Evolución paleoambiental de la Península Ibérica desde hace 1 Ma a partir de los biomarcadores del registro de la Turbera de Padul (Granada)

La Turbera de Padul, en la Provincia de Granada, ofrece unas posibilidades de estudio muy atractivas desde el punto de vista de la reconstrucción paleoambiental. Se trata de una fosa tectónica subsidente de naturaleza detrítica, a cuyo techo aparecen alternantes niveles de turba. El sondeo, de 107 metros, se realizó en un punto donde los estratos de turba aparecen a mayor profundidad, lo que permite obtener un registro geoquímico orgánico con mucho detalle con una antigüedad de hasta 1Ma. Se tomaron muestras cada 20 cm para el análisis de biomarcadores. Estos biomarcadores se obtuvieron mediante extracción Soxhlet, posterior separación de fracciones de diferente polaridad mediante Cromatografía en Columna, con Gel de Sílice y Alúmina, y posteriormente el análisis e identificación por Cromatografía de Gases - Espectrometría de masas, con confirmación de los compuestos químicos identificados por comparación con Bibliotecas de Espectros de Masas. La datación del sondeo se realizó utilizando distintos métodos como datación por 14C, U/Th, y datación por racemización de aminoácidos. Los resultados dataron el muro del sondeo con una antigüedad de 1 millón de años. El estudio de los biomarcadores ha permitido identificar episodios con distintas características en un escenario complejo, como es la Turbera de Padul, donde el aporte de agua por fusión nival complica la interpretación paleoambiental, y es la responsable de la existencia de la lámina de agua en la turbera en periodos secos con temperaturas elevadas. Se han identificado series de n-alcanos, de n-metilcetonas y series de nalcanoles, que han permitido identificar la aportación de materia orgánica de distintas fuentes al sedimento y por tanto la interpretación paleoambiental. La identificación de diterpenoides fenólicos (cis-Totatol, trans-Totarol y Ferruginol) han permitido identificar episodios de clima templado y húmedo con proliferación de cupresáceas, y precipitaciones abundantes. Por otro lado, se han identificado triterpenoides como el Friedelan-3-ona (Friedelin) y el A-norfriedel-8en-10-ona, cuya relación como precursor (Friedelin) y producto (A-norfriedel-8en-10-ona) ha permitido identificar episodios con fluctuaciones del espesor de la lámina de agua y aporte de material vegetal. ABSTRACT The Bog of Padul, in the province of Granada, offers very attractive possibilities for the study of paleoenvironmental reconstruction. It is a subsiding graben of detrital nature, whose upper part appear alternating peat levels. The core of 107 meters, obtained from a borehole drilled in a place where the layers of peat appear deeper, allowing to obtain organic geochemist information along the last 1 million years. Every 20 cm samples for biomarkers analysis were taken. These biomarkers were obtained by Soxhlet extraction, subsequent separation of fractions of different polarity by column chromatography with silica gel and alumina, and then analyzed and identified by gas chromatography - mass spectrometry, with confirmation of the chemicals identified by comparison to mass spectral libraries. The dating of the core was conducted using different methods such as 14C dating, U/Th, and amino acid racemization dating. The results dated the base of the core to be 1 million years old. The study has identified biomarkers episodes with different characteristics in a complex scenario, such as the Bog of Padul, where the contribution of snowmelt water complicates the paleoenvironmental interpretation, and is responsible for the existence of a sheet of water in dry periods with high temperatures. There have been identified series of n-alkanes, n-methyl ketones and series of n-alkanols that have shown the contribution of different organic matter sources to the sediment and therefore allowed to paleo interpretation. The identification of phenolic diterpenoids (cis-Totatol, trans-Totarol and Ferruginol) have identified episodes of mild and humid climate with proliferation of Cupressaceae, and abundant rainfall. In addition, triterpenoids have been identified, as the friedelan-3-one (friedelin) and the A-norfriedel-8en-10-one, whose relationship as precursor (friedelin) and product (A-norfriedel-8en-10-one) has identified episodes with fluctuations on the thickness of the sheet of water and supply of plant material debris.

