The effect of flex fuel vehicles in the Brazilian light road transportation

The retaking of the ethanol program in the year 2003 as a fuel for light road transportation in Brazil through the introduction of flex fuel vehicles fleet was a good strategy to overcome the difficulties of the ethanol production sector and did work to increase its market share relative to gasoline. This process, however, may cause a future disequilibrium on the food production and on the refining oil derivates structure. In order to analyze the substitution process resultant of the competition between two opponents fighting for the same market, in this case the gasoline/ethanol substitution process, a method derived from the biomathematics based on the non-linear differential equations (NLDE) system is utilized. A brief description of the method is presented. Numerical adherence of the method to explain several substitution phenomena that occurred in the past is presented in the previous author`s paper, in which the urban gas pipeline system substitution of bottled LPG in the dwelling sector and the substitution of the urban diesel transportation fleet by compressed natural gas (CNG) buses is presented. The proposed method is particularly suitable for prospective analysis and scenarios assessment. (c) 2008 Elsevier Ltd. All rights reserved.

Petroleum contamination impact on macrobenthic communities under the influence of an oil refinery: Integrating chemical and biological multivariate data

Petroleum contamination impact on macrobenthic communities in the northeast portion of Todos os Santos Bay was assessed combining in multivariate analyses, chemical parameters such as aliphatic and polycyclic aromatic hydrocarbon indices and concentration ratios with benthic ecological parameters. Sediment samples were taken in August 2000 with a 0.05 m(2) van Veen grab at 28 sampling locations. The predominance of n-alkanes with more than 24 carbons, together with CPI values close to one, and the fact that most of the stations showed UCM/resolved aliphatic hydrocarbons ratios (UCM:R) higher than two, indicated a high degree of anthropogenic contribution, the presence of terrestrial plant detritus, petroleum products and evidence of chronic oil pollution. The indices used to determine the origin of PAH indicated the occurrence of a petrogenic contribution. A pyrolytic contribution constituted mainly by fossil fuel combustion derived PAH was also observed. The results of the stepwise multiple regression analysis performed with chemical data and benthic ecological descriptors demonstrated that not only total PAH concentrations but also specific concentration ratios or indices such as >= C24:< C24, An/178 and Fl/Fl + Py, are determining the structure of benthic communities within the study area. According to the BIO-ENV results petroleum related variables seemed to have a main influence on macrofauna community structure. The PCA ordination performed with the chemical data resulted in the formation of three groups of stations. The decrease in macrofauna density, number of species and diversity from groups III to I seemed to be related to the occurrence of high aliphatic hydrocarbon and PAH concentrations associated with fine sediments. Our results showed that macrobenthic communities in the northeast portion of Todos os Santos Bay are subjected to the impact of chronic oil pollution as was reflected by the reduction in the number of species and diversity. These results emphasise the importance to combine in multivariate approaches not only total hydrocarbon concentrations but also indices, isomer pair ratios and specific compound concentrations with biological data to improve the assessment of anthropogenic impact on marine ecosystems. (c) 2008 Elsevier Ltd. All rights reserved.

Arsenic and trace metal contents in sediment profiles from the Admiralty Bay, King George Island, Antarctica

Admiralty Bay (Antarctica) hosts three scientific stations (Ferraz, Arctowski and Macchu Picchu), which require the use of fossil fuel as an energy source. Fossil fuels are also considered the main source of pollution in the area, representing important inputs of major pollutants (organic compounds) and trace metals and metalloids of environmental interest. Accordingly, this work presents the results of As, Cd, Cr, Cu, Ni, Pb and Zn in sediment profiles from Admiralty Bay. The sediment results from Ferraz station were slightly higher than the other sampling sites. The highest contents were observed for Cu and Zn (from 44 to 89 mg kg(-1)). Otherwise, by using enrichment factors and geochronology analysis, the most relevant enrichment was observed for As in the samples collected close to the Ferraz station, indicating that increasing As content may be associated with the activities associated with this site. Published by Elsevier Ltd.

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.

Nitrogen mass balance in the Brazilian Amazon: an update

The main purpose of this study is to perform a nitrogen budget survey for the entire Brazilian Amazon region. The main inputs of nitrogen to the region are biological nitrogen fixation occurring in tropical forests (7.7 Tg. yr(-1)), and biological nitrogen fixation in agricultural lands mainly due to the cultivation of a large area with soybean, which is an important nitrogen-fixing crop (1.68 Tg. yr(-1)). The input due to the use of N fertilizers (0.48 Tg. yr(-1)) is still incipient compared to the other two inputs mentioned above. The major output flux is the riverine flux, equal to 2.80 Tg. yr(-1) and export related to foodstuff, mainly the transport of soybean and beef to other parts of the country. The continuous population growth and high rate of urbanization may pose new threats to the nitrogen cycle of the region through the burning of fossil fuel and dumping of raw domestic sewage in rivers and streams of the region.

