A preliminary physicochemical, exergetic and economic study of hydrogen production utilizing glycerol

This work has as objective to demonstrate technical and economic viability of hydrogen production utilizing glycerol. The volume of this substance, which was initially produced by synthetic ways (from oil-derived products), has increased dramatically due mainly to biodiesel production through transesterification process which has glycerol as main residue. The surplus amount of glycerol has been generally utilized to feed poultry or as fuel in boilers, beyond other applications such as production of soaps, chemical products for food industry, explosives, and others. The difficulty to allocate this additional amount of glycerol has become it in an enormous environment problem, in contrary to the objective of biodiesel chain, which is to diminish environmental impact substituting oil and its derivatives, which release more emissions than biofuels, do not contribute to CO2-cycle and are not renewable sources. Beyond to utilize glycerol in combustion processes, this material could be utilized for hydrogen production. However, a small quantity of works (theoretical and experimental) and reports concerning this theme could be encountered. Firstly, the produced glycerol must be purified since non-reacted amounts of materials, inclusively catalysts, contribute to deactivate catalysts utilized in hydrogen production processes. The volume of non-reacted reactants and non-utilized catalysts during transesterification process could be reutilized. Various technologies of thermochemical generation of hydrogen that utilizes glycerol (and other fuels) were evaluated and the greatest performances and their conditions are encountered as soon as the most efficient technology of hydrogen production. Firstly, a physicochemical analysis must be performed. This step has as objective to evaluate the necessary amount of reactants to produce a determined volume of hydrogen and determine thermodynamic conditions (such as temperature and pressure) where the major performances of hydrogen production could be encountered. The calculations are based on the process where advance degrees are found and hence, fractions of products (especially hydrogen, however, CO2, CO, CH4 and solid carbon could be also encountered) are calculated. To produce 1 Nm3/h of gaseous hydrogen (necessary for a PEMFC - Proton Exchange Membrane Fuel Cell - containing an electric efficiency of about 40%, to generate 1 kWh), 0,558 kg/h of glycerol is necessary in global steam reforming, 0,978 kg/h of glycerol in partial oxidation and cracking processes, and 0,782 kg/h of glycerol in autothermal reforming process. The dry reforming process could not be performed to produce hydrogen utilizing glycerol, in contrary to the utilization of methane, ethanol, and other hydrocarbons. In this study, steam reforming process was preferred due mainly to higher efficiencies of production and the need of minor amount of glycerol as cited above. In the global steam reforming of glycerine, for one mole of glycerol, three moles of water are necessary to produce three moles of CO2 and seven moles of H2. The response reactions process was utilized to predict steam reforming process more accurately. In this mean, the production of solid carbon, CO, and CH4, beyond CO2 and hydrogen was predicted. However, traces of acetaldehyde (C2H2), ethylene (C2H4), ethylene glycol, acetone, and others were encountered in some experimental studies. The rates of determined products obviously depend on the adopted catalysts (and its physical and chemical properties) and thermodynamic conditions of hydrogen production. Eight reactions of steam reforming and cracking were predicted considering only the determined products. In the case of steam reforming at 600°C, the advance degree of this reactor could attain its maximum value, i.e., overall volume of reactants could be obtained whether this reaction is maintained at 1 atm. As soon as temperature of this reaction increases the advance degree also increase, in contrary to the pressure, where advance degree decrease as soon as pressure increase. The fact of temperature of reforming is relatively small, lower costs of installation could be attained, especially cheaper thermocouples and smaller amount of thermo insulators and materials for its assembling. Utilizing the response reactions process in steam reforming, the predicted volumes of products, for the production of 1 Nm3/h of H2 and thermodynamic conditions as cited previously, were 0,264 kg/h of CO (13% of molar fraction of reaction products), 0,038 kg/h of CH4 (3% of molar fraction), 0,028 kg/h of C (3% of molar fraction), and 0,623 kg/h of CO2 (20% of molar fraction). Through process of water-gas shift reactions (WGSR) an additional amount of hydrogen could be produced utilizing mainly the volumes of produced CO and CH4. The overall results (steam reforming plus WGSR) could be similar to global steam reforming. An attention must to be taking into account due to the possibility to produce an additional amount of CH4 (through methanation process) and solid carbon (through Boudouard process). The production of solid carbon must to be avoided because this reactant diminishes (filling the pores) and even deactivate active area of catalysts. To avoid solid carbon production, an additional amount of water is suggested. This method could be also utilized to diminish the volume of CO (through WGSR process) since this product is prejudicial for the activity of low temperature fuel cells (such as PEMFC). In some works, more three or even six moles of water are suggested. A net energy balance of studied hydrogen production processes (at 1 atm only) was developed. In this balance, low heat value of reactant and products and utilized energy for the process (heat supply) were cited. In the case of steam reforming utilizing response reactions, global steam reforming, and cracking processes, the maximum net energy was detected at 700°C. Partial oxidation and autothermal reforming obtained negative net energy in all cited temperatures despite to be exothermic reactions. For global steam reforming, the major value was 114 kJ/h. In the case of steam reforming, the highest value of net energy was detected in this temperature (-170 kJ/h). The major values were detected in the cracking process (up to 2586 kJ/h). The exergetic analysis has as objective, associated with physicochemical analysis, to determine conditions where reactions could be performed at higher efficiencies with lower losses. This study was performed through calculations of exergetic and rational efficiencies, and irreversibilities. In this analysis, as in the previously performed physicochemical analysis, conditions such as temperature of 600°C and pressure of 1 atm for global steam reforming process were suggested due to lower irreversibility and higher efficiencies. Subsequently, higher irreversibilities and lower efficiencies were detected in autothermal reforming, partial oxidation and cracking process. Comparing global reaction of steam reforming with more-accurate steam reforming, it was verified that efficiencies were diminished and irreversibilities were increased. These results could be altered with introduction of WGSR process. An economic analysis could be performed to evaluate the cost of generated hydrogen and determine means to diminish the costs. This analysis suggests an annual period of operation between 5000-7000 hours, interest rates of up to 20% per annum (considering Brazilian conditions), and pay-back of up to 20 years. Another considerations must to be take into account such as tariffs of utilized glycerol and electricity (to be utilized as heat source and (or) for own process as pumps, lamps, valves, and other devices), installation (estimated as US$ 15.000 for a plant of 1 Nm3/h) and maintenance cost. The adoption of emission trading schemes such as carbon credits could be performed since this is a process with potential of mitigates environment impact. Not considering credit carbons, the minor cost of calculated H2 was 0,16288 US$/kWh if glycerol is also utilized as heat sources and 0,17677 US$/kWh if electricity is utilized as heat sources. The range of considered tariff of glycerol was 0-0,1 US$/kWh (taking as basis LHV of H2) and the tariff of electricity is US$ 0,0867 US$/kWh, with demand cost of 12,49 US$/kW. The costs of electricity were obtained by Companhia Bandeirante, localized in São Paulo State. The differences among costs of hydrogen production utilizing glycerol and electricity as heat source was in a range between 0,3-5,8%. This technology in this moment is not mature. However, it allows the employment generation with the additional utilization of glycerol, especially with plants associated with biodiesel plants. The produced hydrogen and electricity could be utilized in own process, increasing its final performance.

