Análises palinofaciológicas e palinológicas da Formação Tremembé na Fazenda Santa Fé (Bacia de Taubaté) aplicadas à caracterização do potencial gerador de hidrocarbonetos

Foram aplicadas as técnicas de petrografia orgânica e palinologia no testemunho do poço TMB-01-SP, localizado na porção central da Bacia de Taubaté. A análise visual de 41 lâminas organopalinológicas e palinológicas permitiu individualizar três palinofácies e posicionar temporalmente a seção. A partir dos resultados das análises quantitativas do conteúdo orgânico, observou-se o predomínio de matéria orgânica amorfa de origem lacustre determinada pela presença de algas Botryococcus braunii e Pediastrum sp. Subordinadamente, verificou-se também a presença de grãos de pólen, esporos, fitoclastos e tecidos cutículares. Devido ao predomínio de matéria orgânica amorfa e algas lacustres com contribuições menores de material proveniente de vegetais superiores, foi possível classificar o querogênio como sendo dos tipos I e III. A matéria orgânica amorfa apresentou fluorescência moderada a alta na maior parte da seção (palinofácies 1 e 3) indicando um ambiente de sedimentação redutor predominante. Os resultados do índice de coloração de esporos (ICE) entre 1,5 e 2,5 indicaram zona imatura de geração de hidrocarbonetos. A partir das análises palinológicas foi possível observar uma rica e diversificada associação com 49 espécies identificadas, incluindo grãos de pólen, esporos, algas e fungos. Os resultados palinoestratigráficos permitiram correlacionar a seção analisada à palinozona Parvisaccites? sp. (Regali et al., 1974) que corresponde ao Oligoceno. Entre os palinomorfos diagnósticos de idade e ambiente deposicional foram identificados: Catinipollis geiseltalensis, Cicatricosisporites dorogensis, Dacrydiumites florinii, Echitriletes muelleri, Ephedripites tertiarius, Perisyncolporites pokornyi, Podocarpidites marwickii, Polypodiaceiosporites potoniei, Psilatricolporites operculatus, Quadraplanus sp., Ulmodeipites krempii e Verrucatosporites usmensis. Os sedimentos estudados foram depositados em um paleoambiente lacustre raso sob condições redutoras ao longo de praticamente toda a seção.

成油藻——布朗葡萄藻的研究

<正> 葡萄藻(Botryococcus braunii)是一种温带普生性种类。主要分布于淡水水体中。藻体是由几十到几百个细胞组成的,大小在30—500μm左右。含有较丰富的油类物质,一般占藻体干重的25—40％,最高可达85％。葡萄藻可形成水华。据报道澳大利亚达尔文水库(4000ha)形成水华时可得3000吨葡萄藻干物质,当地居民可直接用作燃料,因此曾有

Supercritical carbon dioxide extraction of bioactive compounds from microalgae and volatile oils from aromatic plants

A discussion of the most interesting results obtained in our laboratories, during the supercritical CO(2) extraction of bioactive compounds from microalgae and volatile oils from aromatic plants, was carried out. Concerning the microalgae, the studies on Botryococcus braunii and Chlorella vulgaris were selected. Hydrocarbons from the first microalgae, which are mainly linear alkadienes (C(23)-C(31)) with an odd number of carbon atoms, were selectively extracted at 313 K increasing the pressure up to 30.0 MPa. These hydrocarbons are easily extracted at this pressure, since they are located outside the cellular walls. The extraction of carotenoids, mainly canthaxanthin and astaxanthin, from C. vulgaris is more difficult. The extraction yield of these components at 313 K and 35.0 MPa increased with the degree of crushing of the microalga, since they are not extracellular. On the other hand, for the extraction of volatile oils from aromatic plants, studies on Mentha pulegium and Satureja montana L were chosen. For the first aromatic plant, the composition of the volatile and essential oils was similar, the main components being the pulegone and menthone. However, this volatile oil contained small amounts of waxes, which content decreased with decreasing particle size of the plant matrix. For S. montana L it was also observed that both oils have a similar composition, the main components being carvacrol and thymol. The main difference is the relative amount of thymoquinone, which content can be 15 times higher in volatile oil. This oxygenated monoterpene has important biological activities. Moreover, experimental studies on anticholinesterase activity of supercritical extracts of S. montana were also carried out. The supercritical nonvolatile fraction, which presented the highest content of the protocatechuic, vanilic, chlorogenic and (+)-catechin acids, is the most promising inhibitor of the enzyme butyrylcholinesterase. In contrast, the Soxhlet acetone extract did not affect the activity of this enzyme at the concentrations tested. (C) 2011 Elsevier B.V. All rights reserved.

