Sponge halogenated natural products found at parts-per-million levels in marine mammals

Several unknown, abundant brominated compounds (BCs) were recently detected in the blubber of dolphins and other marine mammals from Queensland (northeast Australia). The BC were interpreted as potential natural products due to the lack of anthropogenic sources for these compounds. This study investigated whether some of the BCs accumulated by diverse marine mammal species are identical with natural BCs previously isolated from sponges (Dysidea sp.) living in the same habitat. Isolates from sponges and mollusks (Asteronotus cespitosus) were compared with the signals detected in the mammals' tissue. Mass spectra and gas chromatography retention times on four different capillary columns of the isolates from sponges and mammals were identical in all respects. This proves that the chemical name of the compound previously labeled BC-2 is 4,6-dibromo-2-(2'-dibromo)phenoxyanisole and that the chemical name of BC-11 is 3,5-dibromo-2-(3',5'-dibromo-2'-methoxy)phenoxyanisole. Using a quantitative reference solution of BC-2, we established that the concentrations of the brominated metabolies found in the marine mammals are frequently >1 mg/kg. The highest concentration (3.8 mg/kg), found in a sample of pygmy sperm whale (Kogia breviceps), indicates that BC-2 is a bioaccumulative, natural organohalogen compound. This is supported by the concentrations of the BCs in our samples being equal to the highest concentrations of anthropogenic BCs in any environmental sample. The quantitative determination of BC-2 in blubber of marine mammals from Africa and the Antarctic suggests that BC-2 is wide-spread. These results are direct proof that marine biota can produce persistent organic chemicals that accumulate to substantial concentrations in higher trophic organisms.

Seasonal changes in the diving performance of the bimodally respiring freshwater turtle Rheodytes leukops in a natural setting

The objective of this study was to investigate how seasonally fluctuating environmental conditions influence the diving performance of the highly aquatic, bimodally respiring turtle Rheodytes leukops in a natural setting. Over four consecutive seasons (Austral autumn 2000 to summer 2001), the diving behaviour of adult turtles was recorded via pressure-sensitive time-depth recorders within Marlborough Creek, central Queensland, Australia. Short surfacing intervals recorded for R. leukops in winter suggest that the species utilizes aquatic respiration as an overwintering strategy to prevent the development of a metabolic acidosis during the long inactive dives observed during the season. As water temperature increases and aquatic P-O 2 decreases, R. leukops switches from facultative to obligate air-breathing, presumably because of the increased metabolic cost associated with aquatic respiration under summer conditions. Increases in mean surfacing time from winter to spring and summer are attributed to seasonal changes in behaviour possibly associated with foraging rather than to the physiological state of the turtle, given that no difference in median surfacing time among seasons was observed.

New Steel Alloys for the Design of Heat Recovery Steam Generator Components of Combined Cycle Gas Plants

Demand for power is growing every day, mainly due to emerging economies in countries such as China, Russia, India, and Brazil. During the last 50 years steam pressure and temperature in power plants have been continuously raised to improve thermal efficiency. Recent efforts to improve efficiency leads to the development of a new generation of heat recovery steam generator, where the Benson once-through technology is applied to improve the thermal efficiency. The main purpose of this paper is to analyze the mechanical behavior of a high pressure superheater manifold by applying finite element modeling and a finite element analysis with the objective of analyzing stress propagation, leading to the study of damage mechanism, e.g., uniaxial fatigue, uniaxial creep for life prediction. The objective of this paper is also to analyze the mechanical properties of the new high temperature resistant materials in the market such as 2Cr Bainitic steels (T/P23 and T/P24) and also the 9-12Cr Martensitic steels (T/P91, T/P92, E911, and P/T122). For this study the design rules for construction of power boilers to define the geometry of the HPSH manifold were applied.

