Non-conventional oils for biodiesel production: a study of thermal and oxidative stability

Vegetable oils with variable proportions of oleic, linoleic, and linolenic acids are more susceptible to oxidative processes. In this subject, this study evaluates the physical chemical properties and oxidative stability of non-conventional oils such as andiroba, babassu, sesame, oiticica, jatropha, and grape through accelerated oxidation techniques (pressurized differential scanning calorimetry, Rancimat and PetroOxy). It was verified that babassu and andiroba oil do not showed detectable induction period presenting high oxidative stability; moreover, it was observed that the enthalpic events occurred in 1.19, >10, 0.53, 0.49, 0.49, and 0.60 h for the andiroba oil, babassu oil, sesame seeds, jatropha, oiticica oils, and grapes, respectively, stimulating the conclusion of greater stability for the babassu oil.     

The First VOPO4·2H2O Intercalation Compound Synthesized through a Solid-State Reaction at Room Temperature

This communication reports the first intercalation into VOPO₄·2H₂O performed through a solid-state reaction at room temperature. Ethyleneurea, EU (2-imidazolidone) was intercalated into the oxovanadium phosphate by grinding in a mortar stoichiometric amounts of both reagents at room temperature for 30 min. C, H and N elemental analyses of the obtained intercalation compound gave the formula VOPO₄·(EU)·H₂O. The profile of the absorption bands due to the VOPO₄ lattice vibration around 1000 cm⁻¹ was retained after reaction, providing evidence that an intercalation compound and not merely a salt of V-P-O species was produced. For α-VOPO₄·2H₂O, the interlayer distance is 0.75 nm, whereas for the EU inter-calation compound it is 0.95 nm. The obtained SEM micrographs show that the microstructure of VOPO₄·2H₂O is changed after reaction, with a total exfoliation of the oxovanadium matrix.     

Impact of electrodialytic parameters on cation migration kinetics and fouling nature of ion-exchange membranes during treatment of solutions with different magnesium/calcium ratios

During electrodialysis (ED) treatment of solutions with different Mg/Ca ratios (R = 0, 1/20, 1/10, 1/5 and 2/5) and in different pH conditions (acid, neutral and basic), foulings on ion-exchange membranes were previously characterized and identified, by the way of X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. A mineral fouling was observed in neutral and basic conditions (for R = 1/5 and 2/5) on the anion-exchange membrane (AEM) concentrate side and in basic conditions on the cation-exchange membrane (CEM) concentrate side as well as on the diluate side for R = 1/5 and 2/5. The objectives of this present work were to link the morphological characterization and identification of membrane fouling to electrodialytic parameters and cation migration kinetics. It appeared that the CEM permselectivity was severely affected in basic conditions for R ≥ 1/5. The consequence of this alteration was the migration of OH⁻ through the CEM, a pH increase in the diluate compartment and different treatment durations. The calcite observed on AEM concentrate side for Mg/Ca ≥ 1/5 would be due first to the particular operating conditions such as the recirculation of the concentrate solution, and also to the supersaturated conditions reached or not at the AEM interface and favourable pH conditions.     

Influence of substrate temperature and N2/Ar flow ratio on the stoichiometry,structure and hardness of TaNx coatings deposited by DC reactive sputtering

The effect of substrate temperature and N2/Ar flow ratio on the stoichiometry, structure and hardness of TaN_x coatings prepared on (111) Si substrates by DC reactive sputtering was investigated. For the structural, chemical and morphological analysis, X‐ray diffraction (XRD), Auger electron scanning and atomic force microscopy were respectively used. Hardness values of thin films were determined using the work of indentation model from nanoindentation measurements. TaN stoichiometric coatings were obtained for samples deposited at room temperature. The stoichiometric TaN phase was not obtained by increasing the temperature up to 773 K, even when increasing the N₂/Ar flow ratio. Even when a saturation in nitrogen content was achieved, nitrogen vacancies are still present in those samples. For coatings prepared at 773 K and low N₂/Ar flow ratio, a phase mixture between TaN_x and cubic α‐Ta was observed, while a cubic structure δ‐TaN was formed by increasing the N₂/Ar flow ratio. A maximum in hardness and (38 GPa) was obtained for the sample deposited at 773 K and a N₂/Ar flow ratio of 0.2, which presented a δ‐TaN cubic crystalline structure and a roughness value of 1.6 nm. Copyright © 2015 John Wiley & Sons, Ltd.     

