Direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirits by graphite furnace AAS using tungsten permanent modifier with co-injection of Pd/Mg(N03)2

A method was developed using the multi-element graphite furnace atomic absorption spectrometry technique for the direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirit (cachaça) samples. Also employed was the end-capped transversely heated graphite atomizer (THGA) with platforms pre-treated with W permanent modifier and co-injection of Pd/Mg(N03)2. Pyrolysis and atomization temperature curves were established in a cachaça medium (1+1; v/v) containing 0.2% (v/v) HN03 and spiked with 20 μg L-1 As and Pb and 200 μg L-1Cu. The effect of the concentration of major elements usually present in cachaça matrices (Ca, Mg, Na, and K) and ethanol on the absorbance of As, Cu, and Pb was investigated. Analytical working solutions of As, Cu, and Pb were prepared in 10% (v/v) ethanol plus 5.0 mg L-1 Ca, Mg, Na, and K. Acidified to 0.2% (v/v) HNO3, these solutions were suitable to build calibration curves by matrix matching. The proposed method was applied to the simultaneous determination of As, Cu, and Pb in commercial sugar cane spirits. The characteristic mass for the simultaneous determination was 16 pg As, 119 pg Cu, and 28 pg Pb. The pretreated tube lifetime was about 450 firings. The limit of detection (LOD) was 0.6 μg L-1As, 9.2 μg L-1 Cu, and 0.3 μg L-1Pb. The found concentrations varied from 0.81 to 4.28 μg L-1As, 0.28 to 382 mg L-1 Cu and 0.82 to 518 μg L-1 Pb. The recoveries of the spiked samples varied from 94-112% (As), 97-111% (Cu), and 95-101% (Pb). The relative standard deviation (n=12) was 6.9%, 7.4%, and 7.7% for As, Cu, and Pb, respectively, present in a sample at 0.87 μgL-1, 0.81 mgL-1, and 38.9 μgL-1concentrations.

Heat transfer in a packed sugar cane bagasse bed

Heat transfer in a packed bed of sugar cane bagasse, which is a potential biofuel used in cars and industries, percolated with air flow was studied. The fibers were washed, sieved, oven dried, and afterwards moisture content was adjusted to 4 and 47%. The relative humidity of the air, packing bed technique, and the initial moisture content of the porous media did not have a significant effect on the outlet temperature of the bed. Air flow rate influenced the averaged radial temperature profile, but not the temperature measured at the nearest position to the tube wall. At the end of the experiments, moisture segregation was observed, the lower bed depths being drier than the higher ones. This is an abstract of a paper presented at the 18th International Congress of Chemical Process Engineering (Praque, Czech Republic 8/24-28/2008).

Influence of the vinasse application in sugar cane fields in Patrocínio Paulista, São Paulo State, Brazil

This investigation was carried out in Patrocínio Paulista municipality, located in the state of São Paulo, Brazil. Sugarcane has been extensively cultivated in the area in order to be utilized by the sugar and ethanol industries. The major effluent from the ethanol industry, vinasse, has been applied in the sugarcane fields as an alternative to supply several nutrients in crop production. Because it may represent a major environmental problem in that area, with implications to human health, soil samples from six points were collected and analyzed in order to evaluate the main factors related to the vinasse application in the ground. The importance of clays, iron oxides, organic matter and minor refractory minerals was also considered for explaining several relationships identified from the acquired data. © 2009 WIT Press.

Emissions from sugar cane fires in the Central & Western State of São Paulo and aerosol layers over metropolitan São Paulo observed by IPEN's lidar: Is there a connection?

