Improving photofermentative hydrogen production through metabolic engineering and DOE (Design of Experiments)

A l’heure actuelle, les biocarburants renouvelables et qui ne nuit pas à l'environnement sont à l'étude intensive en raison de l'augmentation des problèmes de santé et de la diminution des combustibles fossiles. H2 est l'un des candidats les plus prometteurs en raison de ses caractéristiques uniques, telles que la densité d'énergie élevée et la génération faible ou inexistante de polluants. Une façon attrayante pour produire la H2 est par les bactéries photosynthétiques qui peuvent capter l'énergie lumineuse pour actionner la production H2 avec leur système de nitrogénase. L'objectif principal de cette étude était d'améliorer le rendement de H2 des bactéries photosynthétiques pourpres non sulfureuses utilisant une combinaison de génie métabolique et le plan des expériences. Une hypothèse est que le rendement en H2 pourrait être améliorée par la redirection de flux de cycle du Calvin-Benson-Bassham envers du système de nitrogénase qui catalyse la réduction des protons en H2. Ainsi, un PRK, phosphoribulose kinase, mutant « knock-out » de Rhodobacter capsulatus JP91 a été créé. L’analyse de la croissance sur des différentes sources de carbone a montré que ce mutant ne peut croître qu’avec l’acétate, sans toutefois produire d' H2. Un mutant spontané, YL1, a été récupéré qui a retenu l'cbbP (codant pour PRK) mutation d'origine, mais qui avait acquis la capacité de se développer sur le glucose et produire H2. Une étude de la production H2 sous différents niveaux d'éclairage a montré que le rendement d’YL1 était de 20-40% supérieure à la souche type sauvage JP91. Cependant, il n'y avait pas d'amélioration notable du taux de production de H2. Une étude cinétique a montré que la croissance et la production d'hydrogène sont fortement liées avec des électrons à partir du glucose principalement dirigés vers la production de H2 et la formation de la biomasse. Sous des intensités lumineuses faibles à intermédiaires, la production d'acides organiques est importante, ce qui suggère une nouvelle amélioration additionnel du rendement H2 pourrait être possible grâce à l'optimisation des processus. Dans une série d'expériences associées, un autre mutant spontané, YL2, qui a un phénotype similaire à YL1, a été testé pour la croissance dans un milieu contenant de l'ammonium. Les résultats ont montré que YL2 ne peut croître que avec de l'acétate comme source de carbone, encore une fois, sans produire de H2. Une incubation prolongée dans les milieux qui ne supportent pas la croissance de YL2 a permis l'isolement de deux mutants spontanés secondaires intéressants, YL3 et YL4. L'analyse par empreint du pied Western a montré que les deux souches ont, dans une gamme de concentrations d'ammonium, l'expression constitutive de la nitrogénase. Les génomes d’YL2, YL3 et YL4 ont été séquencés afin de trouver les mutations responsables de ce phénomène. Fait intéressant, les mutations de nifA1 et nifA2 ont été trouvés dans les deux YL3 et YL4. Il est probable qu'un changement conformationnel de NifA modifie l'interaction protéine-protéine entre NifA et PII protéines (telles que GlnB ou GlnK), lui permettant d'échapper à la régulation par l'ammonium, et donc d'être capable d'activer la transcription de la nitrogénase en présence d'ammonium. On ignore comment le nitrogénase synthétisé est capable de maintenir son activité parce qu’en théorie, il devrait également être soumis à une régulation post-traductionnelle par ammonium. Une autre preuve pourrait être obtenue par l'étude du transcriptome d’YL3 et YL4. Une première étude sur la production d’ H2 par YL3 et YL4 ont montré qu'ils sont capables d’une beaucoup plus grande production d'hydrogène que JP91 en milieu d'ammonium, qui ouvre la porte pour les études futures avec ces souches en utilisant des déchets contenant de l'ammonium en tant que substrats. Enfin, le reformage biologique de l'éthanol à H2 avec la bactérie photosynthétique, Rhodopseudomonas palustris CGA009 a été examiné. La production d'éthanol avec fermentation utilisant des ressources renouvelables microbiennes a été traitée comme une technique mature. Cependant, la plupart des études du reformage de l'éthanol à H2 se sont concentrés sur le reformage chimique à la vapeur, ce qui nécessite généralement une haute charge énergetique et résultats dans les émissions de gaz toxiques. Ainsi le reformage biologique de l'éthanol à H2 avec des bactéries photosynthétiques, qui peuvent capturer la lumière pour répondre aux besoins énergétiques de cette réaction, semble d’être plus prometteuse. Une étude précédente a démontré la production d'hydrogène à partir d'éthanol, toutefois, le rendement ou la durée de cette réaction n'a pas été examiné. Une analyse RSM (méthode de surface de réponse) a été réalisée dans laquelle les concentrations de trois facteurs principaux, l'intensité lumineuse, de l'éthanol et du glutamate ont été variés. Nos résultats ont montré que près de 2 moles de H2 peuvent être obtenus à partir d'une mole d'éthanol, 33% de ce qui est théoriquement possible.

