Obtenção de Mo2C com adição de Co por reação gás-sólido em reator de leito fixo

Sulfur compounds emissions have been, on the late years, subject to more severe environmental laws due to its impact on the environment (causing the acid rain phenomena) and on human health. It has also been object of much attention from the refiners worldwide due to its relationship with equipment’s life, which is decreased by corrosion, and also with products’ quality, as the later may have its color, smell and stability altered by the presence of such compounds. Sulfur removal can be carried out by hydrotreating (HDT) which is a catalytic process. Catalysts for HDS are traditionally based on Co(Ni)-Mo(W)/Al2O3. However, in face of the increased contaminants’ content on crude oil, and stricter legislation on emissions, the development of new, more active and efficient catalysts is pressing. Carbides of refractory material have been identified as potential materials for this use. The addition of a second metal to carbides may enhance catalytic activities by increasing the density of active sites. In the present thesis Mo2C with Co addition was produced in a fixed bed reactor via gas-solid reaction of CH4 (5%) and H2(95%) with a precursor made of a mix of ammonium heptamolybdate [(NH4)6[Mo7O24].4H2O] and cobalt nitrate[Co(NO3)2.6H2O] at stoichiometric amounts. Precursors’ where analyzed by XRF, XRD, SEM and TG/DTA. Carboreduction reactions were carried out at 700 and 750°C with two cobalt compositions (2,5 and 5%). Reaction’s products were characterized by XRF, XRD, SEM, TOC, BET and laser granulometry. It was possible to obtain Mo2C with 2,5 and 5% cobalt addition as a single phase at 750°C with nanoscale crystallite sizes. At 700°C, however, both MoO2 and Mo2C phases were found by XRD. No Co containing phases were found by XRD. XRF, however, confirmed the intended Co content added. SEM images confirmed XRD data. The increase on Co content promoted a more severe agglomeration of the produced powder. The same effect was noted when the reaction temperature was increased. The powder synthesized at 750°C with 2,5% Co addition TOC analysis indicated the complete conversion from oxide material to carbide, with a 8,9% free carbon production. The powder produced at this temperature with 5% Co addition was only partially converted (86%)

Peat Bog Ecosystems: Atmospheric pollution

Peatlands can be damaged by deposition of pollutants from the atmosphere – often termed ‘ acid rain ’ . This results from the release of sulphur and nitrogen pollutants into the atmosphere . Originally associated with the Industrial Revolution, ‘acid rain��� was first described by Robert Angus Smith, a Manchester chemist of the 1800s , whose obser vations were made in close proximity to the peatlands of the South Pennines. Sulphur dioxide (SO 2 ) pollution, which is mainly emitted from coal burning power stations, peaked in the 1970s and has since decreased by over 90% due to emission controls and ch anges in energy supply. N itrogen ous air pollutants have decreased less . N itrogen oxide (NO x ) emissions , which are mainly from vehicle s , have decreased by two thirds since their peak in 1990 , but the decrease in ammonia ( NH 3 ) emissions , which are mainly from intensive livestock farming, is much less certain and may be only about 20%.

Effects of abscisic acid, ethylene and sugars on the mobilization of storage proteins and carbohydrates in seeds of the tropical tree Sesbania virgata (Leguminosae)

Endospermic legumes are abundant in tropical forests and their establishment is closely related to the mobilization of cell-wall storage polysaccharides. Endosperm cells also store large numbers of protein bodies that play an important role as a nitrogen reserve in this seed. In this work, a systems approach was adopted to evaluate some of the changes in carbohydrates and hormones during the development of seedlings of the rain forest tree Sesbania virgata during the period of establishment. Seeds imbibed abscisic acid (ABA), glucose and sucrose in an atmosphere of ethylene, and the effects of these compounds on the protein contents, alpha-galactosidase activity and endogenous production of ABA and ethylene by the seeds were observed. The presence of exogenous ABA retarded the degradation of storage protein in the endosperm and decreased alpha-galactosidase activity in the same tissue during galactomannan degradation, suggesting that ABA represses enzyme action. On the other hand, exogenous ethylene increased alpha-galactosidase activity in both the endosperm and testa during galactomannan degradation, suggesting an inducing effect of this hormone on the hydrolytic enzymes. Furthermore, the detection of endogenous ABA and ethylene production during the period of storage mobilization and the changes observed in the production of these endogenous hormones in the presence of glucose and sucrose, suggested a correlation between the signalling pathway of these hormones and the sugars. These findings suggest that ABA, ethylene and sugars play a role in the control of the hydrolytic enzyme activities in seeds of S. virgata, controlling the process of storage degradation. This is thought to ensure a balanced flow of the carbon and nitrogen for seedling development.