The central and western parts of the State of São Paulo are well-known for vast sugar cane plantations, which during the harvest time are traditionally burnt about 12 hours before manual cutting. This procedure causes the release of large quantities of aerosols and a variety of gases, which can be observed by IPMet's radars, located in Bauru and Presidente Prudente, on days with no or little rain. Depending on the distance of these plumes from the radar, they can be detected up to 5 km amsl or more, and are subsequently being transported by winds to other regions. During the dry winter season of 2008, such plumes, attributed to cane fires, were frequently observed by IPMet's radars and documented in terms of radar reflectivity, time and location during the period 10 th - 21 st July 2008. At the same time, IPEN's Elastic Backscatter Lidar in São Paulo observed layers of aerosols of variable strength and heights above the city. The most significant days, viz. 14 and 15 July 2008 had been selected for calculating backward, as well as forward trajectories, deploying the European Flextra 3.3 Trajectory Model, which was initiated with ECMWF historic data with a 0,25 o×0,25 o grid spacing. The results presented here show an excellent match between the radar-detected sources of the plumes on 11 th July 2008 in the central parts of the State and the observations by IPEN's Lidar over Metropolitan São Paulo on 14 th July 2008, both in terms of forward and backward trajectories, as well as their heights, with a transport duration of approximately 70 hours under the prevailing meteorological conditions. © Sociedad Española de Óptica.

Glass-ceramic material from the SiO 2-Al 2O 3-CaO system using sugar-cane bagasse ash (SCBA)

Brazil is the world's largest producer of alcohol and sugar from sugarcane. Currently, sugarcane bagasse is burned in boilers to produce steam and electrical energy, producing a huge volume of ash. The major component of the ash is SiO 2, and among the minor components there are some mineralizing agents or fluxing. Published works have shown the potential of transforming silicate-based residues into glass-ceramic products of great utility. This work reports the research results of SCBA use to produce glass-ceramics with wollastonite, rankinite and gehlenite as the major phases. These silicates have important applications as building industry materials, principally wollastonite, due to their special properties: high resistance to weathering, zero water absorption, and hardness among others. The glasses (frits) were prepared mixing ash, calcium carbonate and sodium or potassium carbonates as flux agents, in different concentrations. X-ray fluorescence was used to determine the chemical composition of the glasses and their crystallization was assessed by using thermal analysis (DTA/DSC/TGA) and X-ray diffraction. The crystallization kinetics was evaluated using the Kissinger method, giving activation energies ranging from 200 to 600 kJ/mol. © 2011 Ceramic Society of Japan.

Clastogenicity of landfarming soil treated with sugar cane vinasse

The addition of nutrients and/or soil bulking agents is used in bioremediation to increase microbial activity in contaminated soils. For this purpose, some studies have assessed the effectiveness of vinasse in the bioremediation of soils contaminated with petroleum waste. The present study was aimed at investigating the clastogenic/aneugenic potential of landfarming soil from a petroleum refinery before and after addition of sugar cane vinasse using the Allium cepa bioassay. Our results show that the addition of sugar cane vinasse to landfarming soil potentiates the clastogenic effects of the latter probably due the release of metals that were previously adsorbed into the organic matter. These metals may have interacted synergistically with petroleum hydrocarbons present in the landfarming soil treated with sugar cane vinasse. We recommend further tests to monitor the effects of sugar cane vinasse on soils contaminated with organic wastes. © 2012 Springer Science+Business Media B.V.

Quantification of uncertainties associated with space-time estimates of short-term soil CO2 emissions in a sugar cane area