Habitat heterogeneity and use of physical and acoustic space in anuran communities in Southeastern Brazil

Habitat heterogeneity and use of physical and acoustic space in anuran communities in Southeastern Brazil. We intended to verify if structural and physiognomical characteristics of water bodies influence on the degree of overlap among calling sites of 23 anurans species, if anuran species use different calling sites in different water bodies, and if there is some relationship between the degree of advertisement call (based on seven call features) and calling site differentiation. Then, we determined calling sites (based in four variables) and recorded the advertisement call for anuran species that occurred in 10 water bodies of northwestern São Paulo State. We also determined the environmental heterogeneity (based in four environmental descriptors) for each water body. Males of most species used similar calling sites in each water body, probably because of the high uniformity of the environment, as a consequence of agricultural impacts on edge vegetation of the studied ponds. Most species (18 out of 19 species) called from different sites in the ponds where they occurred, which can be associated with differences in horizontal and vertical distribution of vegetation in the studied ponds. From the 19 species analyzed, only males of Pseudopaludicola aff. saltica called in sites with the same characteristics in different ponds. Advertisement call of Hylidae species was more similar to each other than were Leiuperidae and Leptodactylidae among themselves. The aquatic/terrestrial anurans (Bufonidae, Leiuperidae, Leptodactylidae and Microhylidae) occupied similar calling sites but presented quite distinct advertisement calls, while Hylidae species presented an inverse pattern: a high similarity on advertisement call features but used different calling sites, which indicates a niche complementarity between physical (calling site use) and acoustic (advertisement call) space use. © 2008 Departamento de Ciências Biológicas.

Evaluation of hardness and color stability in the soft lining materials after thermocycling and chemical polishing.