Integrated pest management and the (un)sustainable use of pesticides

Doutoramento em Engenharia Agronómica - Instituto Superior de Agronomia - UL

Stability of clay-based catalysts in contact with water vapour

The search for cleaner processes is one of the major challenges in modern chemical industries. In this context clay derived materials are environmentally friendly catalysts that can be easily tailored to optimize their catalytic activity for a precise reaction of interest. Furthermore, clay-based catalysts can be easily separated, recovered and reused and their versatility, low cost, high catalytic activity and/or selectivity render them very attractive materials. Considering that the stability towards water vapour is a crucial aspect for catalytic performance and reuse of the catalysts, we present a study of the pore structure stability, in the presence of water vapour, of clay catalysts prepared by acid activation with HCl solutions and ion-exchange with sodium, aluminium and iron, from a natural clay collected at Serra de Dentro (Porto Santo Island, Portugal) [1]. For elucidating the influence of water vapour on the pore structure stability, water vapour adsorption- -desorption isotherm, at 298 K, was determined on each sample by gravimetric method as well as n-pentane adsorption−desorption isotherms, at 298 K, which were determined before and after the corresponding water adsorption-desorption isotherms. Prior to the measurements, the samples were outgassed during 5 h at 473 K and the adsorptives were outgassed by repeated freeze–thaw cycles. The results to be reported in the communication allow us to state that, upon contact with water vapour, the less acid activated catalysts suffered some reduction in pore volume reflecting changes in the pore structure, while the more acid activated catalysts and those prepared by ion-exchange presented excellent stability upon one cycle of water vapour adsorption-desorption. The results are corroborated by nitrogen adsorption-desorption isotherms determined, at 77 K, before and after the water and n-pentane adsorption-desorption measurements.

Trends and strategies of ozone application in environmental problems

Efforts presented by the scientific community in recent years towards the development of numerous green chemical processes and wastewater treatment technologies are presented and discussed. In the light of these approaches, environmentally friendly technologies, as well as the key role played by the well-known advanced oxidation processes, are discussed, giving special attention to the ones comprising ozone applications. Fundamentals and applied aspects dealing with ozone technology and its application are also presented.

A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation

An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 mu g L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 mu g L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 mu g of PAP and 5.7 mu g of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria. (c) 2010 Elsevier B.V. All rights reserved.

Electrochemical study of modified non-functional bis-silane layers on Al alloy 2024-T3

In the last few years great efforts have been made in order to find and to develop environmentally friendly substitutes for Cr6+ pre-treatments applied on aluminium alloys used in the aircraft industry. Among the potential substitutes, silane layers have attracted considerable interest from researchers and from the industry. The present work investigates the anti-corrosion behaviour of (bis-1, 2-(triethoxysilyl) ethane (BTSE)) silane layers modified with Ce ions and/or silica nanoparticles applied on Al alloy 2024-T3 substrates. The corrosion behaviour was investigated in 0.1 M NaCl solution via d.c. polarization and electrochemical impedance spectroscopy (EIS). Contact angle measurements and XPS were used to assess information on the chemistry of the silane pre-treated surfaces. The results have shown that the introduction of additives improves the corrosion protection properties of the silane layer. (c) 2008 Elsevier Ltd. All rights reserved.