The characterization of soil CO2 emissions (FCO2) is important for the study of the global carbon cycle. This phenomenon presents great variability in space and time, a characteristic that makes attempts at modeling and forecasting FCO2 challenging. Although spatial estimates have been performed in several studies, the association of these estimates with the uncertainties inherent in the estimation procedures is not considered. This study aimed to evaluate the local, spatial, local-temporal and spatial-temporal uncertainties of short-term FCO2 after harvest period in a sugar cane area. The FCO2 was featured in a sampling grid of 60m×60m containing 127 points with minimum separation distances from 0.5 to 10m between points. The FCO2 was evaluated 7 times within a total period of 10 days. The variability of FCO2 was described by descriptive statistics and variogram modeling. To calculate the uncertainties, 300 realizations made by sequential Gaussian simulation were considered. Local uncertainties were evaluated using the probability values exceeding certain critical thresholds, while the spatial uncertainties considering the probability of regions with high probability values together exceed the adopted limits. Using the daily uncertainties, the local-spatial and spatial-temporal uncertainty (Ftemp) was obtained. The daily and mean emissions showed a variability structure that was described by spherical and Gaussian models. The differences between the daily maps were related to variations in the magnitude of FCO2, covering mean values ranging from 1.28±0.11μmolm-2s-1 (F197) to 1.82±0.07μmolm-2s-1 (F195). The Ftemp showed low spatial uncertainty coupled with high local uncertainty estimates. The average emission showed great spatial uncertainty of the simulated values. The evaluation of uncertainties associated with the knowledge of temporal and spatial variability is an important tool for understanding many phenomena over time, such as the quantification of greenhouse gases or the identification of areas with high crop productivity. © 2013 Elsevier B.V.

Thermal behavior of renewable diesel from sugar cane, biodiesel, fossil diesel and their blends

Biofuels and their blends with fossil fuel are important energy resources, whose production and application have been largely increased internationally. This study focuses on the evaluation of the activation energy of the thermal decomposition of three pure fuels: farnesane (renewable diesel from sugar cane), biodiesel and fossil diesel and their blends (20% farnesene and 80% of fossil diesel - 20F80D and 20% farnesane, 50% fossil diesel and 30% biodiesel - 20F50D30B). Activation energy has been determined from thermogravimetry and Model-Free Kinetics. Results showed that not only the cetane number is important to understand the behavior of the fuels regarding ignition delay, but also the profile of the activation energy versus conversion curves shows that the chemical reactions are responsible for the performance at the beginning of the process. In addition, activation energy seemed to be suitable in describing reactivity in the case of blends of renewable and fossil fuels. © 2013 Elsevier B.V.

Energetic, ecologic and fluid-dynamic analysis of a fluidized bed gasifier operating with sugar cane bagasse

This work aims to study the thermodynamic, ecological and fluid-dynamic aspects of a circulating fluidized bed gasifier using sugar cane bagasse as biomass, in order to estimate a model of its normal operation. In the initial stage was analysed the composition of biomass selected (sugar cane bagasse) and its lower heating value (LHV) was calculated. The energy balance of the gasifier was done, being the volumetric flow of air, synthesis gas and biomass estimated. Also the power produced by this gasifier was theoretically estimated. Then the circulating fluidized bed gasifier was designed for operation with approximately 100 kg/h of processed biomass. Cross-sectional area of the reactor, feeder size, diameter of the exit zone of the gases and minimum height of the expanded bed were selected. Some bed gasifier hydrodynamic factors were also studied. The minimum fluidization velocity, fluidization terminal velocity, and average fluidizing velocity were calculated, in order to understand the fluid-dynamic behaviour of gasification of this fuel. It was obtained a theoretical model that can support a possible prototype of circulating fluidized bed gasifier biomass. Finally, there were studied the ecological aspects of the gasifier, through an overall methodology. Ecological efficiencies were estimated for two scenarios: first considering the carbon cycle and thereafter disregarding the carbon cycle. In both cases, it can be proved the ecological viability of the project. © 2013 Elsevier Ltd. All rights reserved.

Use of slag/sugar cane bagasse ash (SCBA) blends in the production of alkali-activated materials

Blast furnace slag (BFS)/sugar cane bagasse ash (SCBA) blends were assessed for the production of alkali-activated pastes and mortars. SCBA was collected from a lagoon in which wastes from a sugar cane industry were poured. After previous dry and grinding processes, SCBA was chemically characterized: it had a large percentage of organic matter (ca. 25%). Solutions of sodium hydroxide and sodium silicate were used as activating reagents. Different BFS/SCBA mixtures were studied, replacing part of the BFS by SCBA from 0 to 40% by weight. The mechanical strength of mortar was measured, obtaining values about 60 MPa of compressive strength for BFS/SCBA systems after 270 days of curing at 20 °C. Also, microstructural properties were assessed by means of SEM, TGA, XRD, pH, electrical conductivity, FTIR spectroscopy and MIP. Results showed a good stability of matrices developed by means of alkali-activation. It was demonstrated that sugar cane bagasse ash is an interesting source for preparing alkali-activated binders. © 2013 by the authors; licensee MDPI, Basel, Switzerland.