Expression pattern of four storage xyloglucan mobilization-related genes during seedling development of the rain forest tree Hymenaea courbaril L.

During seedling establishment, cotyledons of the rain forest tree Hymenaea courbaril mobilize storage cell wall xyloglucan to sustain growth. The polysaccharide is degraded and its products are transported to growing sink tissues. Auxin from the shoot controls the level of xyloglucan hydrolytic enzymes. It is not yet known how important the expression of these genes is for the control of storage xyloglucan degradation. In this work, partial cDNAs of the genes xyloglucan transglycosylase hydrolase (HcXTH1) and beta-galactosidase (HcBGAL1), both related to xyloglucan degradation, and two other genes related to sucrose metabolism [alkaline invertase (HcAlkIN1) and sucrose synthase (HcSUS1)], were isolated. The partial sequences were characterized by comparison with sequences available in the literature, and phylogenetic trees were assembled. Gene expression was evaluated at intervals of 6 h during 24 h in cotyledons, hypocotyl, roots, and leaves, using 45-d-old plantlets. HcXTH1 and HcBGAL1 were correlated to xyloglucan degradation and responded to auxin and light, being down-regulated when transport of auxin was prevented by N-1-naphthylphthalamic acid (NPA) and stimulated by constant light. Genes related to sucrose metabolism, HcAlkIN1 and HcSUS1, responded to inhibition of auxin transport in consonance with storage mobilization in the cotyledons. A model is proposed suggesting that auxin and light are involved in the control of the expression of genes related to storage xyloglucan mobilization in seedlings of H. courbaril. It is concluded that gene expression plays a role in the control of the intercommunication system of the source-sink relationship during seeding growth, favouring its establishment in the shaded environment of the rain forest understorey.

Size and lipid content of nonmyrmecochorous diaspores: Effects on the interaction with litter-foraging ants in the Atlantic rain forest of Brazil

Ants are often attracted to diaspores not adapted for dispersal by ants. These diaspores may occasionally benefit from this interaction. We selected six nonmyrmecochorous plant species (Virola oleifera, Eugenia stictosepala, Cabralea canjerana, Citharexylum myrianthum, Alchornea glandulosa and Hyeronima alchorneoides) whose diaspores differ in size and lipid content, and investigated how these features affect the outcome of ant-diaspore interactions on the floor of a lowland Atlantic forest of Southeast Brazil. A total of 23 ant species were seen interacting with diaspores on the forest floor. Ants were generally rapid at discovering and cleaning the diaspore pulp or aril. Recruitment rate and ant attendance were higher for lipid-rich diaspores than for lipid-poor ones. Removal rate and displacement distance were higher for small diaspores. The large ponerine ant Pachycondyla striata, one of the most frequent attendants to lipid-rich arillate diaspores, transported the latter into their nests and discarded clean intact seeds on refuse piles outside the nest. Germination tests with cleaned and uncleaned diaspores revealed that the removal of pulp or aril may increase germination success in Virola oleifera, Cabralea canjerana, Citharexylum myrianthum and Alchornea glandulosa. Gas chromatography analyses revealed a close similarity in the fatty acid composition of the arils of the lipid-rich diaspores and the elaiosome of a typical myrmecochorous seed (Ricinus communis), corroborating the suggestion that some arils and elaiosomes are chemically similar. Although ant-derived benefits to diaspores - secondary dispersal and/or increased germination - varied among the six plant species studied, the results enhanced the role of ant-diaspore interactions in the post-dispersal fates of nonmyrmecochorous seeds in tropical forests. The size and the lipid-content of the diaspores were shown to be major determinants of the outcome of such interactions.