Determination of total petroleum hydrocarbons in soil from different locations using infrared spectrophotometry and gas chromatography

Total petroleum hydrocarbons (TPH) are important environmental contaminants which are toxic to human and environmental receptors. Several analytical methods have been used to quantify TPH levels in contaminated soils, specifically through infrared spectrometry (IR) and gas chromatography (GC). Despite being two of the most used techniques, some issues remain that have been inadequately studied: a) applicability of both techniques to soils contaminated with two distinct types of fuel (petrol and diesel), b) influence of the soil natural organic matter content on the results achieved by various analytical methods, and c) evaluation of the performance of both techniques in analyses of soils with different levels of contamination (presumably non-contaminated and potentially contaminated). The main objectives of this work were to answer these questions and to provide more complete information about the potentials and limitations of GC and IR techniques. The results led us to the following conclusions: a) IR analysis of soils contaminated with petrol is not suitable due to volatilisation losses, b) there is a significant influence of organic matter in IR analysis, and c) both techniques demonstrated the capacity to accurately quantify TPH in soils, irrespective of their contamination levels.

Gas emissions on rice culture and its importance on air quality

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente Perfil Gestão de Sistemas Ambientais

Development of a "green process" for the isolation of natural functional extracts with anti-cancer activity - Application of high-pressure technology

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Isolation and encapsulation of a natural colourant using green technologies

The use of natural pigments instead of synthetic colourants is receiving growing interest in the food industry. In this field, cactus pears (Opuntia spp.) have been identified to be a promising betalainic crops covering a wide coloured spectrum. The aim of this work was to develop adequate clean and mild methodologies for the isolation and encapsulation of betacyanins, from cactus pear fruits (Opuntia spp.). Firstly, two different emerging technologies, namely PLE (Pressurized Liquid Extraction) and HPCDAE (High Pressure Carbon Dioxide-Assisted Extraction), were exploited to isolation of betacyanins form cactus pear fruits. Different process conditions were tested for the maximum recovery of betacyanins. Results showed that highest extraction yields were achieved for HPCDAE and mass ratio of pressurized carbon dioxide vs. acidified water was the parameter that most affected the betacyanins extraction. At optimum conditions of HPCDAE, Opuntia spp. extract presented a total betacyanin content of 211 ± 10 mg/100 g whereas extracts obtained using conventional extraction, PLE in static and in dynamic mode presented a total betacyanin content of 85 ± 3, 191 ± 2 and 153 ± 5 mg/100 g, respectively. HPCDAE has proven to be a successful technology to extract betacyanins from Opuntia spp. fruits. Afterward, Supercritical Fluid Technology was exploited to develop lipidic particles of betalain-rich extract. A betacyanin-rich conventional extract was encapsulated by PGSS® (Particles from Gas Saturated Solutions) technique. Different process conditions were tested in order to model the encapsulation of betacyanins. The pressure had a negative effect on betacyanin encapsulation. Lower pressures leads to an increase in the betacyanin encapsulation. This effect was more pronounced at higher temperatures and lower equilibrium time. At these conditions, Opuntia spp. particles presented 64.4 ± 4.5 mg/100 g and high antioxidant capacity. When compared with the Opuntia spp. dried extract, lipidic particles contributed to a better homogenization of the pink colour after incorporation in ice cream.

As relações UE-Ucrânia ao abrigo da parceria oriental: a projecção de poder da UE perante a Rússia e a criação de um limite entre dois cosmos