Thermogravimetric monitoring of oil refinery sludge

The present work has two dimensions: analytical and environmental. On the one hand we proved that thermogravimetric analysis can be used to perform fast characterization of oil refinery sludge. To this end, thermogravimetric curves were deconvoluted by using autocatalytic kinetics to take into account acceleratory phases in a thermal degradation performed in oxygen-containing atmosphere or at high heating rates. Based on thermogravimetric results, oil refinery sludge was modeled in terms of various fractions (pseudo-components) which degrade as major oil cuts. On the other hand, as an alternative to landfill, we have seen that Soxhlet extraction allows recovery almost half of the weight of sludge as a mixture of hydrocarbons, similar to gas–oil, which burns without residue. This ensures both, waste inerting and significant reduction in sludge volume.

Reactive processing methods for functionalisation of polymers and in-situ compatibilisation of poly(ethylene terephthalate)-based blends

One of the main objectives of this study was to functionalise various rubbers (i.e. ethylene propylene copolymer (EP), ethylene propylene diene terpolymer (EPDM), and natural rubber (NR)) using functional monomers, maleic anhydride (MA) and glycidyl methacrylate (GMA), via reactive processing routes. The functionalisation of the rubber was carried out via different reactive processing methods in an internal mixer. GMA was free-radically grafted onto EP and EPDM in the melt state in the absence and presence of a comonomer, trimethylolpropane triacrylate (TRlS). To optinuse the grafting conditions and the compositions, the effects of various paranleters on the grafting yields and the extent of side reactions were investigated. Precipitation method and Soxhlet extraction method was established to purifY the GMA modified rubbers and the grafting degree was determined by FTIR and titration. It was found that without TRlS the grafting degree of GMA increased with increasing peroxide concentration. However, grafting was low and the homopolymerisation of GMA and crosslinking of the polymers were identified as the main side reactions competing with the desired grafting reaction for EP and EPDM, respectively. The use of the tri-functional comonomer, TRlS, was shown to greatly enhance the GMA grafting and reduce the side reactions in terms of the higher GMA grafting degree, less alteration of the rheological properties of the polymer substrates and very little formation of polyGMA. The grafting mechanisms were investigated. MA was grafted onto NR using both thermal initiation and peroxide initiation. The results showed clearly that the reaction of MA with NR could be thermally initiated above 140°C in the absence of peroxide. At a preferable temperature of 200°C, the grafting degree was increased with increasing MA concentration. The grafting reaction could also be initiated with peroxide. It was found that 2,5-dimethyl-2,5-bis(ter-butylproxy) hexane (TIOI) was a suitable peroxide to initiate the reaction efficiently above I50°C. The second objective of the work was to utilize the functionalised rubbers in a second step to achieve an in-situ compatibilisation of blends based on poly(ethylene terephthalate) (PET), in particular, with GMA-grafted-EP and -EPDM and the reactive blending was carried out in an internal mixer. The effects of GMA grafting degree, viscosities of GMAgrafted- EP and -EPDM and the presence of polyGMA in the rubber samples on the compatibilisation of PET blends in terms of morphology, dynamical mechanical properties and tensile properties were investigated. It was found that the GMA modified rubbers were very efficient in compatibilising the PET blends and this was supported by the much finer morphology and the better tensile properties. The evidence obtained from the analysis of the PET blends strongly supports the existence of the copolymers through the interfacial reactions between the grafted epoxy group in the GMA modified rubber and the terminal groups of PET in the blends.

Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction

The potential use of the solvothermal extraction (SE) as a preliminary step to calcination for detemplating SBA-15 mesophases is investigated; aiming to reduce the amount of organics to be burnt and thereby the corresponding structural shrinkage. A systematic study was carried out by soxhlet extraction on mesophases hydrothermally aged between 90 and 130 C. The mesophases containing variable amounts of template were then treated by calcination or pyrolysis/calcination. TGA was applied to quantify the template amount after the various treatments. The as obtained materials were characterized by SAXS and Ar ad/desorption for structural and textural information while 1H NMR gave information about the integrity of the as-recycled template. The study shows that solvothermal conditions remove considerably the template, typically from 50 to 10-20 wt.%, mainly extracted from the primary mesopores. Possible reuse of the extracted template is questionable as it is poor in polyethyleneoxide compared to the synthesis block-copolymer, Pluronic P123. For all thermal protocols applied (direct calcination, calcination after solvent-extraction or pyrolysis/calcination after solvent extraction), the thermal shrinkage decreases with the aging temperature; that is consistent with the condensation degree of the silica. For each mesophase, it was found that the thermal shrinkage becomes less pronounced when the material is fully templated; thus the template can serve as structural support or can control the mass transfer of O2 and thereby the oxidation rate of the template burning. © 2013 Elsevier Inc. All rights reserved.

Determinação da composição química de quatro variedades de feijão caupi (Vigna unguiculata L. Walp) cultivadas em solo potiguar

The cowpea (Vigna unguiculata L. Walp) is a major food crops in northeastern Brazil. In Rio Grande do Norte, the cowpea, vigna beans or cowpea, as it is known, has great socioeconomic importance as a source of nutrients in food, with great emphasis among agricultural products. To improve productivity and resistance to pests, two cultivars were developed exclusively by EMPARN (Agricultural Research Corporation of Rio Grande do Norte), for breeding. The samples were provided by EMPARN, two improved (Potiguar and Laugh year) and two landraces (Rib of beef and Canapu). The seeds were ground and made into flour samples and the determination of moisture and ash by graviméticos methods, lipids by Soxhlet extraction, fibers with determiner fiber, carbohydrates by difference and minerals by ICP-OES were performed except the match analyzed by UVvis. The results showed a high fiber content (55.55% and 55.32% and 50.04% improved samples and 50.32% creole samples) and protein (25.52% and 25.27% improved and 27 samples, 23% and 24.99% creole samples). Comparing the results of the mineral content, the improved cultivars stood out in relation to Ca, Co, P, Mg, Mo and Na. Creole cultivars showed better results for Cu, Cr (low), Fe, Mn, Ni, K and Zn. The results will be important in future nutritional research and to build a table of Brazilian chemical composition of foods.

Utilização da espectroscopia no infravermelho próximo para o controle de qualidade do camarão (Litopenaeus vannamei)

This work was developed with the objective of proposing a simple, fast and versatile methodological routine using near-infrared spectroscopy (NIR) combined with multivariate analysis for the determination of ash content, moisture, protein and total lipids present in the gray shrimp (Litopenaeus vannamei ) which is conventionally performed gravimetrically after ashing at 550 ° C gravimetrically after drying at 105 ° C for the determination of moisture gravimetrically after a Soxhlet extraction using volumetric and after digestion and distillation Kjedhal respectively. Was first collected the spectra of 63 samples processed boiled shrimp Litopenaeus vannamei species. Then, the determinations by conventional standard methods were carried out. The spectra centered average underwent multiplicative scattering correction of light, smoothing Saviztky-Golay 15 points and first derivative, eliminated the noisy region, the working range was from 1100,36 to 2502,37 nm. Thus, the PLS models for predicting ash showed R 0,9471; 0,1017 and RMSEP RMSEC 0,1548; Moisture R was 0,9241; 2,5483 and RMSEP RMSEC 4,1979; R protein to 0,9201; 1,9391 and RMSEP RMSEC 2,7066; for lipids R 0,8801; 0,2827 and RMSEP RMSEC 0,2329 So that the results showed that the relative errors found between the reference method and the NIR were small and satisfactory. These results are an excellent indication that you can use the NIR to these analyzes, which is quite advantageous, since conventional techniques are time consuming, they spend a lot of reagents and involve a number of professionals, which requires a reasonable runtime while after the validation of the methodology execution using NIR reduces all this time to a few minutes, saving reagents, time and without waste generation, and that this is a non-destructive technique.

