Ozone formation potentials of volatile organic compounds and ozone sensitivity to their emission in the megacity of Sao Paulo, Brazil

In the present study, a three-dimensional Eulerian photochemical model was employed to estimate the impact that organic compounds have on tropospheric ozone formation in the Metropolitan Area of Sao Paulo (MASP). In the year 2000, base case simulations were conducted in two periods: August 22-24 and March 13-15. Based on the pollutant concentrations calculated by the model, the correlation coefficient relative to observations for ozone ranged from 0.91 to 0.93 in both periods. In the simulations employed to evaluate the ozone potential of individual VOCs, as well as the sensitivity of ozone to the VOC/NO(x) emission ratio, the variation in anthropogenic emissions was estimated at 15% (according to tests performed previously variations of 15% were stable). Although there were significant differences between the two periods, ozone concentrations were found to be much more sensitive to VOCs than to NO(x) in both periods and throughout the study domain. In addition, considering their individual rates of emission from vehicles, the species/classes that were most important for ozone formation were as follows: aromatics with a kOH>2x 10(4) ppm(-1) min(-1); olefins with a kOH 7 x 10(4) ppm(-1) min(-1); olefins with a kOH 7 x 10(4) ppm(-1) min(-1); ethene; and formaldehyde, which are the principal species related to the production, transport, storage and combustion of fossil fuels.

Bioethanol from lignocelluloses: Status and perspectives in Brazil

The National Alcohol Program - ProAlcool, created by the government of Brazil in 1975 resulted less dependency on fossil fuels. The addition of 25% ethanol to gasoline reduced the import of 550 million barrels oil and also reduced the emission CO(2) by 110 million tons. Today, 44% of the Brazilian energy matrix is renewable and 13.5% is derived from sugarcane. Brazil has a land area of 851 million hectares, of which 54% are preserved, including the Amazon forest (350 million hectares). From the land available for agriculture (340 million hectares), only 0.9% is occupied by sugarcane as energy crop, showing a great expansion potential. Studies have shown that in the coming years, ethanol yield per hectare of sugarcane, which presently is 6000 L/ha, could reach 10,000 L/ha, if 50% of the produced bagasse would be converted to ethanol. This article describes the efforts of different Brazilian institutions and research groups on second generation bioethanol production, especially from sugarcane bagasse. (C) 2009 Elsevier Ltd. All rights reserved.

The decline of the world`s energy intensity

Energy intensity of the total primary energy supply (TPES), total final energy consumption (TFC) and LOSSES in the conversion from TPES to TFC were analyzed for the World, OECD and Rest of the World (ROW) countries. LOSSES increased significantly for all groups of countries due to the increase of electricity production from coal in the period studied (1971-2008). Electricity share final consumption almost doubled, increasing from 8.8% to 17.2% in the period studied. However the energy intensity of LOSSES remained practically constant, which reflects the fact that the efficiency of electricity generation from coal (the main source of electricity) remained practically constant in that period. Despite the attractiveness of end-use devices running on electricity such as computers, which is typical of modern societies, the CO(2) emissions are bound to increase unless coal is replaced by less carbon emitting sources such as natural gas, renewables and nuclear energy. (C) 2011 Elsevier Ltd. All rights reserved.

The ""decarbonization"" of the world`s energy matrix

Decarbonizing the world`s energy matrix is the strategy being implemented by most countries to reduce CO(2) emissions and thus contribute to achieve the ultimate objectives of the Climate Convention. The evolution of the carbon intensity (I(c)=CO(2)/GDP) in the period 1990-2007 was encouraging but not sufficient to reduce the growth of carbon emission. As a result of COP-15 in Copenhagen these countries (and regions) made pledges that could lead to more reduction: for the United States a 17% reduction in CO(2) emissions by 2020 below the level of 2005: for the European Union a 20% reduction in CO(2) emissions by 2020 below the 1990 level: for China a 40-45% reduction in the carbon intensity and for India a 20-25% reduction in carbon intensity by 2020. We analyzed the consequences of such pledges and concluded that the expected yearly rate of decrease of the carbon intensity follows basically the ""business as usual"" trend in the period 1990-2007 and will, in all likelihood, be insufficient to reduce carbon emissions up to 2020. (C) 2010 Elsevier Ltd. All rights reserved.