Supercritical fluid chromatography with photodiode array detection for pesticide analysis in papaya and avocado samples

To improve the analysis of pesticides in complex food matrices with economic importance, alternative chromatographic techniques, such as supercritical fluid chromatography, can be used. Supercritical fluid chromatography has barely been applied for pesticide analysis in food matrices. In this paper, an analytical method using supercritical fluid chromatography coupled to a photodiode array detection has been established for the first time for the quantification of pesticides in papaya and avocado. The extraction of methyl parathion, atrazine, ametryn, carbofuran, and carbaryl was performed through the quick, easy, cheap, effective, rugged, and safe methodology. The method was validated using papaya and avocado samples. For papaya, the correlation coefficient values were higher than 0.99; limits of detection and quantification ranged from 130–380 and 220–640 μg/kg, respectively; recovery values ranged from 72.8–94.6%; precision was lower than 3%. For avocado, limit of detection values were ?450 μg/kg; precision was lower than 11%; recoveries ranged from 50.0–94.2%. Method feasibility was tested for lime, banana, mango, and melon samples. Our results demonstrate that the proposed method is applicable to methyl parathion, atrazine, ametryn, and carbaryl, toxics pesticides used worldwide. The methodology presented in this work could be applicable to other fruits.     

Effects of Ultraviolet Radiation (UVA+UVB) and Copper on the Morphology,Ultrastructural Organization and Physiological Responses of the Red Alga Pterocladiella capillacea

The effect of ultraviolet (UV) radiation and copper (Cu) on apical segments of Pterocladiella capillacea was examined under two different conditions of radiation, PAR (control) and PAR+UVA+UVB (PAR+UVAB), and three copper concentrations, ranging from 0 (control) to 0.62, 1.25 and 2.50 μm . Algae were exposed in vitro to photosynthetically active radiation (PAR) at 70 μmol photons m^?2 s^?1, PAR + UVB at 0.35 W m^?2 and PAR +UVA at 0.70 W m^?2 during a 12‐h photocycle for 3 h each day for 7 days. The effects of radiation and copper on growth rates, content of photosynthetic pigments and photosynthetic performance were analyzed. In addition, samples were processed for light and transmission electron microscopy. The content of photosynthetic pigments decreased after exposure to radiation and Cu. Compared with PAR radiation and copper treatments modified the kinetics patterns of the photosynthesis/irradiance curve. The treatments also caused changes in the ultrastructure of cortical and subcortical cells, including increased cell wall thickness and accumulation of plastoglobuli, as well as changes in the organization of chloroplasts. The results indicate that the synergistic interaction between UV radiation and Cu in P. capillacea, led to the failure of protective mechanisms and causing more drastic changes and cellular imbalances.     

Assessment of daily dietary intake of Hg and some essential elements in diets of children from the Amazon region

Summary Daily dietary intake of Hg and some essential elements in diets of children from communities in the Jaú National Park, Amazon region, were assessed. Diet samples were analyzed for total Hg content using cold vapor atomic absorption spectrometry and Ca, Fe, K, Na, Se and Zn contents by instrumental neutron activation analysis. The weekly tolerable provisional intake for Hg in the communities studied varied from 13 to 57 mg of Hg per kg of body weight, exceeding the limit of 5 mg ^. kg^-1 set by the WHO. Comparison of the daily dietary intake values to the new Dietary Reference Intakes (4-8 years), showed prevalence of inadequacy.     

Effects of pH and Carbon Source on <Emphasis Type="Italic">Synechococcus</Emphasis> PCC 7002 Cultivation: Biomass and Carbohydrate Production with Different Strategies for pH Control

Synechococcus PCC 7002 is an interesting species in view of industrial production of carbohydrates. The cultivation performances of this species are strongly affected by the pH of the medium, which also influences the carbohydrate accumulation. In this work, different methods of pH control were analyzed, in order to obtain a higher production of both Synechococcus biomass and carbohydrates. To better understand the influence of pH on growth and carbohydrate productivity, manual and automatic pH regulation in CO₂ and bicarbonate system were applied. The pH value of 8.5 resulted the best to achieve both of these goals. From an industrial point of view, an alternative way to maintain the pH practically constant during the entire period of cultivation is the exploitation of the bicarbonate-CO₂ buffer system, with the double aim to maintain the pH in the viability range and also to provide the amount of carbon required by growth. In this condition, a high concentration of biomass (6 g L^?1) and carbohydrate content (around 60 %) were obtained, which are promising in view of a potential use for bioethanol production. The chemical equilibrium of C-N-P species was also evaluated by applying the ionic balance equations, and a relation between the sodium bicarbonate added in the medium and the equilibrium value of pH was discussed.     

Thermodynamics of a quasi-two-dimensional electron gas: Effects of magnetic fields, temperature and finite width

The effects of nonzero temperature, finite thickness and magnetic fields on an electron gas confined in a quasi-two-dimensional (Q2DEG) region are studied. Finite values of the thickness allow the existence of energy bands and give new characteristics to the system. Here we study some thermodynamic and transport properties to get a better understanding of these effects. For electronic densities of the order of 10¹² electrons per cm², and temperatures lower than 4 K, it is found that the chemical potential, free energy, magnetization, magnetic susceptibility and the inverse of Hall conductivity are independent of the thickness up to it reaches a threshold value. Systems with thicknesses a little above of the critical value lose the two-dimensional character, but they do not have the properties of a three-dimensional electron gas.