Extração de ácidos triterpénicos a partir da casca de eucalipto utilizando líquidos iónicos

Os recursos renováveis têm sido um forte alvo de investigação científica nos últimos anos, onde o aproveitamento de biomassa e seus resíduos para a obtenção de compostos de valor acrescentado, combustíveis e energia têm sido abordados no conceito de biorrefinaria integrada. As indústrias de papel geram quantidades significativas de resíduos, nomeadamente a casca de eucalipto que é atualmente queimada para a geração de energia. De forma a valorizar este resíduo, a presente dissertação teve como objetivo extrair compostos triterpénicos, a partir casca externa de Eucalyptus globulus, utilizando solventes de extração alternativos - soluções aquosas de líquidos iónicos (LIs) – para substituir os solventes orgânicos actualmente utilizados. Os ácidos triterpénicos apresentam um elevado interesse na indústria cosmética, farmacêutica e alimentar graças às suas propriedades antiinflamatórias, antitumurais, entre outras. Primeiramente, caracterizou-se a casca externa de Eucalyptus globulus, e posteriormente procedeu-se ao estudo de solubilidade de ácido ursólico (AU, utilizado como molécula modelo) a 25 ºC em soluções aquosas de LIs e surfactantes de modo a selecionar os solventes mais eficientes para a extração. Deste trabalho conclui-se que a capacidade surfactante das soluções aquosas de LIs, particularmente [C4C1im][C8H17SO4], [C16C1im]Cl e [C14C1im]Cl, desempenham um papel fundamental para a solubilização de AU em água, podendo aumentar quase 16000 vezes a sua solubilidade, e permitiu recuperar cerca de 89% deste composto com simples adição de água como anti-solvente. Por fim, compararam-se as quantidades de ácidos triterpénicos extraídas a partir da casca de eucalipto com soluções aquosas de [C14C1im]Cl, metanol e com extração em soxhlet com diclorometano.

Cytotoxic, anti-inflammatory and antioxidant activities of four different extracts of Galega officinalis L (Goat’s rue)

Purpose: To evaluate the cytotoxic, anti-inflammatory and antioxidant activities of four different solvent extracts obtained from the aerial parts of Galega officinalis L Methods: The hexane, DCM, methanol and water extracts of G. officinalis were successively obtained by soxhlet extraction method. The cytotoxic activity of the extracts was assessed against human lung carcinoma (A-549), human colorectal adenocarcinoma (HT-29), human brain glioblastoma (U-87), and colon adenocarcinoma (DLD-1) by Resazurine test. The antioxidant activity of extracts were determined by Folin-Ciocalteau, oxygen radical absorbing capacity (ORAC), and 2’.7’-dichlorofluorescin-diacetate (DCFH-DA) cell-based assay while their anti-inflammatory activity was determined by nitric oxide (NO) assay. Results: DCM extract showed strong cytotoxic activity against lung adenocarcinoma and brain glioblastoma cell lines, with IC50 (concentration inhibiting 50 % of cell growth) values of 11 ± 0.4 and 16 ± 3 μg/mL, respectively. The hexane extract showed moderate anticancer activity against the same cell lines (59 ± 13 and 63 ± 16 μg/mL, respectively). DCM extract also showed significant anti-inflammatory activity, inhibiting NO release by 86.7 % at 40 μg/mL in lipopolysaccharide (LPS) - stimulated murine RAW 264.7 macrophages. Of all test extracts, the methanol extract of G. officinalis showed the highest antioxidant activity with 2.33 ± 0.09 μmol Trolox/mg , 7.10 ± 0.9 g tannic acid equivalent (TAE), and IC50 of 44 ± 4 μg/mL. Conclusion: The findings of this study suggest that DCM extract may possess anticancer effect against lung adenocarcinoma and brain glioblastoma, as well as serve as an anti-inflammatory agent.

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

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.

