Parameterization of bio-optical models for estimating chlorophyll-a concentration in a tropical eutrophic reservoir

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A Spatial Propensity Score Matching Evaluation of the Social Impacts of Sugarcane Growing on Municipalities in Brazil

The expansion of sugarcane growing in Brazil, spurred particularly by increased demand for ethanol, has triggered the need to evaluate the economic, social, and environmental impacts of this process, both on the country as a whole and on the growing regions. Even though the balance of costs and benefits is positive from an overall standpoint, this may not be so in specific producing regions, due to negative externalities. The objective of this paper is to estimate the effect of growing sugarcane on the human development index (HDI) and its sub-indices in cane producing regions. In the literature on matching effects, this is interpreted as the effect of the treatment on the treated. Location effects are controlled by spatial econometric techniques, giving rise to the spatial propensity score matching model. The authors analyze 424 minimum comparable areas (MCAs) in the treatment group, compared with 907 MCAs in the control group. The results suggest that the presence of sugarcane growing in these areas is not relevant to determine their social conditions, whether for better or worse. It is thus likely that public policies, especially those focused directly on improving education, health, and income generation/distribution, have much more noticeable effects on the municipal HDI.

Life cycle assessment of sugarcane ethanol and palm oil biodiesel joint production

Sugarcane (Saccharum spp.) and palm tree (Elaeis guianeensis) are crops with high biofuel yields, 7.6 m(3) ha (1) y(-)1 of ethanol and 4 Mg ha(-1) y(-1) of oil, respectively. The joint production of these crops enhances the sustainability of ethanol. The objective of this work was comparing a traditional sugarcane ethanol production system (TSES) with a joint production system (JSEB), in which ethanol and biodiesel are produced at the same biorefinery but only ethanol is traded. The comparison is based on ISO 14.040:2006 and ISO 14044:2006, and appropriate indicators. Production systems in Cerrado (typical savannah), Cerradao (woody savannah) and pastureland ecosystems were considered. Energy and carbon balances, and land use change impacts were evaluated. The joint system includes 100% substitution of biodiesel for diesel, which is all consumed in different cropping stages. Data were collected by direct field observation methods, and questionnaires applied to Brazilian facilities. Three sugarcane mills situated in Sao Paulo State and one palm oil refinery located in Para State were surveyed. The information was supplemented by secondary sources. Results demonstrated that fossil fuel use and greenhouse gas emissions decreased, whereas energy efficiency increased when JSEB was compared to TSES. In comparison with TSES, the energy balance of JSEB was 1.7 greater. In addition, JSEB released 23% fewer GHG emissions than TSES. The ecosystem carbon payback time for Cerrado, Cerradao, and Degraded Grassland of JSEB was respectively 4, 7.7 and -7.6 years. These are typical land use types of the Brazilian Cerrado region for which JSEB was conceived. (C) 2012 Elsevier Ltd. All rights reserved.

Turbidimetric Spectroscopy for the Evaluation of Metalworking Fluids Stability

The stability of oil-in-water (O/W) emulsions used as metalworking fluids is a key factor for the economical and environmental balance of the entire metalworking process because used and broken fluids must be recycled or disposed. In this study, the ability of turbidimetric spectroscopy in the ultraviolet and visible light range to detect metalworking fluids destabilization was evaluated. Destabilization was achieved by adding calcium chloride, thus achieving accelerated aging, which leads to coalescence, creaming, and complete emulsion separation. The stability of the metalworking fluids at 5% volumetric concentration in deionized water was monitored using a spectroscopic turbidimeter composed of an optical probe for in-line measurements. Destabilization was also monitored by measuring the vertical profile of backscattered and transmitted light. The results of this offline measurement system were compared with those from the in-line spectroscopic sensor, indicating that the latter can provide local, real-time information on emulsion destabilization, thus enabling control actions.

Acute cocaine treatment increases thimet oligopeptidase in the striatum of rat brain

Many studies indicate that thimet oligopeptidase (EC3.4.24.15; TOP) can be implicated in the metabolism of bioactive peptides, including dynorphin 1-8, alpha-neoendorphin, beta-neoendorphin and GnRH. Furthermore, the higher levels of this peptidase are found in neuroendocrine tissue and testis. In the present study, we have evaluated the effect of acute cocaine administration in male rats on TOP specific activity and mRNA levels in prosencephalic brain areas related with the reward circuitry; ventral striatum, hippocampus, and frontal cortex. No significant differences on TOP specific activity were detected in the hippocampus and frontal cortex of cocaine treated animals compared to control vehicle group. However, a significant increase in activity was observed in the ventral striatum of cocaine treated-rats. The increase occurred in both, TOP specific activity and TOP relative mRNA amount determined by real time RT-PCR. As TOP can be implicated in the processing of many neuropeptides, and previous studies have shown that cocaine also alters the gene expression of proenkephalin and prodynorphin in the striatum, the present findings suggest that TOP changes in the brain could play important role in the balance of neuropeptide level correlated with cocaine effects. (C) 2012 Elsevier Inc. All rights reserved.