A crise política que teve início com a suspensão do Acordo de Associação da Ucrânia, em Setembro de 2014, reacendeu o debate sobre as implicações e consequências das relações da União Europeia (UE) ao nível da Parceria Oriental para com as suas relações bilaterais com a Rússia. A Ucrânia, que se encontra numa tradicional esfera de influência para a Rússia, e que por motivos históricos, económicos e políticos, se assume de grande relevo para a Europa, conheceu diversas fases de aproximação e contenção nas suas relações com a UE. Apesar da existência de uma fronteira geográfica entre a UE e a sua periferia, a UE estende-se, através das suas políticas desenvolvidas ao abrigo da Parceria Oriental, para além das linhas de Schengen. A Política Europeia de Vizinhança, contribui para o diluir das barreiras naturais através dos seus programas políticos, culturais e económicos. No entanto, a UE não conhece ainda uma verdadeira fronteira civilizacional – um limite no qual o mundo externo é demasiado diferente da sua génese e não poderá ser integrado no seu centro. A Rússia - um limite natural para a UE-, procura também estender a sua influência para além das suas fronteiras. Ambos se cruzam na região abrangida pela Parceria Oriental, procurando encontrar um limite real para o seu cosmos. A UE utiliza diversos instrumentos e capacidades por forma a desenvolver as relações com a sua vizinhança. Estes estão, no entanto, amplamente condicionados pela coesão interna da própria UE – a sua capacidade de gerar consenso por forma a formular políticas e desenvolver instrumentos. As relações desenvolvidas ao abrigo da Parceria Oriental são ainda influenciadas pela sua própria periferia, nomeadamente na vontade de assimilar ou não as políticas da UE. No caso específico da Ucrânia, que se manteve durante muito tempo num limbo geopolítico, no qual não se alinhou nem com a Rússia, nem com a UE, mas apenas com políticas específicas de ambos os cosmos, esta decisão acarta consequências drásticas na relação com o cosmo excluído. E, acima de tudo, a associação da Ucrânia à UE impacta directamente as relações bilaterais com a Rússia. Apesar da assinatura do Acordo de Associação com a UE, a Ucrânia não tomou ainda uma decisão civilizacional de integração num destes dois cosmos. E, a própria UE, também ainda apresenta sinais de hesitação. Neste contexto, a presente dissertação pretende compreender de que forma a Parceria Oriental tem contribuído para estas questões, analisando as consequências das relações UE-Ucrânia, desenvolvidas ao abrigo da Parceria Oriental, para a projecção de poder da UE perante a Rússia.

Study on the degradation of natural fiber geotextiles

Current societal challenges increasingly demand the need to seek for efficient and sustainable solutions to daily problems. Construction, as a result of its activity, is one of the main responsible industry for the exploitation of resources and greenhouse gas emissions. In this way, several research works are being undertaken to change some of the current practices. This paper presents the work being done at University of Minho to study de degradation of natural fibers when used as a sustainable solution for soil reinforcement. Jute and sisal fibrous structures (0º/90º) were studied in terms of their degradation over time, when incorporated into soil and when subject to accelerated aging tests in a QUV weathering test equipment. Results show that the process of biodegradation of natural fibers is clearly accelerated by the action of temperature, moisture and solar radiation, explaining further degradation of jute and sisal fibers when exposed to these factors, although more pronounced in jute fabric structures.

Natural evidence for rapid abiogenic hydrothermal generation of CH4

Although recent hydrothermal experiments imply that abiogenic methane (CH4) generation from hydrothermal reduction of CO2 can occur, evidence from natural systems was still lacking. Based on the chemical and isotopic equilibrium signatures of low-temperature fumarolic gas discharges, we are able to provide hard evidence for its natural occurrence, namely in three subduction-related bi-phase hydrothermal systems of the Mediterranean, whose temperatures range from 260 to 470 degrees C. The attainment of equilibrium and the time spans of recent volcanic dormancy allowed us to calculate minimum rates for chemical and isotopic equilibration. These are significantly higher than those previously reported and might be due to the presence of a saturated water vapor phase in the investigated systems. The fact that nature provides conditions enabling relatively fast production of hydrocarbons from CO2 strongly supports the concerns that were recently raised from laboratory experiments. These address the use of the carbon isotope composition of reduced carbon in Archean sediments as a tracer of early life and the occurrence of CH4 on extraterrestrial planets as a bioindicator. In view of the potential role of abiogenic CH4 as a precursor of life, we also present an estimate of abiogenic hydrothermal CH4 fluxes throughout the Archean. It is not expected that these fluxes exceeded 80 Mt/yr during the past 4.0 Ga. This, however, would have been enough to facilitate HCN production on the prebiotic Earth. (C) 2007 Elsevier Ltd. All rights reserved.