Lupane triterpenes from the leaves of the tropical rain forest tree Hopea odorata Roxb. and their cytotoxic activities, supplementary information

Chromatographic fractionation of the cytotoxic n-hexane extract of Hopea odorata Roxb. leaves led to the isolation of eight lupane triterpenes, which constitutes the first report of lupane-type triterpenes from this plant source. Furthermore, 3,30-dioxolup-20(29)-en-28-oic acid (6) was isolated for the first time from a natural source. Their structures were determined on the basis of spectroscopic methods, including 2D NMR analysis, and by comparison of their spectral data with literature values. Complete NMR assignments of the 1H and 13C NMR data were achieved for all compounds. Finally, the cytotoxic activities of the isolated compounds against four human cell lines (PC3, MDA-MB-231, HT-29 and HCT116) was also reported.

Amelioration of a degraded acid soil from SW Spain by no-tillage and Ca-amendment

En los suelos, el exceso de acidez lleva asociado deficiencias en ciertos nutrientes y una alta disponibilidad de aluminio, tóxico para los cultivos propios del ambiente mediterráneo. Su laboreo, provoca la pérdida de materia orgánica (MO), deteriora su estructura y reduce la actividad biológica, provocando en última instancia una menor calidad del suelo. Es de esperar pues que cuando se labran suelos ácidos, sus problemáticas particulares tiendan a agravarse. En nuestra zona de estudio, la “raña” de Cañamero (Extremadura, España), predominan los suelos muy ácidos y degradados por un laboreo inadecuado. Las rañas constituyen amplias plataformas casi horizontales, con unos suelos muy viejos (Palexerults), que se caracterizan por tener el complejo de cambio dominado por el aluminio, y un pH ácido que decrece en profundidad. Poseen un potente horizonte Bt rico en arcillas caoliníticas, que propicia que en periodos con exceso de lluvia, se generen capas colgadas de agua cercanas a la superficie. En torno a los años 1940’s estos suelos, que previamente sostenían un alcornocal, o su matorral de sustitución, se pusieron en cultivo. El laboreo aceleró la mineralización de la materia orgánica, agravó los problemas derivados del exceso de acidez y condujo al abandono de los campos cultivados por falta de productividad. Para recuperar la calidad de estos suelos degradados y obtener unos rendimientos compatibles con su uso agrícola es necesario, por un lado, aplicar enmiendas que eleven el pH y reduzcan la toxicidad del aluminio y, por otro, favorecer el incremento en el contenido en MO. En 2005 se implantó en esta raña un ensayo de campo para estudiar la influencia del no laboreo y de la utilización de una enmienda cálcica en parámetros relacionados con la calidad del suelo en un cultivo forrajero. El diseño experimental fue en parcelas divididas con cuatro repeticiones donde el factor principal fue el tipo de laboreo, no laboreo (NL) frente a laboreo convencional (LC), y el factor secundario el uso o no de una enmienda cálcica. La enmienda consistió básicamente en una mezcla de espuma de azucarería y yeso rojo y se incorporó al comienzo del ensayo hasta los 7 cm de profundidad. Desde el comienzo del ensayo el NL influyó positivamente en el contenido de carbono orgánico total (COT) y particulado (COP), mientras que la enmienda tuvo una ligera influencia al principio del ensayo en ambos pero su efecto positivo se desvaneció con el paso del tiempo. Los mayores contenidos en COT y POC se observaron cuando se combinó el NL con la enmienda. La enmienda incrementó con rapidez el pH, y el Ca, y disminuyó el contenido en aluminio hasta una profundidad de 50 cm, incluso en NL, y mejoró ligeramente la agregación del suelo. El NL por sí solo, gracias al aumento en POC, TOC y las proteínas del suelo relacionadas con la glomalina (PSRG), que son capaces de formar compuestos estables no tóxicos con el aluminio, también contribuyó a la reducción de la toxicidad de aluminio en la capa más superficial. Cuando en las campañas con exceso de precipitaciones se generaron capas colgadas de agua próximas a la superficie, el NL generó unas condiciones más favorables para la germinación y desarrollo del cultivo, resultando en una producción más alta que el LC. A ello contribuyó la mayor capacidad de almacenamiento de agua y la mayor transmisividad de esta hacia abajo, en la capa más superficial (0-5 cm) que propició una menor saturación por agua que el LC. Respecto a los parámetros relacionados con la agregación, el NL aumentó los macroagregados hasta los 10 cm de profundidad y favoreció la acumulación de CO y N en todas las fracciones de tamaño de agregados. Sin embargo, la recuperación del grado de macroagregación tras el cese del laboreo resulta lenta en comparación con otros suelos, posiblemente debido al bajo contenido en arcilla en el horizonte Ap. En comparación con el NL, la enmienda mostró también un efecto positivo, aunque muy ligero, en la agregación del suelo. En contradicción con otros estudios en suelos ácidos, nuestros resultados indican la existencia de una jerarquía de agregados, y destacan el papel importante de la MO en la mejora de la agregación. Tanto el NL como la enmienda favorecieron por separado varias propiedades químicas, físicas y biológicas del suelo, pero, en general, encontramos los mayores beneficios con su uso combinado. Además, a largo plazo el efecto positivo de NL en las propiedades del suelo fue en aumento, mientras que el efecto beneficioso de la enmienda se limitó básicamente a las propiedades químicas y se desvaneció en pocos años. Destacamos que las condiciones meteorológicas a lo largo del ensayo beneficiaron la producción de biomasa en NL, y en consecuencia las propiedades relacionadas con la materia orgánica, por lo que son un factor a tener en cuenta a la hora de evaluar los efectos de la