The sustainability of ethanol production from sugarcane

The rapid expansion of ethanol production from sugarcane in Brazil has raised a number of questions regarding its negative consequences and sustainability. Positive impacts are the elimination of lead compounds from gasoline and the reduction of noxious emissions. There is also the reduction of CO2 emissions, since sugarcane ethanol requires only a small amount of fossil fuels for its production, being thus a renewable fuel. These positive impacts are particularly noticeable in the air quality improvement of metropolitan areas but also in rural areas where mechanized harvesting of green cane is being introduced, eliminating the burning of sugarcane. Negative impacts such as future large-scale ethanol production from sugarcane might lead to the destruction or damage of high-biodiversity areas, deforestation, degradation or damaging of soils through the use of chemicals and soil decarbonization, water resources contamination or depletion, competition between food and fuel production decreasing food security and a worsening of labor conditions on the fields. These questions are discussed here, with the purpose of clarifying the sustainability aspects of ethanol production from sugarcane mainly in Sao Paulo State, where more than 60% of Brazil`s sugarcane plantations are located and are responsible for 62% of ethanol production. (c) 2008 Elsevier Ltd. All rights reserved.

Results from a 15-year study on hydrocarbon concentrations in water and sediment from Admiralty Bay, King George Island, Antarctica

Admiralty Bay on the King George Island hosts the Brazilian, Polish and Peruvian research stations as well as the American and Ecuadorian field stations. Human activities in this region require the use of fossil fuels as an energy source, thereby placing the region at risk of hydrocarbon contamination. Hydrocarbon monitoring was conducted on water and sediment samples from the bay over 15 years. Fluorescence spectroscopy was used for the analysis of total polycyclic aromatic hydrocarbons (PAHs) in seawater samples and gas chromatography with flame ionization and/or mass spectrometric detection was used to analyse individual n-alkanes and PAHs in sediment samples. The results revealed that most sites contaminated by these Compounds are around the Brazilian and Polish research stations due to the intense human activities, mainly during the summer. Moreover, the sediments revealed the presence of hydrocarbons from different sources, suggesting a mixture of the direct input of oil or derivatives and derived from hydrocarbon combustion. A decrease in PAH concentrations occurred following improvement of the sewage treatment facilities at the Brazilian research station, indicating that the contribution from human waste may be significant.

Whole-genome sequencing of the efficient industrial fuel-ethanol fermentative Saccharomyces cerevisiae strain CAT-1

The Saccharomyces cerevisiae strains widely used for industrial fuel-ethanol production have been developed by selection, but their underlying beneficial genetic polymorphisms remain unknown. Here, we report the draft whole-genome sequence of the S. cerevisiae strain CAT-1, which is a dominant fuel-ethanol fermentative strain from the sugarcane industry in Brazil. Our results indicate that strain CAT-1 is a highly heterozygous diploid yeast strain, and the similar to 12-Mb genome of CAT-1, when compared with the reference S228c genome, contains similar to 36,000 homozygous and similar to 30,000 heterozygous single nucleotide polymorphisms, exhibiting an uneven distribution among chromosomes due to large genomic regions of loss of heterozygosity (LOH). In total, 58 % of the 6,652 predicted protein-coding genes of the CAT-1 genome constitute different alleles when compared with the genes present in the reference S288c genome. The CAT-1 genome contains a reduced number of transposable elements, as well as several gene deletions and duplications, especially at telomeric regions, some correlated with several of the physiological characteristics of this industrial fuel-ethanol strain. Phylogenetic analyses revealed that some genes were likely associated with traits important for bioethanol production. Identifying and characterizing the allelic variations controlling traits relevant to industrial fermentation should provide the basis for a forward genetics approach for developing better fermenting yeast strains.