Statistical evidences of cyclic changes in volcanic gas chemistry composition by inverse modelling

The identification of compositional changes in fumarolic gases of active and quiescent volcanoes is one of the mostimportant targets in monitoring programs. From a general point of view, many systematic (often cyclic) and randomprocesses control the chemistry of gas discharges, making difficult to produce a convincing mathematical-statisticalmodelling.Changes in the chemical composition of volcanic gases sampled at Vulcano Island (Aeolian Arc, Sicily, Italy) fromeight different fumaroles located in the northern sector of the summit crater (La Fossa) have been analysed byconsidering their dependence from time in the period 2000-2007. Each intermediate chemical composition has beenconsidered as potentially derived from the contribution of the two temporal extremes represented by the 2000 and 2007samples, respectively, by using inverse modelling methodologies for compositional data. Data pertaining to fumarolesF5 and F27, located on the rim and in the inner part of La Fossa crater, respectively, have been used to achieve theproposed aim. The statistical approach has allowed us to highlight the presence of random and not random fluctuations,features useful to understand how the volcanic system works, opening new perspectives in sampling strategies and inthe evaluation of the natural risk related to a quiescent volcano

Transcriptional profiling of Gram-positive Arthrobacter in the phyllosphere: induction of pollutant degradation genes by natural plant phenolic compounds.

Arthrobacter chlorophenolicus A6 is a Gram-positive, 4-chlorophenol-degrading soil bacterium that was recently shown to be an effective colonizer of plant leaf surfaces. The genetic basis for this phyllosphere competency is unknown. In this paper, we describe the genome-wide expression profile of A.chlorophenolicus on leaves of common bean (Phaseolus vulgaris) compared with growth on agar surfaces. In phyllosphere-grown cells, we found elevated expression of several genes known to contribute to epiphytic fitness, for example those involved in nutrient acquisition, attachment, stress response and horizontal gene transfer. A surprising result was the leaf-induced expression of a subset of the so-called cph genes for the degradation of 4-chlorophenol. This subset encodes the conversion of the phenolic compound hydroquinone to 3-oxoadipate, and was shown to be induced not only by 4-chlorophenol but also hydroquinone, its glycosylated derivative arbutin, and phenol. Small amounts of hydroquinone, but not arbutin or phenol, were detected in leaf surface washes of P.vulgaris by gas chromatography-mass spectrometry. Our findings illustrate the utility of genomics approaches for exploration and improved understanding of a microbial habitat. Also, they highlight the potential for phyllosphere-based priming of bacteria to stimulate pollutant degradation, which holds promise for the application of phylloremediation.

Nationalisme économique et réalisme mercantile : la politique énergétique russe sous Poutine (2000-2008)

