Changes of social relevance in the transplantation of theories: the examples of economics and agronomics

Includes bibliography

Access to information, participation and justice in environmental matters in Latin America and the Caribbean: situation, outlook and examples of good practice [Principle 10 of the Rio Declaration on Environment and Development, 1992]

Principle 10 of the Rio Declaration on Environment and Development, 1992

Access to information, participation and justice in environmental matters in Latin America and the Caribbean: situation, outlook and examples of good practice

Includes bibliography

A real-time thermal field theoretical analysis of Kubo-type shear viscosity: Numerical understanding with simple examples

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

Emergetic ternary diagrams: five examples for application in environmental accounting for decision-making

In a recent paper, "A combined tool for environmental scientists and decision makers: ternary diagrams and emergy accounting." [Giannettti BF, Barrella FA, Almeida CMVB. A combined tool for environment scientists and decision makers: ternary diagrams and emergy accounting. J Clean Prod, in press http://dx.doi.org/10.1016/j.jclepro.2004.09.002] Ternary diagrams were proposed as a graphical tool to assist emergy analysis. The graphical representation of the emergy accounting data makes it possible to compare processes and systems with and without ecosystem services, to evaluate improvements and to follow the system performance over time. The graphic tool is versatile and adaptable to represent products, processes, systems, countries, and different periods of time.The use and the versatility of ternary diagrams for assisting in performing emergy analyses are illustrated by means of five examples taken from the literature, which are presented and discussed. It is shown that emergetic ternary diagram's properties assist the assessment of the system of the system efficiency, its dependance upon renewable and non-renewable inputs and the environmental support for dilution and abatement of process emissions. With the aid of ternary diagrams, details such as the interaction between systems and between systems and the environment are recognized and evaluated. Such a tool for graphical analysis allows a transparent presentation of the results and can serve as an interface between emergy scientists and decision makers, provided the meaning of each line in the diagram is carefully explained and understood. (c) 2005 Elsevier Ltd. All rights reserved.

BIOMOLECULES EXTRACTED BY ATPS: PRACTICAL EXAMPLES

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

Biomolecules extracted by ATPs: practical examples

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

Coordination of water to organolead(IV) nitrates: The examples of [PbPh2(NO3)(2)(H2O)(2)] and [PbMe3(NO3)(H2O)]

The compound [PbPh2(NO3)(2)(H2O)(2)] was synthesized and characterized by spectroscopic methods (IR; H-1, C-13 and Pb-207 NMR) and mass spectrometry. An X-ray diffraction study showed that the crystal is a supramolecular tridimensional network of hydrogen-bonded PbPh2(NO3)(2)(H2O)(2) units in which the Pb atom is octacoordinated and adopts a distorted hexagonal bipyramidal geometry, with four O (bidentate nitrate) and two O (water) atoms in equatorial positions and two C-phenyl atoms in axial positions. The crystal of [PbMe3(NO3)(H2O)], obtained as a byproduct in the synthesis of PbMe2(NO3)(2), contains chains of hydrogen-bonded PbMe3(NO3)(H2O) units in which the Pb atom is pentacoordinated with a slightly distorted trigonal bipyramidal environment. In this arrangement the three C-methyl atoms are equatorial and the O atoms from the monodentate nitrate and the water molecule are axial. (C) 2011 Elsevier Ltd. All rights reserved.

BANACH SPACES WITHOUT MINIMAL SUBSPACES - EXAMPLES

We analyse several examples of separable Banach spaces, some of them new, and relate them to several dichotomies obtained in [11], by classifying them according to which side of the dichotomies they fall.

Children and teenagers working in artistic labor: Brazilian situation and international examples

This descriptive study about children and adolescents artistic labor verifies the applicable legislation, in Brazil, regarding the participation of children and adolescents in the entertainment industry and in advertising campaigns, as well as the judicial processes about the theme known by the Brazilian Superior Court of Justice up to October, 2010. The results permit to conclude that, due to the lack of specific regulation and general rule of child labor prohibition, the restrictions that tend to protect the health and security of children and adolescents that act in the artistic niche (television, advertising, fashion, movies etc.) have been, in Brazil, at subjective criteria of the judges and, in many cases, in the hands of producers themselves. Brief considerations on how other countries regulate the theme are also presented (the USA, Portugal and Argentina).