Poly(2,5-bibenzimidazole) Membranes: Physico-Chemical Characterization Focused on Fuel Cell Applications

Membranes of Poly(2,5-benzimidazole) (ABPBI), prepared by polycondensation in polyphosphoric acid, were characterized from the fuel cell application point of view: mechanical properties of the membranes for different acid doping levels, thermal stability, permeability for the different gases/vapors susceptible of use in the cell (hydrogen, oxygen, methanol and ethanol), electro-osmotic water drag coefficient, oxidation stability to hydroxyl radicals, phosphoric acid leaching rate and, finally, in-plane membrane conductivity. ABPBI membranes presented an excellent thermal stability, above 500 degrees C in oxygen, suitable mechanical properties for high phosphoric acid doping levels, a low methanol and ethanol limiting permeation currents, and oxygen permeability compared to Nafion membranes, and a low phosphoric acid leaching rate when exposed to water vapor. On the contrary, hydrogen permeation current was higher than that of Nafion, and the chemical stability was very limited. Membrane conductivity achieved 0.07 S cm(-1) after equilibration with a humid environment. Fuel cell tests showed reasonable good performances, with a maximum power peak of 170 mW cm(-2) for H-2/air at 170 degrees C operating under a humidified hydrogen stream, 39.9 mW cm(-2) for CH3OH/O-2 at 200 degrees C for a methanol/water weight ratio of 1: 2, and 31.5 mW cm(-2) for CH3CH2OH/O-2 at the same conditions than for methanol. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.014207jes] All rights reserved.

An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved. (C) 2012 Elsevier B.V. All rights reserved.

Investigation of a Pt3Sn/C Electro-Catalyst in a Direct Ethanol Fuel Cell Operating at Low Temperatures for Portable Applications

A 20% Pt3Sn/C catalyst was prepared by reduction with formic acid and used in a direct ethanol fuel cell at low temperatures. The electro-catalytic activity of this bimetallic catalyst was compared to that of a commercial 20% Pt/C catalyst. The PtSn catalyst showed better results in the investigated temperature range (30 degrees-70 degrees C). Generally, Sn promotes ethanol oxidation by adsorption of OH species at considerably lower potentials compared to Pt, allowing the occurrence of a bifunctional mechanism. The bimetallic catalyst was physico-chemically characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. The presence of SnO2 in the bulk and surface of the catalyst was observed. It appears that SnO2 can enhance the ethanol electro-oxidation activity at low potentials due to the supply of oxygen-containing species for the oxidative removal of CO and CH3CO species adsorbed on adjacent Pt active sites.

New fossil pulmonate snails from the Paleocene of Itaborai Basin, Brazil (Pulmonata: Cerionidae, Strophocheilidae, Orthalicidae)

The limestones of ltaborai Basin (Middle Paleocene), Rio de Janeiro, Brazil, harbor a rich fossil fauna of pulmonate snails. Here two new pulmonate species are described: Brasilennea guttula sp. nov. (Cerionidae) and Eoborus rotundus sp. nov. (Strophocheilidae). B. guttula is the third species of its genus endemic from Itaborai, characterized mainly by its conspicuous shell shaped like a "water drop", with an acuminated spire. E. rotundus is the second of its genus from ltaborai, characterized mainly by its rounded outline and its relative small size. Moreover, a record of Plagiodontes aff. dental us (WOOD 1828) (Orthalicidae) is presented here for the first time for Itaborai Basin.

PtSnIr/C Anode Electrocatalysts: Promoting Effect in Direct Ethanol Fuel Cells

This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH2, PtO2, SnO2 and IrO2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded.

NEW FOSSIL RECORDS OF PLEISTOCENE MARINE MOLLUSKS IN SOUTHERN BRAZIL

Fossils of the gastropods Diodora patagonica, Zidona dufresnei, Olivancillaria carcellesi, Lamniconus lemniscatus carcellesi and the bivalve Arcinella brasiliana are registered for the first time from the outcrops of Chui Creek, on the coastal plain of Rio Grande do Sul State, southernmost Brazil, together with other taxa previously known elsewhere. The specimens were collected in a shallow Pleistocene marine facies exposed at the base of the banks of the creek, in a fossil concentration possibly formed by storm events. The taxa described here live in shallow environments (with the exception of A. brasiliana and Z. dufresnei) with sandy bottoms (except for D. patagonica, T patagonica, B. odites, C. rhizophorae and A. brasiliana). The presence of L. lemniscatus carcellesi, found living today only in Uruguay and Argentina, indicates a wider distribution for this taxon during the late Pleistocene.

Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

The effect of the relationship between particle size (d), inter-particle distance (x(i)), and metal loading (y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x(i)/d (>5) values, was evaluated. It was found that for y < 30 wt%, the optimum values of both d and x(i)/d can be always obtained. For y >= 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y < 30 wt% is concomitant to a decrease of the effective catalyst surface area due to an increase of d and/or a decrease of x(i)/d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x(i)/d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x(i)/d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.