparação entre as notas obtidas em exames por escrito de alunos que tiveram e não tiveram contato com a ferramenta didática. Ao todo, 89 alunos participaram das duas etapas da avaliação. Constatamos, de forma geral, uma avaliação positiva e um desempenho significativamente maior dos alunos que interagiram com a ferramenta didática no exame por escrito

Organic and mineral matter changes due to oil generation, saturation and expulsion processes based on artificial maturation experiments

Hydrous pyrolysis experiments were conducted on immature organic-rich rock with type-I kerogen to evaluate petroleum generation, saturation and expulsion processes. The experiments were carried out under isothermal conditions at ten different temperatures (280° through 360°C) for nine different time spans between 18 and 144h. Rock samples recovered from the experiments were analyzed for total organic carbon (TOC¿weight%), Rock-Eval pyrolysis, vitrinite reflectance (Ro%), spectral fluorescence and visual characterization of organic matter under the microscopy. TOC, S2 and HI tend to decrease with increasing temperature and duration of the experiments as expected. The Ro% values reach up to 1.14% in the most severe experiment (i.e. 360°C/96h). The Ro% is believed to be suppressed due to hydrogen incorporation from bitumen. The bitumen production was observed with the increase of transformation index (TI) and two types of bitumen were differentiated by fluorescence color. The bitumen with yellow fluorescence was mainly composed of saturate and aromatic hydrocarbons that were probably generated earlier than the bitumen with brown fluorescence which is rich in NSO compounds. The greatest bitumen saturation occurs at TI around of 41% to 45%, when the S1 reaches its highest values. The decrease of bitumen saturation and consequent oil expulsion is marked by a reduction in S1 values and fluorescence color. This phenomenon occurs simultaneously with the development of fractures and voids in the mineral matrix which reduces the oil retention capability and facilitates the expulsion process. These observations enhanced the understanding of oil generation and saturation processes, as well as primary migration, expulsion and type of generated bitumen

Organic and mineral matter changes due to oil generation, saturation and expulsion processes based on artificial maturation experiments

Hydrous pyrolysis experiments were conducted on immature organic-rich rock with type-I kerogen to evaluate petroleum generation, saturation and expulsion processes. The experiments were carried out under isothermal conditions at ten different temperatures (280° through 360°C) for nine different time spans between 18 and 144h. Rock samples recovered from the experiments were analyzed for total organic carbon (TOC-weight%), Rock-Eval pyrolysis, vitrinite reflectance (Ro%), spectral fluorescence and visual characterization of organic matter under the microscopy. TOC, S2 and HI tend to decrease with increasing temperature and duration of the experiments as expected. The Ro% values reach up to 1.14% in the most severe experiment (i.e. 360°C/96h). The Ro% is believed to be suppressed due to hydrogen incorporation from bitumen. The bitumen production was observed with the increase of transformation index (TI) and two types of bitumen were differentiated by fluorescence color. The bitumen with yellow fluorescence was mainly composed of saturate and aromatic hydrocarbons that were probably generated earlier than the bitumen with brown fluorescence which is rich in NSO compounds. The greatest bitumen saturation occurs at TI around of 41% to 45%, when the S1 reaches its highest values. The decrease of bitumen saturation and consequent oil expulsion is marked by a reduction in S1 values and fluorescence color. This phenomenon occurs simultaneously with the development of fractures and voids in the mineral matrix which reduces the oil retention capability and facilitates the expulsion process. These observations enhanced the understanding of oil generation and saturation processes, as well as primary migration, expulsion and type of generated bitumen