The aim of this study was to evaluate the Shore A hardness and color stability of two soft lining materials after thermocycling and when chemical polishing was used or omitted. Two acrylic-based soft lining materials were tested: Coe-Soft and Soft Confort, 14 specimens were made for each material. They were distributed in four groups according to the treatment performed. The specimens were thermocycled (1000 cycles) and half of the group submitted to chemical polishing (methyl methacrylate). Shore A hardness was determined and color stability was calculated by means of Commission International de l'Eclairage Lab uniform color scale using a spectrophotometer, the measurements were made immediately after deflasked, chemical polishing and thermocycling. Analysis of variance (ANOVA) and Tukey's tests were performed at p < 0.01. Color changes (deltaE) were observed after thermocycling in both soft lining materials: Soft Confort (10.60) showed significantly higher values than Coe-Soft (4.57). Coe-Soft (26.42) showed higher Shore A hardness values than Soft Confort (19.42). Chemical polishing did not influence in the color stability of both materials; however, influenced in the hardness values of Coe-Soft.

Colors and some morphological traits as defensive mechanisms in anurans

Anurans may be brightly colored or completely cryptic. Generally, in the former situation, we are dealing with aposematism, and the latter is an example of camouflage. However, these are only simple views of what such colorations really mean and which defensive strategy is implied. For instance, a brightly colored frog may be part of a mimicry ring, which could be either Batesian, Müllerian, or Browerian. These are only examples of the diversity of color-usage systems as defensive strategies. Unfortunately, reports on the use of colors as defensive mechanisms are widespread in the available literature, and the possible functions are rarely mentioned. Therefore, we reviewed the literature and added new data to this subject. Then, we the use of colors (as defensive mechanism) into categories. Mimicry was divided into the subcategories camouflage, homotypy, and nondeceitful homotypy, and these groups were also subcategorized. Dissuasive coloration was divided into behavioral display of colors, polymorphism, and polyphenism. Aposematism was treated apart, but aposematic colorations may be present in other defensive strategies. Finally, we propose functions and forms of evolution for some color systems in post-metamorphic anurans and hope that this review can be the basis for future research, even on other animal groups. © 2009 L. F. Toledo and C. F. B. Haddad.

Select bibliography on coastal area development and environmental, physical and regional planning in the Caribbean region

Bibliografía sobre desarrollo de las áreas costeras, planificación del medio ambiente, recursos marinos, planificación regional y física, y puertos del Caribe.

Aquatic macroinvertebrates survey and assessment of two artificial reservoirs into conservation units from the Southeast Region of Brazil

This study aims to inventory and assess the aquatic macroinvertebrates fauna in two artificial reservoirs into conservation units with differences regarding conservation level and to anthropogenic impacts. The samplings were carried out in Caetetus Ecological Station and Bauru City Zoological Park, where some physical and chemical variables also were measured. The results obtained indicated that the Caetetus Ecological Station is more effective in the conservation of the diversity of aquatic macroinvertebrates compared to Bauru City Zoological Park. These results can be attributed to the strong anthropogenic impact suffered by the reservoir in Bauru and demonstrate the importance of these areas in maintaining the diversity of aquatic macroinvertebrates community.

Biomass production and chemical composition of essential oil of Piper callosum as affected by spacing in Manaus, Amazonas State, Brazil

The family Piperaceae contains nearly 2000 species, most of them distributed in two genera, Piper and Peperomia. In Brazil circa 170 Piper species are found, mainly in tropical areas Their use ranges from flavoring and culinary to raw material for pharmaceutical and cosmetic industry. One of these species, Piper callosum, is used in folk medicine in the Amazon area. The objective of this study was to evaluate the production of biomass (aerial parts) as well as yield and composition of the essential oil from the leaves, according to different spacing between cultivated plants at Embrapa Western Amazon, in Manaus, State of Amazonas, Brazil. The experimental design was randomized blocks, with four treatments and seven replicates with six plants. Biomass production was inversely proportional to the spatial arrangements, with the greatest biomass production (1034.93 kg/ha) in the shortest spacing (E1), although no statistical difference was verified between E3 and E4. The same response was observed for the production of essential oil. The chemical composition of the oil was not affected by spacing, and major compounds found were safrole (59.1%), beta-pinene (8.3%), alpha-pinene (6.5%), methyl eugenol (6.3%) and 1,8-cineole (4.1).

The swing-by effect in the Vesta-Magnya case. Single and multiple encounters.