Lipid content of frozen fish: comparison of different extraction methods and variability during freezing storage

In this work, a microwave-assisted extraction (MAE) methodology was compared with several conventional extraction methods (Soxhlet, Bligh & Dyer, modified Bligh & Dyer, Folch, modified Folch, Hara & Radin, Roese-Gottlieb) for quantification of total lipid content of three fish species: horse mackerel (Trachurus trachurus), chub mackerel (Scomber japonicus), and sardine (Sardina pilchardus). The influence of species, extraction method and frozen storage time (varying from fresh to 9 months of freezing) on total lipid content was analysed in detail. The efficiencies of methods MAE, Bligh & Dyer, Folch, modified Folch and Hara & Radin were the highest and although they were not statistically different, differences existed in terms of variability, with MAE showing the highest repeatability (CV = 0.034). Roese-Gottlieb, Soxhlet, and modified Bligh & Dyer methods were very poor in terms of efficiency as well as repeatability (CV between 0.13 and 0.18).

Termoestabilidade de processos extrativos de Nasturtium officinale R. Br., brassicaceae por sistema Soxhlet modificado

This work had as objective verified the term-stability of the Soxhlet modified system with analytical and pharmacothecnical application in extractive processes of Nasturtium officinale. It has proven that the process is thermo-stable. The analysis with analytical have determined 3.606 mg g-1 in chlorogenic acid and 11.813 mg g-1 in rutin (extract 1:20 w/v) and with pharmacotecnical 3.427 mg g-1 in chlorogenic acid and 11.278 mg g-1 in rutin (extract 1:6 w/v). The income of the pharmacothecnical process was inferior to the analytical, suggesting that the pharmacothecnical process would need of at least the double of time in each extraction system.

Physicochemical properties and antioxidant activity of Tunisian date palm (Phoenix dactylifera L.) oil as affected by different extraction methods

The chemical analysis of flesh and seed of date palm fruit (Kentichi) was evaluated. Carbohydrates were the predominant component in all studied date cultivars (~78.69-83.46 g/100g dry matter), followed by moisture content (~9.23-11.17%), along with moderate amount of fat (~0.56-7.10 g/100g dry matter), protein (~2.16-2.80 g/100g dry matter), and ash (~1.18-1.64 g/100 g dry matter). Some antioxidants (Ascorbic acid, total phenolic, total flavonoid, chlorophyll and carotenoids) were found in different values in both date fruit and seed. The physicochemical properties and antioxidant activity of both flesh and seed oil which was extracted using Hexane, Soxhlet and Modified Bligh - Dyer extraction methods were determined. The experimental results showed that temperature, different solvents and extraction time had significant effect on the yield of the date palm oil and physicochemical properties. Date Flesh oil showed an important free radical scavenging activity towards 1-1-diphenyl-2-picrylhydrazyl (DPPH) free radical.

Supercritical fluid extraction from Lippia alba: global yields, kinetic data, and extract chemical composition

In this work, experimental data for the system Lippia alba + CO2 is presented. The major constituents of the L. alba volatile oil are limonene and carvone. Thus, literature data for the systems limonene + CO2 and carvone + CO2, and the Peng-Robinson equation of state (PR-EOS) were used to select the operating temperature and pressure, which maximize the global yield in L. alba extract. Global yields were determined at 80, 100, and 120 bar and 40, 45, and 50 degrees C. L. alba extracts were also obtained by conventional processes (hydrodistillation, low-pressure ethanol extraction and Soxhlet ethanol). The chemical compositions of the extracts were determined by gas and thin layer chromatography (TLC). The secretor structures of L. alba were observed by scanning electron microscopy (SEM) before and after supercritical extraction. The largest yield (similar to 7%, mass of extract/mass of dry solid) of the CO2-extract was obtained at 318 K and 100 bar. The chemical compositions of the CO2-extracts were different from those of the extracts obtained by Soxhlet and low-pressure solvent extraction (LPSE) because of the co-extraction of heavy substances by ethanol. The operating conditions that maximized the carvone and limomene yields were 80 bar and 323 K (80 mass%) and 120 bar and 323 K (17 mass%), respectively. (c) 2004 Elsevier B.V All rights reserved.