Holocene fires in East Amazonia (Caraja`s), new evidences, chronology and relation with paleoclimate

Past studies have evidenced the presence of charcoal in soils and lacustrine sediments of Amazonia region and suggested occurrences of widespread fires during the Middle Holocene. However, the available records do not indicate the changes in fire regime with enough time resolution. We quantified charcoal fragments in lacustrine sediments in a lake of North Carajas plateau in East Amazonia (5 degrees 50`-6 degrees 35`S and 49 degrees 30`-52 degrees 00`W). The charcoal quantification was compared to other sediment proxies, allowing a connection between paleofires and climate changes. Large variations in sediment characteristics led to distinct stages of sedimentation. From 11,800 (base of CSN 93/4) to 4750 cal yr B.P., low accumulation rates of organic matter are observed. Between 7600 cal yr B.P. (base of CSN 93/3 core) and 4750 cal yr B.P., this initial phase of sedimentation is characterized by low chlorophyll derivate accumulation rates and high accumulation rates of Botryococcus braunii, an alga resistant to episodic drought. The first phase of sedimentation would therefore correspond to, a low take level and a drier climate than today. Large biomass burning events occurred between 7450 cal yr B.P. and 4750 cal yr B.P., as indicated by the high charcoal particle concentration. From 4750 cal yr B.P. to 2800 cal yr B.P., accumulation rates of charcoal particles decreased, and the accumulation rate of chlorophyll derivate was low. From 2800 cal yr B.P. to 1300 cal yr B.P., the charcoal accumulation rates reached their lowest values in the core and a rapid increase in lacustrine production is evidenced by the increase in chlorophyll derivates and carbon accumulation rate. From 1300 cal yr B.P. to the last century, the charcoal accumulation rates increased. During the most recent period, the record is characterized by high accumulation rates of chlorophyll derivates while the charcoal particle accumulation rate decreased. This region is still unaffected by the current increase of anthropogenic fires. (c) 2007 Elsevier B.V. All rights reserved.

Use of solvents and environmental friendly materials for applications in Green Chemistry

The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective “greenness” has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The “green” features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the “greenest” solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as “fully green” alternative solvents; however this epithet does not take into account several “brown” aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.

Pyrolysis of peptides and proteins. Analytical study and environmental applications

Analytical pyrolysis was used to investigate the formation of diketopiperazines (DKPs) which are cyclic dipeptides formed from the thermal degradation of proteins. A quali/quantitative procedure was developed combining microscale flash pyrolysis at 500 °C with gas chromatography-mass spectrometry (GC-MS) of DKPs trapped onto an adsorbent phase. Polar DKPs were silylated prior to GC-MS. Particular attention was paid to the identification of proline (Pro) containing DKPs due to their greater facility of formation. The GC-MS characteristics of more than 80 original and silylated DKPs were collected from the pyrolysis of sixteen linear dipeptides and four model proteins (e.g. bovine serum albumin, BSA). The structure of a novel DKP, cyclo(pyroglutamic-Pro) was established by NMR and ESI-MS analysis, while the structures of other novel DKPs remained tentative. DKPs resulted rather specific markers of amino acid sequence in proteins, even though the thermal degradation of DKPs should be taken into account. Structural information of DKPs gathered from the pyrolysis of model compounds was employed to the identification of these compounds in the pyrolysate of proteinaceous samples, including intrinsecally unfolded protein (IUP). Analysis of the liquid fraction (bio-oil) obtained from the pyrolysis of microalgae Nannochloropsis gaditana, Scenedesmus spp with a bench scale reactor showed that DKPs constituted an important pool of nitrogen-containing compounds. Conversely, the level of DKPs was rather low in the bio-oil of Botryococcus braunii. The developed micropyrolysis procedure was applied in combination with thermogravimetry (TGA) and infrared spectroscopy (FT-IR) to investigate surface interaction between BSA and synthetic chrysotile. The results showed that the thermal behavior of BSA (e.g. DKPs formation) was affected by the different form of doped synthetic chrysotile. The typical DKPs evolved from collagen were quantified in the pyrolysates of archaeological bones from Vicenne Necropolis in order to evaluate their conservation status in combination with TGA, FTIR and XRD analysis.