Effect of the interaction between food state and the action of estrogen on oxytocinergic system activity

Increased plasma osmolality by food intake evokes augmentation of plasma oxytocin (OT). Ovarian steroids may also influence the balance of body fluids by acting on OT neurones. Our aim was to determine if estrogen influences the activity of OT neurones in paraventricular nucleus (PVN) and supraoptic nucleus (SON) under different osmotic situations. Ovariectomized rats (OVX) were treated with either estradiol (E-2) or vehicle and were divided into three groups: group I was fed ad libitum, group II underwent 48 h of fasting, and group III was refed after 48 h of fasting. On the day of the experiment, blood samples were collected to determine the plasma osmolality and OT. The animals were subsequently perfused, and OT/FOS immunofluorescence analysis was conducted on neurones in the PVN and the SON. When compared to animals which were fasted or fed ad libitum, the plasma osmolality of refed animals was higher, regardless of whether they were treated with vehicle or E-2. We observed neural activation of OT cells in vehicle-or E-2-treated OVX rats refed after 48 h of fasting, but not in animals fed ad libitum or in animals that only underwent 48 h of fasting. Finally, the percentage of neurones that co-expressed OT and FOS was lower in both the PVN and the SON of animals treated with E-2 and refed, when compared to vehicle-treated animals. These results suggest that E-2 may have an inhibitory effect on OT neurones and may modulate the secretion of OT in response to the increase of osmolality induced by refeeding. Journal of Endocrinology (2012) 212, 129-138

NUTRITIONAL BALANCE, ESSENTIAL OIL AND WOOD PRODUCTION FROM Corymbia citriodora Hill & Johnson WITH SEWAGE SLUDGE AND MINERAL FERTILIZER APPLICATIONS

The Corymbia citriodora is one of the most important forest species in Brazil and the reason is the diversity of its use, because it produces good quality wood and the leaves may be used for essential oil production. Although, there are not many studies about species and the handling effect in the nutritional balance. This study aimed to evaluate the biomass production and nutrient balance in the conventional production of essential oil and wood of Corymbia citriodora with sewage sludge application. The experiment design established was the randomized blocks, with four replicates and two treatments: 1 - fertilization with 10 tons ha(-1) (dry mass) of sewage sludge, supplemented with K and B, and 2 - mineral fertilization. It was evaluated the aerial biomass production, the nutrient export of the leaves, the essential oil and wood production at four years old. The trees that received application of sewage sludge produced 20 % more leaves biomass than the trees with mineral fertilization, resulting in larger oil production. Besides, the trees with sewage sludge application produced 14.2 tons ha(-1) yr(-1) of woody biomass that was 27 % higher than the treatment with mineral fertilization. For both treatments the N balance was negative, but treatment with sewage sludge application (-45 kg ha(-1)) was four times lower than the observed on mineral fertilization treatment (-185 kg ha(-1)). It may be concluded in this paper that the application of sewage sludge benefits the production of leaves biomass, essential oil and wood, besides result better nutritional balance of the Corymbia citriodora production system.

Performance and selectivity of PtxSn/C electro-catalysts for ethanol oxidation prepared by reduction with different formic acid concentrations

Carbon supported Pt-Sn catalysts were prepared by reduction of Pt and Sn precursors with formic acid and characterized in terms of structure, morphology and surface properties. The electrocatalytic activity for ethanol oxidation was studied in a direct ethanol fuel cell (DEFC) at 70 degrees C and 90 degrees C. Electrochemical and physico-chemical data indicated that a proper balance of Pt and Sn species in the near surface region was necessary to maximize the reaction rate. The best atomic surface composition, in terms of electrochemical performance, was Pt:Sn 65:35 corresponding to a bulk composition 75:25 namely Pt3Sn1/C. The reaction products of ethanol electro-oxidation in single cell and their distribution as a function of the nature of catalyst were determined. Essentially, acetaldehyde and acetic acid were detected as the main reaction products; whereas, a lower content of CO2 was formed. The selectivity toward acetic acid vs. acetaldehyde increased with the increase of the Sn content and decreased by decreasing the concentration of the reducing agent used in the catalyst preparation. According to the recent literature, these results have been interpreted on the basis of ethanol adsorption characteristics and ligand effects occurring for Sn-rich electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

Hydrodynamic analysis of particle collection efficiency: comparing downflow and upflow filtration

Models of the filtration phenomenon describe the mass balance in bed filtration in terms of particle removal mechanisms, and allow for the determination of global particle removal efficiencies. These models are defined in terms of the geometry and characteristic elements of granule collectors, particles and fluid, and also the composition of the balance of forces that act in the particle collector system. This work analyzes particles collection efficiency comparing downflow and upflow direct filtration, taking into account the contribution of the gravitational factor of the settling removal efficiency in future proposal of initial collection efficiency models for upflow filtration. A qualitative analysis is also made of the proposal for the collection efficiency models for particle removal in direct downflow and upflow filtration using a Computational Fluid Dynamics (CFD) tool. This analysis showed a strong influence of gravitational factor in initial collection efficiency (t = 0) of particles, as well as the reasons of their values to be smaller for upflow filtration in comparison with the downflow filtration.