It was verified that the asteroid Magnya has some physical and chemical characteristics similar to the bodies from Vesta family. However, astronomical observations revealed that Magnya is distant from these bodies. In the present work, we assumed that Magnya originated from Vesta and we try to justify its current distant orbital location taking into account the effects of close encounters between Magnya and Vesta. The methodology adopted involved an analytical approach considering the technique of the gravity assisted maneuver, also known as swing-by. We found that the energy variation achieved through a single swing-by between Vesta and Magnya are very small when compared to the variation that would be required to change the orbit of Magnya. The effects of multiple close encounters were also considered and discussed. We concluded that the possibility of multiple encounters is limited, and therefore, that Magnya should suffer other perturbations (such as resonances, collisions or close encounters with other bodies, for instance) that would provide the supposed change in its orbit.

Delineation of specific management areas for coffee cultivation based on the soil-relief relationship and numerical classification

Predicting and mapping productivity areas allows crop producers to improve their planning of agricultural activities. The primary aims of this work were the identification and mapping of specific management areas allowing coffee bean quality to be predicted from soil attributes and their relationships to relief. The study area was located in the Southeast of the Minas Gerais state, Brazil. A grid containing a total of 145 uniformly spaced nodes 50 m apart was established over an area of 31. 7 ha from which samples were collected at depths of 0. 00-0. 20 m in order to determine physical and chemical attributes of the soil. These data were analysed in conjunction with plant attributes including production, proportion of beans retained by different sieves and drink quality. The results of principal component analysis (PCA) in combination with geostatistical data showed the attributes clay content and available iron to be the best choices for identifying four crop production environments. Environment A, which exhibited high clay and available iron contents, and low pH and base saturation, was that providing the highest yield (30. 4l ha-1) and best coffee beverage quality (61 sacks ha-1). Based on the results, we believe that multivariate analysis, geostatistics and the soil-relief relationships contained in the digital elevation model (DEM) can be effectively used in combination for the hybrid mapping of areas of varying suitability for coffee production. © 2012 Springer Science+Business Media New York.

Polymorphisms in FGFBP1 and FGFBP2 genes associated with carcass and meat quality traits in chickens

In the past, the focus of broiler breeding programs on yield and carcass traits improvement led to problems related to meat quality. Awareness of public concern for quality resulted in inclusion of meat quality traits in the evaluation process. Nevertheless, few genes associated with meat quality attributes are known. Previous studies mapped quantitative trait loci for weight at 35 and 42 days in a region of GGA4 flanked by the microsatellite markers, MCW0240 and LEI0063. In this region, there are 2 fibroblast growth factor binding protein (FGFBP) genes that play an important role in embryogenesis, cellulardifferentiation, and proliferation in chickens. The objective of this study was to identify and associate single nucleotide polymorphisms (SNPs) in FGFBP1 and FGFBP2 with performance, carcass, and meat quality in experimental and commercial chicken populations. In the commercial population, SNP g.2014G>A in FGFBP1 was associated with decreased carcass weight (P < 0.05), and SNP g.651G>A in FGFBP2 was associated with thawing loss and meat redness content (P < 0.05). Four haplotypes were constructed based on 2 SNPs and were associated with breast weight, thawing loss, and meat redness content. The diplotypes were associated with thawing loss, lightness, and redness content. The SNPs evaluated in the present study may be used as markers in poultry breeding programs to aid in improving growth and meat quality traits. © FUNPEC-RP.

Carcass and meat quality traits of rabbits under heat stress

Rabbits are very sensitive to heat stress because they have difficulty eliminating excess body heat. The objective of the current study was to evaluate the effects of heat stress on slaughter weight, dressing percentage and carcass and meat quality traits of rabbits from two genetic groups. Ninety-six weaned rabbits were used: half were from the Botucatu genetic group and half were crossbreds between New Zealand White sires and Botucatu does. They were assigned to a completely randomized design in a 2 × 3 factorial arrangement (two genetic groups and three ambient temperatures: 18°C, 25°C and 30°C) and kept under controlled conditions in three environmental chambers from 5 to 10 weeks of age. Slaughter took place at 10 weeks, on 2 consecutive days. Meat quality measurements were made in the longissimus muscle. Actual average ambient temperature and relative humidity in the three chambers were 18.4°C and 63.9%, 24.4°C and 80.2% and 29.6°C and 75.9%, respectively. Purebred rabbits were heavier at slaughter and had heavier commercial and reference carcasses than crossbreds at 30°C; however, no differences between genetic groups for these traits were found at lower temperatures. No genetic group × ambient temperature interaction was detected for any other carcass or meat quality traits. The percentages of distal parts of legs, skin and carcass forepart were higher in crossbred rabbits, indicating a lower degree of maturity at slaughter in this group. The percentage of thoracic viscera was higher in the purebreds. Lightness of the longissimus muscle was higher in the purebreds, whereas redness was higher in the crossbreds. Slaughter, commercial and reference carcass weights and the percentages of thoracic viscera, liver and kidneys were negatively related with ambient temperature. Commercial and reference carcass yields, and the percentage of distal parts of legs, on the other hand, had a positive linear relationship with ambient temperature. Meat redness and yellowness diminished as ambient temperature increased, whereas cooking loss was linearly elevated with ambient temperature. Meat color traits revealed paler meat in the purebreds, but no differences in instrumental texture properties and water-holding capacity between genetic groups. Purebred rabbits were less susceptible to heat stress than the crossbreds. Heat stress resulted in lower slaughter and carcass weights and proportional reductions of organ weights, which contributed to a higher carcass yield. Moreover, it exerted a small, but negative, effect on meat quality traits. © 2012 The Animal Consortium.