Occurrence of Cu and Cr in the sedimentary humic substances and pore water from a typical sugar cane cultivation area in São Paulo, Brazil

Purpose: The purpose of this paper is to study the interactions of sedimentary humic substances (SHS) from a sugarcane cultivation area with Cu(II) and Cr(III) and to evaluate the occurrence of these metals in the pore water and SHS. Materials and methods: For this study, the northwestern region of the State of São Paulo, Brazil, which is considered the region with the highest production of sugar cane in the state, was selected. Samples of sediment were collected from four sampling sites in the Preto, Turvo, and Grande rivers. The SHS and pore water were extracted from the sediment using the method suggested by the International Humic Substances Society and centrifugation, respectively. The complexing capacity (CC) of the SHS for Cu(II) and Cr(III) was determined by individually titrating these metals with an ultrafiltration system using tangential flow. The total concentrations of Cr and Cu were determined for the pore water, sediments, and humic substances with graphite furnace atomic absorption spectrometry and Zeeman background correction after an acid digestion, according to the methods described in US EPA Method 3050B. Results and discussion: The SHS from a site in the Turvo River, which is typically cultivated with sugarcane, possessed the highest concentration of Cu bound to SHS (25.0%), the largest CC (0.63 mmol Cu g-1 HS) and the highest concentration of this metal in the pore water (1.38 mg Cu Kg-1 sed.). For Cr, the SHS collected from a location on the Preto River dam had the largest CC (0.90 mmol Cr g-1 HS) and the lowest Cr content in the pore water (0.29 mg Cr Kg-1 sed.), indicating that there was an inverse relationship between the CC and the concentration of metal available in the pore water. Conclusions: Sedimentary humic substances might be one of the regulatory factors controlling the availability of Cu and Cr in the sediments found in a typical region that has been planted with sugarcane. Distinct behaviors were observed between the two elements investigated; higher CC and a larger fraction of Cu(II) were found in the pore water of samples originating from sugarcane crops. The opposite behavior was observed for the Cr(III) species. © 2013 Springer-Verlag Berlin Heidelberg.

Anthropogenic influences on Cd, Cr,Cu, Ni, Pb and Zn concentrations in soils and sediments in a watershed with sugar cane crops at São Paulo State, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The enzymatic recalcitrance of internodes of sugar cane hybrids with contrasting lignin contents

The recalcitrance in grasses varies according to cell type and maturation. The origin of the recalcitrance in different regions from sugar cane internodes with varied lignin contents was evaluated. The efficiency of enzymatic hydrolysis was correlated with the chemical, micromorphological and microspectrophotometric characteristics of the samples. The internodes of three sugar cane hybrids were dissected into four different fractions. The outermost fraction and the rind were the most recalcitrant regions, whereas the pith-rind interface and the pith were less recalcitrant. Cellulose conversion reached 86% after 72h of enzymatic digestion of the pith from the hybrid with the lowest lignin content. There was an inversely proportional correlation between the area occupied by vascular bundles and the efficiency of cellulose hydrolysis. High cellulose and low lignin or hemicellulose contents enhanced the efficiency of enzymatic hydrolysis of the polysaccharides. The critical evaluation of the results permitted to propose an empirical parameter for predicting cellulose conversion levels that accounts for the positive effect of high cellulose and low lignin plus hemicellulose and the detrimental effect of abundant vascular bundles. The cellulose conversion levels fit well to this calculated parameter, following a second order polynomial with an r2 value of 0.96. © 2013 Elsevier B.V.