Generation of the Cape Ghir upwelling filament: a numerical study

[EN] Filaments are narrow, shallow structures of cool water originating from the coast. They are typical features of the four main eastern boundary upwelling systems (EBUS). In spite of their significant biological and chemical roles, through the offshore exportation of nutrient-rich waters, the physical processes that generate them are still not completely understood. This paper is a process-oriented study of filament generation mechanisms. Our goal is twofold: firstly, to obtain a numerical solution able to well represent the characteristics of the filament off Cape Ghir (30°38'N, northwestern Africa) in the Canary EBUS and secondly, to explain its formation by a simple mechanism based on the balance of potential vorticity. The first goal is achieved by the use of the ROMS model (Regional Ocean Modeling System) in embedded domains around Cape Ghir, with a horizontal resolution going up to 1.5 km for the finest domain. The latter gets its initial and boundary conditions from a parent solution and is forced by climatological, high-resolution atmospheric fields. The modeled filaments display spatial, temporal and physical characteristics in agreement with the available in situ and satellite observations. This model solution is used as a reference to compare the results with a set of process-oriented experiments. These experiments allow us to reach the second objective. Their respective solution serves to highlight the contribution of various processes in the filament generation. Since the study is focused on general processes present under climatological forcing conditions, inter-annual forcing is not necessary. The underlying idea for the filament generation is the balance of potential vorticity in the Canary EBUS: the upwelling jet is characterized by negative relative vorticity and flows southward along a narrow band of uniform potential vorticity. In the vicinity of the cape, an injection of relative vorticity induced by the wind breaks the existing vorticity balance. The upwelling jet is prevented from continuing its way southward and has to turn offshore to follow lines of equal potential vorticity. The model results highlight the essential role of wind, associated with the particular topography (coastline and bottom) around the cape. The mechanism presented here is general and thus can be applied to other EBUS.

A new conceptual model of nitrification: A key factor in resolving the metabolic state of the ocean

Máster en Oceanografía

Transcriptional functions of DNA Topoisomerases at a genome-wide scale and a single gene levels

The DNA topology is an important modifier of DNA functions. Torsional stress is generated when right handed DNA is either over- or underwound, producing structural deformations which drive or are driven by processes such as replication, transcription, recombination and repair. DNA topoisomerases are molecular machines that regulate the topological state of the DNA in the cell. These enzymes accomplish this task by either passing one strand of the DNA through a break in the opposing strand or by passing a region of the duplex from the same or a different molecule through a double-stranded cut generated in the DNA. Because of their ability to cut one or two strands of DNA they are also target for some of the most successful anticancer drugs used in standard combination therapies of human cancers. An effective anticancer drug is Camptothecin (CPT) that specifically targets DNA topoisomerase 1 (TOP 1). The research project of the present thesis has been focused on the role of human TOP 1 during transcription and on the transcriptional consequences associated with TOP 1 inhibition by CPT in human cell lines. Previous findings demonstrate that TOP 1 inhibition by CPT perturbs RNA polymerase (RNAP II) density at promoters and along transcribed genes suggesting an involvement of TOP 1 in RNAP II promoter proximal pausing site. Within the transcription cycle, promoter pausing is a fundamental step the importance of which has been well established as a means of coupling elongation to RNA maturation. By measuring nascent RNA transcripts bound to chromatin, we demonstrated that TOP 1 inhibition by CPT can enhance RNAP II escape from promoter proximal pausing site of the human Hypoxia Inducible Factor 1 (HIF-1) and c-MYC genes in a dose dependent manner. This effect is dependent from Cdk7/Cdk9 activities since it can be reversed by the kinases inhibitor DRB. Since CPT affects RNAP II by promoting the hyperphosphorylation of its Rpb1 subunit the findings suggest that TOP 1inhibition by CPT may increase the activity of Cdks which in turn phosphorylate the Rpb1 subunit of RNAP II enhancing its escape from pausing. Interestingly, the transcriptional consequences of CPT induced topological stress are wider than expected. CPT increased co-transcriptional splicing of exon1 and 2 and markedly affected alternative splicing at exon 11. Surprisingly despite its well-established transcription inhibitory activity, CPT can trigger the production of a novel long RNA (5’aHIF-1) antisense to the human HIF-1 mRNA and a known antisense RNA at the 3’ end of the gene, while decreasing mRNA levels. The effects require TOP 1 and are independent from CPT induced DNA damage. Thus, when the supercoiling imbalance promoted by CPT occurs at promoter, it may trigger deregulation of the RNAP II pausing, increased chromatin accessibility and activation/derepression of antisense transcripts in a Cdks dependent manner. A changed balance of antisense transcripts and mRNAs may regulate the activity of HIF-1 and contribute to the control of tumor progression After focusing our TOP 1 investigations at a single gene level, we have extended the study to the whole genome by developing the “Topo-Seq” approach which generates a map of genome-wide distribution of sites of TOP 1 activity sites in human cells. The preliminary data revealed that TOP 1 preferentially localizes at intragenic regions and in particular at 5’ and 3’ ends of genes. Surprisingly upon TOP 1 downregulation, which impairs protein expression by 80%, TOP 1 molecules are mostly localized around 3’ ends of genes, thus suggesting that its activity is essential at these regions and can be compensate at 5’ ends. The developed procedure is a pioneer tool for the detection of TOP 1 cleavage sites across the genome and can open the way to further investigations of the enzyme roles in different nuclear processes.

Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.

Structure and properties of composite polyolefin materials

This thesis is based on three main studies, all dealing with structure-property investigation of semicrystalline polyolefin-based composites. Low density poly(ethylene) (LDPE) and isotactic poly(propylene) (iPP) were chosen as parts of the composites materials and they were investigated either separately (as homoploymers), either in blend systems with the composition LDPE/iPP 80/20 or as filled matrix with layered silicate (montmorillonite). The beneficial influence of adding ethylene-co-propylene polymer of amorphous nature, to low density poly(ethylene)/isotactic poly(propylene) (80/20) blend is demonstrated. This effect is expressed by the major improvement of mechanical properties of ternary blends as examined at a macroscopic size scale by means of tensile measurements. The structure investigation also reveals a clear dependence of the morphology on adding ethylene-copropylene polymer. Both the nature and the content of ethylene-co-propylene polymer affect structure and properties. It is further demonstrated that the extent of improvement in mechanical properties is to be related to the molecular details of the compatibilizer. Combination of high molecular weight and high ethylene content is appropriate for the studied system where the poly(ethylene) plays the role of matrix. A new way to characterize semicrystalline systems by means of Brillouin spectroscopy is presented in this study. By this method based on inelastic light scattering, we were able to measure the high frequency elastic constant (c11) of the two microphases in the case where the spherulites size is exhibit size larger than the size of the probing phonon wavelength. In this considered case, the sample film is inhomogeneous over the relevant length scales and there is an access to the transverse phonon in the crystalline phase yielding the elastic constant c44 as well. Isotactic poly(propylene) is well suited for this type of investigation since its morphology can be tailored through different thermal treatment from the melt. Two distinctly different types of films were used; quenched (low crystallinity) and annealed (high crystallinity). The Brillouin scattering data are discussed with respect to the spherulites size, lamellae thickness, long period, crystallinity degree and well documented by AFM images. The structure and the properties of isotactic poly(propylene) matrix modified by inorganic layered silicate, montmorillonite, are discussed with respect to the clay content. Isotactic poly(propylene)-graft-maleic anhydride was used as compatibilizer. It is clearly demonstrated that the property enhancement is largely due to the ability of layered silicate to exfoliate. The intimate dispersion of the nanometer-thick silicate result from a delicate balance of the content ratio between the isotactic poly(propylene)-graft-maleic anhydride compatibilizer and the inorganic clay.

The shaping of foreign policy: Vietnamese grand strategy after the Cold War

This study examines the case of Vietnam and uses the method of process tracing to explore the sources of foreign policy choice and change. Foreign policy is derived from grand strategy, which refers to the full package of a state’s domestic and foreign policies. I argue that a state’s grand strategy results from the interaction of four factors—its society’s historical experience, social motivation, international power, and political contest among domestic groups. Grand strategies emerge as a response to perceived shifts in the balance of international economic, political, and military power. However, this is not to say that international pressures and incentives are translated into foreign policy. Rather, pressures and incentives are given meaning by worldviews, which reflect a society’s historical experiences of its place in the international system at traumatic junctures of its encounter with the outside world. Strategic changes in foreign policy follow what I call the “strategic algorithm,” which incorporates four major mechanisms—balancing against threat, bandwagoning with power, learning, and survival by transformation. This case study generates hypotheses for a theory of strategic choice, a theory of foreign policy transformation, and a theory of grand strategy emergence.