Fungal pathogens as classical biological control agents against arthropods

Fungal entomopathogens have been used more frequently than other types of pathogens for classical biological control. Among 136 programs using different groups of arthropod pathogens, 49.3% have introduced fungal pathogens (including both the traditional fungi and microsporidia). The most commonly introduced species was Metarhizium anisopliae (Metschnikoff) Sorokin, with 13 introductions, followed by Entomophaga maimaiga Humber, Shimazu & Soper, which was released seven times. The majority of introduction programs have focused on controlling invasive species of insects or mites (70.7%) rather than on native hosts (29.4%). Almost half of the introductions of traditional fungi targeted species of Hemiptera and 75% of the microsporidia introduced have been introduced against lepidopteran species. The United States was the country where most introductions of fungi took place (n = 24). From 1993 to 2007, no arthropod pathogens were released in the US due to the rigorous regulatory structure, but in 2008 two species of microsporidia were introduced against the gypsy moth, Lymantria dispar (L.). Establishment of entomopathogenic fungi in programs introducing traditional fungi was 32.1% and establishment was 50.0% for programs introducing microsporidia. In some programs, releases have resulted in permanent successful establishment with no non-target effects. In summary, classical biological control using fungal entomopathogens can provide a successful and environmentally friendly avenue for controlling arthropod pests, including the increasing numbers of invasive non-native species.

Investigating the gap between citizens` sustainability attitudes and food purchasing behaviour: empirical evidence from Brazilian pork consumers

Consumers worldwide are increasingly concerned with sustainable production and consumption. Recently, a comprehensive study ranked 17 countries in regard to their environmentally friendly behaviour among consumers. Brazil was one of the top countries in the list. Yet, several studies highlight significant differences between consumers` intentions to consume ethically, and their actual purchase behaviour: the so-called `Attitude-Behaviour Gap`. In developing countries, few studies have been conducted on this issue. The objective of this study is therefore to investigate the gap between citizens` sustainability-related attitudes and food purchasing behaviour using empirical data from Brazil. To this end, Brazilian citizens` attitudes towards pig production systems were mapped through conjoint analysis and their coexistence with relevant pork product-related purchasing behaviour of consumers was investigated through cluster analysis. The conjoint experiment was carried Out with empirical data collected from 475 respondents surveyed in the South and Center-West regions of Brazil. The results of the conjoint analysis were used for a subsequent cluster analysis in order to identify clusters of Brazilian citizens with diversified attitudes towards pig production systems, using socio-demographics, attitudes towards sustainability-related themes that are expected to influence the way they evaluate pig production systems, and consumption frequency of various pork products as clusters` background information. Three clusters were identified as `indifferent`, `environmental conscious` and `sustainability-oriented` citizens. Although attitudes towards environment and nature had indeed an influence on citizens` specific attitudes towards pig farming at the cluster level, the relationship between `citizenship` and consumption behaviour was found to be weak. This finding is similar to previous research conducted with European consumers: what people (in their role of citizens) think about pig production systems does not appear to significantly influence their pork consumption choices. Improvements in the integrated management of this chain would better meet consumers` sustainability-related expectations towards pig production systems.

In the eye of the storm: exploring the introduction of environmental issues in the production function in Brazilian companies

This article aims to analyse the introduction of environmental issues in the context of the production function, which has been referred to as the organisational area to lead corporate environmental management. With that purpose, the theoretical references for corporate environmental management and the necessary alterations in production function have been organised to include environmental aspects, especially in terms of product and process development, quality management, and logistics. Considering that this research field still lacks empirical evidence for Brazilian companies, four case studies were conducted using companies located in the country. The environmental management maturity level of those companies tends to follow the rate with which the environmental issue is introduced in production sub-areas, especially in the product development process. However, in most cases we found that the companies had difficulties in structuring the insertion of the environmental dimension in logistics. The final notes point out the distance observed between what is recommended by international literature and the reality of Brazilian companies in the challenge of making the production function environmentally friendly.

Carbamazepine oxidation catalyzed by iron and manganese porphyrins supported on aminofunctionalized matrices

This work describes the catalytic activity of manganese and iron porphyrins, Mn and Fe(TFPP)Cl, covalently immobilized on the aminofunctionalized supports montmorillonite K-10 (MontX) and silica (SilX), where X= 1 or 2 represents the length of the organic chain (""arms"") binding the metalloporphyrin to the support. These systems were characterized by UV-vis and Electronic Paramagnetic Resonance (EPR), and they were used as catalysts in the oxidation of carbamazepine (CBZ) by the oxidants iodosylbenzene (PhIO) and hydrogen peroxide. The manganese porphyrin (MnP) catalysts proved to be efficient and selective for the epoxide, the main CBZ metabolite in natural systems. MnMont1 was an excellent catalyst when PhIO was used as oxidant, even better than the same MnP in homogeneous system. Supports bearing short ""arms"" led to the best yields. Although H2O2 is an environmentally friendly oxidant, low product yields were obtained when it was employed in CBZ oxidation. Fe(TFPP)CI immobilized on aminofunctionalized supports was not an efficient catalyst, probably due to the presence of Fe(H) species in the matrix, which led to the less reactive intermediate PFe(IV)(O). (c) 2007 Elsevier B.V. All rights reserved.