Pirolisi catalitica di microalghe con zeoliti

L’aumento delle concentrazioni del diossido di carbonio in atmosfera dovuto alla combustione dei combustibili fossili è una fonte di grande preoccupazione a causa del suo impatto sul clima globale. La biomassa è l’unica fonte rinnovabile a poter essere convertita in combustibili e, tra i metodi di conversione, la pirolisi produce un liquido (bio-olio) che presenta potenzialità come combustibile. Le alghe sono una biomassa di interesse, ma il bio-olio che si ottiene è caratterizzato da composti contenenti ossigeno, zolfo e azoto che ne riducono la qualità. Tali elementi possono essere eliminati attraverso la scissione (cracking) con zeoliti con la produzione di idrocarburi. L’obiettivo dello studio è stato quello di valutare le caratteristiche del cracking catalitico di tre microalghe: Arthrospira platensis, Botryococcus braunii e Desmodesmus communis per la produzione di idrocarburi. Le biomasse sono state pirolizzate a 500 °C e i vapori prodotti termicamente sono stati fatti passare nella zeolite dove subiscono il cracking. Sono state utilizzate due zeolite a diversa acidità: un pellet H-ZSM5 (SiO2/Al2O3=38) e un monolite a base di HZSM5 (SiO2/Al2O3=80) e sepiolite. Dal cracking si ottengono sei frazioni pirolitiche: char, coke, fase acquosa, bio-olio, frazione volatile e gas non condensabili. Le frazioni sono state caratterizzate tramite analisi elementari e molecolari e dai dati ottenuti sono stati calcolati i bilanci di N, C e del potere calorifico. Per tutte le alghe si ottiene un bio-olio con un elevato contenuto di carbonio e fortemente deossigenato, ma le rese sono relativamente basse. I prodotti che contengono una maggior frazione del carbonio della biomassa iniziale sono il char ed il coke, seguiti dalla fase organica e dai gas. La distribuzione dell’azoto è simile ma con una maggiore frazione nella fase acquosa. Entrambi i catalizzatori agiscono migliorando la qualità del bio-olio tramite la riduzione dei composti azotati ed ossigenati e formando idrocarburi monoaromatici, tipici delle benzine, e poliaromatici. Il monolite, con zeolite meno acida, produce una maggior frazione di bio-olio caratterizzato, però, da una minor percentuale di composti aromatici. Si ritiene che l’aumento delle rese del bio-olio e la valorizzazione dei sottoprodotti (biochar, fase acquosa) siano indispensabili per la sostenibilità del processo.

Separating ITCZ- and ENSO-related rainfall changes in the Galápagos over the last 3 kyr using D/H ratios of multiple lipid biomarkers

We present a 3000-yr rainfall reconstruction from the Galápagos Islands that is based on paired biomarker records from the sediment of El Junco Lake. Located in the eastern equatorial Pacific, the climate of the Galápagos Islands is governed by movements of the Intertropical Convergence Zone (ITCZ) and the El Niño-Southern Oscillation (ENSO). We use a novel method for reconstructing past ENSO- and ITCZ-related rainfall changes through analysis of molecular and isotopic biomarker records representing several types of plants and algae that grow under differing climatic conditions. We propose that ?D values of dinosterol, a sterol produced by dinoflagellates, record changes in mean rainfall in El Junco Lake, while dD values of C34 botryococcene, a hydrocarbon unique to the green alga Botryococcus braunii, record changes in rainfall associated with moderate-to-strong El Niño events. We use these proxies to infer changes in mean rainfall and El Niño-related rainfall over the past 3000 yr. During periods in which the inferred change in El Niño-related rainfall opposed the change in mean rainfall, we infer changes in the amount of ITCZ-related rainfall. Simulations with an idealized isotope hydrology model of El Junco Lake help illustrate the interpretation of these proxy reconstructions. Opposing changes in El Niño- and ITCZ-related rainfall appear to account for several of the largest inferred hydrologic changes in El Junco Lake. We propose that these reconstructions can be used to infer changes in frequency and/or intensity of El Niño events and changes in the position of the ITCZ in the eastern equatorial Pacific over the past 3000 yr. Comparison with El Junco Lake sediment grain size records indicates general agreement of inferred rainfall changes over the late Holocene.

The Global Plankton Database: an inventory and data from the Former Soviet Union expeditions

At present time, there is a lack of knowledge on the interannual climate-related variability of zooplankton communities of the tropical Atlantic, central Mediterranean Sea, Caspian Sea, and Aral Sea, due to the absence of appropriate databases. In the mid latitudes, the North Atlantic Oscillation (NAO) is the dominant mode of atmospheric fluctuations over eastern North America, the northern Atlantic Ocean and Europe. Therefore, one of the issues that need to be addressed through data synthesis is the evaluation of interannual patterns in species abundance and species diversity over these regions in regard to the NAO. The database has been used to investigate the ecological role of the NAO in interannual variations of mesozooplankton abundance and biomass along the zonal array of the NAO influence. Basic approach to the proposed research involved: (1) development of co-operation between experts and data holders in Ukraine, Russia, Kazakhstan, Azerbaijan, UK, and USA to rescue and compile the oceanographic data sets and release them on CD-ROM, (2) organization and compilation of a database based on FSU cruises to the above regions, (3) analysis of the basin-scale interannual variability of the zooplankton species abundance, biomass, and species diversity.