The potential for first-generation ethanol production from sugarcane

Ethanol production from sugarcane, mainly in Brazil, on the basis of first-generation technology (22.5 billion liters, in 2007/2008 season, in 3.4 million hectares) replaces 1% of the gasoline used in the world today and is highly competitive in economic terms with ethanol produced from other crops in the USA and Europe. In this paper we discuss the potential for sugarcane ethanol expansion from two angles: (1) productivity gains which would allow greater production in the same area and (2) geographical expansion to larger areas. The potential of first-generation technology for the production of ethanol from sugarcane is far from being exhausted. There are gains in productivity of approximately a factor of two from genetically modified varieties and a geographical expansion by a factor of ten of the present level of production in many sugar-producing countries. The replacement of 10% of the gasoline used in the world by ethanol from sugarcane seems possible before second-generation technology reaches technological maturity and possibly economic competitiveness. (C) 2009 Society of Chemical Industry and John Wiley & Sons, Ltd

Historical carbon budget of the brazilian ethanol program

This work models the carbon neutralization capacity of Brazil`s ethanol program since 1975. In addition to biofuel, we also assessed the mitigation potential of other energy products, such as, bioelectricity, and CO(2) emissions captured during fermentation of sugar cane`s juice. Finally, we projected the neutralization capacity of sugar cane`s bio-energy system over the next 32 years. The balance between several carbon stocks and flows was considered in the model, including the effects of land-use change. Our results show that the neutralization of the carbon released due to land-use change was attained only in 1992, and the maximum mitigation potential of the sugar cane sector was 128 tonnes Of CO(2) per ha in 2006. An ideal reconstitution of the deployment of the sugar cane sector, including the full exploitation of bio-electricity`s potential, plus the capture Of CO(2) released during fermentation, shows that the neutralization of land-use change emissions would have been achieved in 1988, and its mitigation potential would have been 390 tCO(2)/ha. Finally, forecasts of the sector up to 2039 shows that the mitigation potential in 2039 corresponds to 836 tCO(2)/ha, which corresponds to 5.51 kg Of CO(2) per liter of ethanol produced, or 55% above the negative emission level. (C) 2009 Elsevier Ltd. All rights reserved.

Are biofuels a feasible option?

Recently a number of objections have been raised against the use of ethanol produced from agricultural products such as maize, sugarcane, wheat or sugar beets as a replacement for gasoline, despite some of their advantages such as being cleaner and to some extent renewable. We address these objections in this paper. Topics discussed include the ""corn connection"" (which was theorized to be a cause of deforestation in the Amazonia), the rise of food prices due to ethanol production and the real possibilities of ethanol in reducing greenhouse gas emissions. It has been shown that such concerns are grossly exaggerated and that ethanol from sugarcane, as produced in Brazil, is the preferred option for the production of fuel not only in terms of cost but also as a favourable energy balance. Finally, the possibility of expanding ethanol production to other sugar-producing countries is also discussed. (C) 2008 Elsevier Ltd. All rights reserved.

Insights into the dynamics and sources of atmospheric lead and particulate matter in Sao Paulo, Brazil, from high temporal resolution sampling

We present the first results of a study investigating the processes that control concentrations and sources of Pb and particulate matter in the atmosphere of Sao Paulo City Brazil Aerosols were collected with high temporal resolution (3 hours) during a four-day period in July 2005 The highest Pb concentrations measured coincided with large fireworks during celebration events and associated to high traffic occurrence Our high-resolution data highlights the impact that a singular transient event can have on air quality even in a megacity Under meteorological conditions non-conducive to pollutant dispersion Pb and particulate matter concentrations accumulated during the night leading to the highest concentrations in aerosols collected early in the morning of the following day The stable isotopes of Pb suggest that emissions from traffic remain an Important source of Pb in Sao Paulo City due to the large traffic fleet despite low Pb concentrations in fuels (C) 2010 Elsevier BV All rights reserved

CARBON CREDITS AND ENERGY EFFICIENCY

International carbon credit markets are based in differences between developing and developed countries greenhouse gases emissions mitigation costs and technological limits faced by developed countries. Potential of energy efficiency measures to reduce fossil fuel usage in Brazilian industrial segments is assessed, and analysis of such potentials singles out those segments and regions more apt to generate carbon credits through Clean Development Mechanism (CDM) projects. Though there are currently few Brazilian CDM projects, their number may be significantly increased, which is a positive outcome. For this purpose, it is crucial that energy conservation programs estimate how CDM may improve their economic competitiveness.

Composition and antifungal activity against Candida albicans, Candida parapsilosis, Candida krusei and Cryptococcus neoformans of essential oils from leaves of Piper and Peperomia species

This study was addressed to investigate the composition and antifungal activity of essential oils from leaves of Piperaceae species (Piper aduncum, Piper amalago, Piper cernuum, Piper diospyrifolium, Piper crassinervium, Piper gaudichaudianum, Piper solmsianum, Piper regnellii, Piper tuberculatum, Piper umbelata and Peperomia obtusifolia) against Candida albicans, C. parapsilosis, C. krusei and Cryptococcus neoformans. The essential oils from P. aduncum, P. gaudichaudianum and P. solmsianum showed the highest antifungal activity against Cryptococcus neoformans with the MIC of 62.5, 62.5 and 3.9 mg.mL-1, respectively. The oil from P. gaudichaudianum showed activity against C. krusei with MIC of 31.25 mg.mL-1.