Study of the ℤ3 symmetry in QCD at finite temperature and chemical potential using a worm algorithm

Traditional Monte Carlo simulations of QCD in the presence of a baryon chemical potential are plagued by the complex phase problem and new numerical approaches are necessary for studying the phase diagram of the theory. In this work we consider a ℤ3 Polyakov loop model for the deconfining phase transition in QCD and discuss how a flux representation of the model in terms of dimer and monomer variable solves the complex action problem. We present results of numerical simulations using a worm algorithm for the specific heat and two-point correlation function of Polyakov loops. Evidences of a first order deconfinement phase transition are discussed. © 2013 American Institute of Physics.

Morphological modifications and surface amorphization in ZnO sonochemically treated nanoparticles

Application of nanoscale materials in photovoltaic and photocatalysis devices and photosensors are dramatically affected by surface morphology of nanoparticles, which plays a fundamental role in the understanding of the physical and chemical properties of nanoscale materials. Zinc oxide nanoparticles with an average size of 20 nm were obtained by the use of a sonochemical technique. X-ray diffraction (XRD) associated to Rietveld refinements and transmission electron microscopy (TEM) were used to study structural and morphological characteristics of the samples. An amorphous shell approximately 10 nm thick was observed in the ultrasonically treated sample, and a large reduction in particle size and changes in the lattice parameters were also observed. © 2012 Elsevier B.V. All rights reserved.

Modeling Habitat Split: Landscape and Life History Traits Determine Amphibian Extinction Thresholds

Habitat split is a major force behind the worldwide decline of amphibian populations, causing community change in richness and species composition. In fragmented landscapes, natural remnants, the terrestrial habitat of the adults, are frequently separated from streams, the aquatic habitat of the larvae. An important question is how this landscape configuration affects population levels and if it can drive species to extinction locally. Here, we put forward the first theoretical model on habitat split which is particularly concerned on how split distance - the distance between the two required habitats - affects population size and persistence in isolated fragments. Our diffusive model shows that habitat split alone is able to generate extinction thresholds. Fragments occurring between the aquatic habitat and a given critical split distance are expected to hold viable populations, while fragments located farther away are expected to be unoccupied. Species with higher reproductive success and higher diffusion rate of post-metamorphic youngs are expected to have farther critical split distances. Furthermore, the model indicates that negative effects of habitat split are poorly compensated by positive effects of fragment size. The habitat split model improves our understanding about spatially structured populations and has relevant implications for landscape design for conservation. It puts on a firm theoretical basis the relation between habitat split and the decline of amphibian populations. © 2013 Fonseca et al.

Sonochemical synthesis and magnetism in co-doped ZnO nanoparticles

The understanding and control of ferromagnetism in diluted magnetic semiconducting oxides (DMO) is a special challenge in solid-state physics and materials science due to its impact in magneto-optical devices and spintronics. Several studies and mechanisms have been proposed to explain intrinsic ferromagnetism in DMO compounds since the theoretical prediction of room-temperature ferromagnetism. However, genuine and intrinsic ferromagnetism in 3d-transition metal-doped n-type ZnO semiconductors is still a controversial issue. Furthermore, for DMO nanoparticles, some special physical and chemical effects may also play a role. In this contribution, structural and magnetic properties of sonochemically prepared cobalt-doped ZnO nanoparticles were investigated. A set of ZnO samples was prepared varying cobalt molar concentration and time of ultrasonic exposure. The obtained results showed that single phase samples can be obtained by the sonochemical method. However, cobalt nanoclusters can be detected depending on synthesis conditions. Magnetic measurements indicated a possible ferromagnetic response, associated to defects and cobalt substitutions at the zinc site by cobalt. However, ferromagnetism is depleted at higher magnetic fields. Also, an antiferromagnetic response is detected due to cobalt oxide cluster at high cobalt molar concentrations. © 2012 Springer Science+Business Media, LLC.