enmienda y el laboreo sobre las propiedades del suelo, especialmente en zonas donde esas condiciones son muy variables entre una campaña y otra. Los resultados de este estudio han puesto de manifiesto que el NL no ha mermado la eficacia de la enmienda caliza, posiblemente gracias a la alta solubilidad de la enmienda aplicada, es más, el manejo con NL y enmienda es el que ha favorecido en mayor medida ciertos parámetros de calidad del suelo. Por el contrario el LC sí parece anular los beneficios de la enmienda en relación con las propiedades relacionadas con la MO. Por tanto, cabe concluir que la combinación de NL y la enmienda es una práctica adecuada para mejorar las propiedades químicas y físicas de suelos ácidos degradados por el laboreo. ABSTRACT Excessive acidity in soils is associated with deficiencies in certain nutrients and high concentrations of available aluminum, which is toxic for most Mediterranean crops. Tilling these soils results in the loss of soil organic matter (SOM), damages soil structure and reduces biological activity, ultimately degrading soil quality. It is expected, therefore, that when acid soils are tilled, their particular problems will tend to get worse. In our study area, the "Cañamero’s Raña” (Extremadura, Spain), acid soils degraded by an inappropriate tillage prevail. Rañas are large and flat platforms with very old soils (Palexerults), which are characterized by an exchange complex dominated by aluminum and an acid pH which decreases with depth. These soils have a strong Bt horizon rich in kaolinite clays, which encourages the formation of perched water-tables near the soil surface during periods of excessive rain. During the first third of the 20th century, these soils, that previously supported cork oak or its scrub replacement, were cultivated. Tillage accelerated the mineralization of the SOM, aggravating the problems of excessive acidity, which finally led to the abandonment of the land due to low productivity. To recover the quality of these degraded soils and to obtain consistent yields it is necessary, first, to apply amendments to raise the pH and reduce aluminum toxicity, and second to encourage the accumulation of SOM. In 2005 a field trial was established in the Raña to study the influence of no-tillage and the use of a Ca-amendment on soil quality related parameters in a forage crop agrosystem. The experimental design was a split-plot with four replicates where the main factor was tillage type, no-tillage (NT) versus traditional tillage (TT) and the secondary factor was the use or not of a Ca-amendment. The Ca-amendment was a mixture of sugar foam and red gypsum that was incorporated into the top 7 cm of the soil. Since the beginning of the experiment, NT had a positive influence on total and particulate organic carbon (TOC and POC, respectively), while the Ca-amendment had a small positive influence at the beginning of the study but its effect diminished with time. The highest TOC and POC contents were observed when NT and the Ca-amendment were combined. The Ca-amendment, even under NT, rapidly increased pH and Ca, and decreased the aluminum content to a depth of 50 cm, as well as improving soil aggregation slightly. NT, due to the increased POC, TOC and Glomalin-related soil proteins (GRSP), which can form stable non-toxic compounds with aluminum, also contributed to the reduction of aluminum toxicity in the upper layer. When perched water-tables near the soil surface were formed in campaigns with excessive rainfall, NT provided more favorable conditions for germination and crop development, resulting in higher yields compared with TT. This was directly related to the higher water storage capacity and the greater transmissivity of the water downwards from the upper layers, which led to lower water saturation under NT compared with TT. With regards to the aggregation-related parameters, NT increased macroaggregation to a depth of 10 cm and favored the accumulation of OC and N in all aggregate size fractions. However, the degree of recovery of macroaggregation after tillage ceased was slow compared with other soils, possibly due to the low clay content in the Ap horizon. Compared with NT, the Ca-amendment had a slight positive effect on soil aggregation. In contrast to other studies in acid soils, our results indicate the existence of an aggregate hierarchy, and highlight the important role of SOM in improving aggregation. Both NT and the Ca-amendment separately favored various chemical, physical and biological soil properties, but in general we found the greatest benefits when the two treatments were combined. In addition, the positive effect of NT on soil properties increased with time, while the beneficial effect of the Ca-amendment, which was limited to the chemical properties, vanished after a few years. It is important to note that the meteorological conditions throughout the experiment benefited biomass production under NT and, as a consequence, organic matter related properties. This suggests that meteorological conditions are a factor to consider when evaluating the effects of Ca-amendments and tillage on soil properties, especially in areas where such conditions vary significantly from one campaign to another. The results of this study show that NT did not diminish the effectiveness of the Ca-amendment, possibly due to the high solubility of the selected amendment. Moreover, the combination of NT and the Ca-amendment was actually the management that favored certain soil quality parameters the most. By contrast, TT seemed to nullify the benefits of the Ca-amendment with regards to the OM related properties. In conclusion, the combination of NT and the application of a Ca-amendment is an advisable practice for improving the chemical and physical properties of acid soils degraded by tillage.