Improved Prediction of Hydrocarbon Flash Points from Boiling Point Data

Flash points (T(FP)) of hydrocarbons are calculated from their flash point numbers, N(FP), with the relationship T(FP) (K) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901 In turn, the N(FP) values can be predicted from experimental boiling point numbers (Y(BP)) and molecular structure with the equation N(FP) = 0.987 Y(BP) + 0.176D + 0.687T + 0.712B - 0.176 where D is the number of olefinic double bonds in the structure, T is the number of triple bonds, and B is the number of aromatic rings. For a data set consisting of 300 diverse hydrocarbons, the average absolute deviation between the literature and predicted flash points was 2.9 K.

Geranylation of benzoic acid derivatives by enzymatic extracts from Piper crassinervium (Piperaceae)

The ability to carry out geranylations on aromatic substrates using enzymatic extracts from the leaves of Piper crassinervium (Piperaceae) was evaluated. A literature analysis pointed out its importance as a source of prenylated bioactive molecules. The screening performed on aromatic acceptors (benzoic acids, phenols and phenylpropanoids) including geranyl diphosphate as prenyl donor, showed the biotransformation of the 3,4-dihydroxybenzoic acid by the crude extract, and the p-hydroxybenzoic acid by both the microsomal fraction and the crude extract, after treating leaves with glucose. The analysis of the products allowed the identification of C- and O-geranylated derivatives, and the protease (subtilisin and pepsin) inhibition performed on the O-geranylated compounds showed weak inhibition. Electrophoretic profiles indicated the presence of bands/spots among 56-58 kDa and pI 6-7, which are compatible with prenyltransferases. These findings show that P. crassinervium could be considered as a source of extracts with geranyltransferase activity to perform biotransformations on aromatic substrates. (C) 2010 Elsevier Ltd. All rights reserved.

Vanadium oxide-porphyrin nanocomposites as gas sensor interfaces for probing low water content in ethanol

Vanadium pentoxide xerogels (VXG) incorporating meso(3- and 4-pyridyl)porphyrin cobalt(III) species coordinated to four [Ru(bipy)(2)Cl](+) complexes were employed as gas sensing materials capable of detecting small amounts of water in commercial ethanol and fuel supplies. According to their X-ray diffraction data, the original VXG lamellar framework was maintained in the nanocomposite material, but the interlamellar distance increased from 11.7 to 15.2 angstrom, reflecting the intercalation of the porphyrin species into the vanadium pentoxide matrix. The films generated by direct deposition of the nanocomposite aqueous suspensions exhibited good electrical and electrochemical performance for application in resistive sensors. The analysis of water in ethanol and fuels was carried out successfully using an especially designed electric setup incorporating a laminar gas flow chamber and interdigitated gold electrodes coated with the nanocomposites. (C) 2010 Elsevier B.V. All rights reserved.

Calculating Flash Point Numbers from Molecular Structure: An Improved Method for Predicting the Flash Points of Acyclic Alkanes

We report a novel method for calculating flash points of acyclic alkanes from flash point numbers, N(FP), which can be calculated from experimental or calculated boiling point numbers (Y(BP)) with the equation N(FP) = 1.020Y(BP) - 1.083 Flash points (FP) are then determined from the relationship FP(K) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901 For it data set of 102 linear and branched alkanes, the correlation of literature and predicted flash points has R(2) = 0.985 and an average absolute deviation of 3.38 K. N(FP) values can also be estimated directly from molecular structure to produce an even closer correspondence of literature and predicted FP values. Furthermore, N(FP) values provide a new method to evaluate the reliability of literature flash point data.

Development of a heavy metal sorption system through the P=S functionalization of coconut (Cocos nucifera) fibers

Lignocellulosic residues are interesting materials for the production of heavy metal adsorbents for aquatic systems. Whole fibers taken from coconut (Cocos nucifera) husks were functionalized with the thiophosphoryl (P=S) group by means of the direct reaction with CI(3)P=S, (CH(3)O)(2)CIP=S or (CH(3)CH(2)O)(2)CIP=S in order to obtain an adsorptive system for `soft` metal ions, particularly Cd(2+). These functionalized fibers (FFs) were characterized by means of elemental analysis, infrared spectroscopy, thermal analysis and acid-base titration. Adsorption isotherms for Cd(2+) fitted the Langmuir model, with binding capacities of 0.2-5 mmol g(-1) of FF at 25 degrees C. (C) 2009 Elsevier Ltd. All rights reserved.