Wildlife-based tourism & increased support for nature conservation financially and otherwise: evidence from sea-turtle ecotourism at Mon Repos

The arguments of most conservationists supporting ecotourism have been based on the view that it is environmentally friendly as a resource-use and that receipts from it can counter demands to use the natural resources involved for more extractive economic purposes. But wildlife-based ecotourism can also have positive impacts in itself on the willingness of tourists to pay for wildlife conservation, strengthen the pro-conservation attitudes of tourists, and foster personal actions by them that contribute to wildlife conservation. These aspects are explored in this article on the basis of a survey of tourists visiting Mon Repos Beach near Bundaberg, Queensland, for the purpose of watching marine turtles. The results enable several of the conservation impacts of this experience on tourists to be quantified, and highlight important relationships between specific socio-economic variables and the willingness of tourists to pay for the protection of sea turtles. Furthermore, it is shown that the on-site experiences of ecotourists have positive impacts on the willingness of tourists to pay for the conservation of wildlife, and that willingness to pay is sensitive to whether or not wildlife is seen. It is suggested that in situ ecotourism is likely to be a more powerful force for fostering pro-conservation attitudes and actions among visitors than ex situ wildlife-based tourism in aquaria and zoos.

The limits of environmental responsibility - A stormwater case study

The motivation for concern about the environment beyond one's neighborhood is still relatively poorly understood. This article examines the determinants of feelings of responsibility at a regional watershed level. Using demographic, attitudinal, self-reported behavior and neighborhood mapping measures from four cities in Australia, five hypotheses were derived. These were that wider environmental concerns would depend on (a) the physical and social characteristics of the respondents' neighborhoods, (b) the size of their perceived neighborhoods, (c) the length of residence at their localities, (d) educational level and attitudes toward environmental moral responsibility (and the interaction between them), and (e) the level of reported environmentally friendly behavior. Support was gained for all hypotheses except length of residence and the role of general moral attitudes toward the environment. It is concluded that to explain community action at the regional level, it is important to include both spatial and psychological insights and methodologies in research.

The influence of curing conditions on the mechanical performance of concrete made with recycled concrete waste

Research on the use of Construction and Demolition Waste (CDW) as recycled aggregate (in particular crushed concrete) for the production of new concrete has by now established the feasibility of this environmentally-friendly use of otherwise harmful waste. However, contrary to conventional concrete (CC), no large applications of concrete made with recycled concrete have been made and there is still a lack of knowledge in some areas of production and performance of recycled aggregate concrete (RAC). One issue concerns curing conditions: these greatly affect the performance of concrete made on site and some potential users of RAC wonder how RAC is affected by far-from-ideal curing conditions. This paper shows the main results of experiments to determine the influence of different curing conditions on the mechanical performance of concrete made with coarse recycled aggregate from crushed concrete. The properties analyzed include compressive strength, splitting tensile strength, modulus of elasticity, and abrasion resistance. The general conclusion in terms of mechanical performance is that RAC is affected by curing conditions roughly in the same way as CC. (C) 2011 Elsevier Ltd. All rights reserved.

Renewable-based generation integration in electricity markets with virtual power producers

The development of renewable energy sources and Distributed Generation (DG) of electricity is of main importance in the way towards a sustainable development. However, the management, in large scale, of these technologies is complicated because of the intermittency of primary resources (wind, sunshine, etc.) and small scale of some plants. The aggregation of DG plants gives place to a new concept: the Virtual Power Producer (VPP). VPPs can reinforce the importance of these generation technologies making them valuable in electricity markets. VPPs can ensure a secure, environmentally friendly generation and optimal management of heat, electricity and cold as well as optimal operation and maintenance of electrical equipment, including the sale of electricity in the energy market. For attaining these goals, there are important issues to deal with, such as reserve management strategies, strategies for bids formulation, the producers’ remuneration, and the producers’ characterization for coalition formation. This chapter presents the most important concepts related with renewable-based generation integration in electricity markets, using VPP paradigm. The presented case studies make use of two main computer applications:ViProd and MASCEM. ViProd simulates VPP operation, including the management of plants in operation. MASCEM is a multi-agent based electricity market simulator that supports the inclusion of VPPs in the players set.

Arquitetura para aquisição de respostas a perguntas frequentes

Dissertação de natureza científica realizada para obtenção do grau de Mestre em Engenharia Informática e de Computadores