Mon travail met en évidence la restructuration de l'industrie énergétique russe sous les deux mandats Poutine (2000-2008) via le rôle prédominant de l'État dans une perspective historique. Une nouvelle élite politique russe (les Silovikis) issue des structures de force de l'Etat favorise le nationalisme économique axé sur le rétablissement de l'autorité du gouvernement central au sein de l'industrie énergétique nationale au détriment des pouvoirs régionaux, des sociétés privées étrangères et des oligarques indépendants. Dans cette perspective, on peut citer "l'affaire Youkos" en 2003 caractérisée par l'arrestation de l'oligarque Mikhaïl Khodorkhovsky; les tentatives silovikiennes de reprendre l'ascendant sur les compagnies pétrolières régionales Tatneft et Bachneft gérées par les gouvernements tatar et bachkir, la pression fiscale envers les majors pétrolières étrangères à l'instar du conflit russo- britannique relatif à la joint-venture TNK-BP. Quant à la politique énergétique étrangère russe, elle est inspirée par line vision réaliste mercantile; le gouvernement silovikien vise à défendre l'intérêt national, le prestige et la puissance de la Russie via ses "champions" énergétiques Rosneft et Gazprom utilisés comme levier politique, notamment à l'égard des pays de la CEI considéré par Moscou comme sa sphère d'influence historique. Dans cette perspective, nous pouvons mentionner l'interruption des approvisionnements pétroliers et gaziers russes à l'Ukraine, aux Etats baltes ou encore à la Géorgie; la concurrence entre les majors russes et étrangères en Asie centrale / Caucase pour les champs pétrolifères et les tracés de pipelines (nouveau «Grand Jeu»); la diversification des marchés russes à l'exportation à travers la promotion de nouveaux pipelines partant des champs pétrolifères sibériens vers la Chine et l'océan Pacifique.¦My work highlights the restructuration of the Russian energy industry under the 2 Putin madates (2000-2008) by the predominant role of the state in a historical perspective. A new Russian politic elite (Siloviki) from state structure forces promotes the economic nationalism focused on the reestablishment of the central governmental authority in the national energy industry against regional powers, private foreign companies and independent oligarchs. In this perspective, we can mention the "Yukos Affair" in 2003 with the arrest of the oligarch Mikhail Khodorkhovsky; the silovikian attempts to take over the regional oil companies Tatneft and Bachneft handled by the Tatar and Bashkir governments; the fiscal silovikian pressure against foreign companies such as the Russo-Britannic joint- venture TNK-BP. As for the Russian energy Foreign policy, it is inspired by a mercantile realism vision; the silovikian government aims to defend the national interest, the prestige and the power of Russia through its energy companies Rosneft and Gazprom as a political leverage especially toward the CEI Countries considered by Moscow as it historical sphere of influence. In this perspective, we can mention the interruption of Russian oil&gas supply toward Ukraine, Baltic states or Georgia; the competition between Russian and foreign companies in Central Asia/Caucasus for oil and gas fields and pipeline routes (new "Great Game"); the diversification of Russian export markets through the promotion ο new pipelines from Siberian oil&gas fields to China and the Pacific Ocean.

The carbon isotope composition of natural SiC (moissanite) from the Earth's mantle: New discoveries from ophiolites

Moissanite (natural SiC) has been recovered from podiform chromitites of several ophiolite complexes, including the Luobusa and Donqiao ophiolites in Tibet, the Semail ophiolite in Oman and the United Arab Emirates, and the Ray-Iz ophiolite of the Polar Urals, Russia. Taking these new occurrences with the numerous earlier reports of moissanite in diamondiferous kimberlites leads to the conclusion that natural SiC is a widespread mineral in the Earth's mantle, which implies at least locally extremely low redox conditions. The ophiolite moissanite grains are mostly fragments (20 to 150 mu m) with one or more crystal faces, but some euhedral hexagonal grains have also been recovered. Twinned crystals are common in chromitites from the Luobusa ophiolite. The moissanite is rarely colorless, more commonly light bluish-gray to blue or green. Many grains contain inclusions of native Si and Fe-Si alloys (FeSi(2), Fe(3)Si(7)). Secondary ion mass spectrometric (SIMS) analysis shows that the ophiolite-hosted moissanite has a distinctive (13)C-depleted isotopic composition (delta(13)C from -18 to -35 parts per thousand, n=36), much lighter than the main carbon reservoir in the upper mantle (delta(13)C near -5 parts per thousand). The compiled data from moissanite from kimberlites and other mantle settings share the characteristic of strongly (13)C-depleted isotopic composition. This suggests that moissanite originates from a separate carbon reservoir in the mantle or that its formation involved strong isotopic fractionation. The degree of fractionation needed to produce the observed moissanite compositions from the main C-reservoir would be unrealistically large at the high temperatures required for moissanite formation. Subduction of biogenic carbonaceous material could potentially satisfy both the unusual isotopic and redox constraints on moissanite formation, but this material would need to stay chemically isolated from the upper mantle until it reached the high-T stability field of moissanite. The origin of moissanite in the mantle is still unsolved, but all evidence from the upper mantle indicates that it cannot have formed there, barring special and local redox conditions. We suggest, alternatively, that moissanite may have formed in the lower mantle, where the existence of (13)C-depleted carbon is strongly supported by studies of extraterrestrial carbon (Mars, Moon, meteorites). (C) 2009 Elsevier B. V. All rights reserved.

Contrasting tree-ring data with fire record in a pine-dominated landscape in the Komi Republic (Eastern European Russia) : recovering a common climate signal

Abstract