Modal hedges in para-pharmaceutical product instructions: some examples from English and Serbian

[EN] The paper investigates how modal hedges (Coates 1983) understood as expressions of procedural meaning , i.e. expressions which instruct the addressee/reader how to process the propositional content of an utterance/statement (Watts 2004) are used in product descriptions, advertisements and consumer instructions leaflets for a number of products belonging to the Consumer Health Care category for the purposes of complying with consumer protection laws on the one hand and serving as an implicit disclaimer of manufacturer’s responsibility on the other. The analysis is carried out contrastively for two languages, English and Serbian. The results obtained are discussed and viewed as a matter of cultural variety and difference, especially taking into consideration the fact that consumer protection laws seem to be equally strict in US, UK and Commonwealth, Europe and Serbia.

Tectonics and kinematics of curved mountain belts: examples from the Andes and the Alps

Curved mountain belts have always fascinated geologists and geophysicists because of their peculiar structural setting and geodynamic mechanisms of formation. The need of studying orogenic bends arises from the numerous questions to which geologists and geophysicists have tried to answer to during the last two decades, such as: what are the mechanisms governing orogenic bends formation? Why do they form? Do they develop in particular geological conditions? And if so, what are the most favorable conditions? What are their relationships with the deformational history of the belt? Why is the shape of arcuate orogens in many parts of the Earth so different? What are the factors controlling the shape of orogenic bends? Paleomagnetism demonstrated to be one of the most effective techniques in order to document the deformation of a curved belt through the determination of vertical axis rotations. In fact, the pattern of rotations within a curved belt can reveal the occurrence of a bending, and its timing. Nevertheless, paleomagnetic data alone are not sufficient to constrain the tectonic evolution of a curved belt. Usually, structural analysis integrates paleomagnetic data, in defining the kinematics of a belt through kinematic indicators on brittle fault planes (i.e., slickensides, mineral fibers growth, SC-structures). My research program has been focused on the study of curved mountain belts through paleomagnetism, in order to define their kinematics, timing, and mechanisms of formation. Structural analysis, performed only in some regions, supported and integrated paleomagnetic data. In particular, three arcuate orogenic systems have been investigated: the Western Alpine Arc (NW Italy), the Bolivian Orocline (Central Andes, NW Argentina), and the Patagonian Orocline (Tierra del Fuego, southern Argentina). The bending of the Western Alpine Arc has been investigated so far using different approaches, though few based on reliable paleomagnetic data. Results from our paleomagnetic study carried out in the Tertiary Piedmont Basin, located on top of Alpine nappes, indicate that the Western Alpine Arc is a primary bend that has been subsequently tightened by further ~50° during Aquitanian-Serravallian times (23-12 Ma). This mid-Miocene oroclinal bending, superimposing onto a pre-existing Eocene nonrotational arc, is the result of a composite geodynamic mechanism, where slab rollback, mantle flows, and rotating thrust emplacement are intimately linked. Relying on our paleomagnetic and structural evidence, the Bolivian Orocline can be considered as a progressive bend, whose formation has been driven by the along-strike gradient of crustal shortening. The documented clockwise rotations up to 45° are compatible with a secondary-bending type mechanism occurring after Eocene-Oligocene times (30-40 Ma), and their nature is probably related to the widespread shearing taking place between zones of differential shortening. Since ~15 Ma ago, the activity of N-S left-lateral strike-slip faults in the Eastern Cordillera at the border with the Altiplano-Puna plateau induced up to ~40° counterclockwise rotations along the fault zone, locally annulling the regional clockwise rotation. We proposed that mid-Miocene strike-slip activity developed in response of a compressive stress (related to body forces) at the plateau margins, caused by the progressive lateral (southward) growth of the Altiplano-Puna plateau, laterally spreading from the overthickened crustal region of the salient apex. The growth of plateaux by lateral spreading seems to be a mechanism common to other major plateaux in the Earth (i.e., Tibetan plateau). Results from the Patagonian Orocline represent the first reliable constraint to the timing of bending in the southern tip of South America. They indicate that the Patagonian Orocline did not undergo any significant rotation since early Eocene times (~50 Ma), implying that it may be considered either a primary bend, or an orocline formed during the late Cretaceous-early Eocene deformation phase. This result has important implications on the opening of the Drake Passage at ~32 Ma, since it is definitely not related to the formation of the Patagonian orocline, but the sole consequence of the Scotia plate spreading. Finally, relying on the results and implications from the study of the Western Alpine Arc, the Bolivian Orocline, and the Patagonian Orocline, general conclusions on curved mountain belt formation have been inferred.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).