No evidence for association of ataxia-telangiectasia mutated gene T2119C and C3161G amino acid substitution variants with risk of breast cancer

Background There is evidence that certain mutations in the double-strand break repair pathway ataxia-telangiectasia mutated gene act in a dominant-negative manner to increase the risk of breast cancer. There are also some reports to suggest that the amino acid substitution variants T2119C Ser707Pro and C3161G Pro1054Arg may be associated with breast cancer risk. We investigate the breast cancer risk associated with these two nonconservative amino acid substitution variants using a large Australian population-based case–control study. Methods The polymorphisms were genotyped in more than 1300 cases and 600 controls using 5' exonuclease assays. Case–control analyses and genotype distributions were compared by logistic regression. Results The 2119C variant was rare, occurring at frequencies of 1.4 and 1.3% in cases and controls, respectively (P = 0.8). There was no difference in genotype distribution between cases and controls (P = 0.8), and the TC genotype was not associated with increased risk of breast cancer (adjusted odds ratio = 1.08, 95% confidence interval = 0.59–1.97, P = 0.8). Similarly, the 3161G variant was no more common in cases than in controls (2.9% versus 2.2%, P = 0.2), there was no difference in genotype distribution between cases and controls (P = 0.1), and the CG genotype was not associated with an increased risk of breast cancer (adjusted odds ratio = 1.30, 95% confidence interval = 0.85–1.98, P = 0.2). This lack of evidence for an association persisted within groups defined by the family history of breast cancer or by age. Conclusion The 2119C and 3161G amino acid substitution variants are not associated with moderate or high risks of breast cancer in Australian women.

Best after rain : waterfall discharges and the tourist experience

Waterfalls attract tourists because they are aesthetically appealing landscape features that are not part of everyday experience. It is generally understood that falls are usually seen at their best when there is a copious flow of water, especially after heavy rain. Guidebooks often contain this observation when referring to waterfalls, sometimes warning readers that the flow may be severely reduced during dry periods. Indeed, many visitors are disappointed when they see falls at such times. Some are saddened when the discharge of a waterfall has been depleted by the abstraction of water upstream for power generation or other purposes. While, for those in search of the Sublime or merely the superlative, size is often important, small waterfalls can give great pleasure to lovers of landscape beauty. According to guidebooks, however, even these falls are usually best seen after rain. Drawing on tourist and travel literature and personal journals from the eighteenth century to the present, and with reference to examples from different parts of the world, this paper discusses the importance of discharge in the tourist experience of waterfalls.