Julian Martínez

Amazon River carbon dioxide outgassing fuelled by wetlands

River systems connect the terrestrial biosphere, the atmosphere and the ocean in the global carbon cycle. A recent estimate suggests that up to 3 petagrams of carbon per year could be emitted as carbon dioxide (CO2) from global inland waters, offsetting the carbon uptake by terrestrial ecosystems. It is generally assumed that inland waters emit carbon that has been previously fixed upstream by land plant photosynthesis, then transferred to soils, and subsequently transported downstream in run-off. But at the scale of entire drainage basins, the lateral carbon fluxes carried by small rivers upstream do not account for all of the CO2 emitted from inundated areas downstream. Three-quarters of the world’s flooded land consists of temporary wetlands, but the contribution of these productive ecosystems to the inland water carbon budget has been largely overlooked. Here we show that wetlands pump large amounts of atmospheric CO2 into river waters in the floodplains of the central Amazon. Flooded forests and floating vegetation export large amounts of carbon to river waters and the dissolved CO2 can be transported dozens to hundreds of kilometres downstream before being emitted. We estimate that Amazonian wetlands export half of their gross primary production to river waters as dissolved CO2 and organic carbon, compared with only a few per cent of gross primary production exported in upland (not flooded) ecosystems. Moreover, we suggest that wetland carbon export is potentially large enough to account for at least the 0.21 petagrams of carbon emitted per year as CO2 from the central Amazon River and its floodplains. Global carbon budgets should explicitly address temporary or vegetated flooded areas, because these ecosystems combine high aerial primary production with large, fast carbon export, potentially supporting a substantial fraction of CO2 evasion from inland waters.

Supercritical fluid extraction from spent coffee grounds and coffee husks: antioxidant activity and effect of operational variables on extract composition.

The present study describes the chemical composition and the antioxidant activity of spent coffee grounds and coffee husks extracts, obtained by supercritical fluid extraction (SFE) with CO(2) and with CO(2) and co-solvent. In order to evaluate the high pressure method in terms of process yield, extract composition and antioxidant activity, low pressure methods, such as ultrasound (UE) and soxhlet (SOX) with different organic solvents, were also applied to obtain the extracts. The conditions for the SFE were: temperatures of 313.15K, 323.15K and 333.15K and pressures from 100 bar to 300 bar. The SFE kinetics and the mathematical modeling of the overall extraction curves (OEC) were also investigated. The extracts obtained by LPE (low pressure extraction) with ethanol showed the best results for the global extraction yield (X(0)) when compared to SFE results. The best extraction yield was 15±2% for spent coffee grounds with ethanol and 3.1±04% for coffee husks. The antioxidant potential was evaluated by DPPH method, ABTS method and Folin-Ciocalteau method. The best antioxidant activity was showed by coffee husk extracts obtained by LPE. The quantification and the identification of the extracts were accomplished using HPLC analysis. The main compounds identified were caffeine and chlorogenic acid for the supercritical extracts from coffee husks.

Supercritical fluid extraction of peach (Prunus persica) almond oil: Process yield and extract composition

Peach kernels are industrial residues from the peach processing, contain oil with important therapeutic properties and attractive nutritional aspects because of the high concentration of oleic and linoleic acids. The extraction method used to obtain natural compounds from raw matter is critical for product quality definition. Thus, the aim of this work was to compare peach almond extraction yields obtained by different procedures: soxhlet extractions (Sox) with different solvents; hydrodistillation (HD); ethanolic maceration (Mac) followed by fractionation with various solvents, and supercritical fluid extraction (SFE) at 30, 40 and 50 degrees C and at 100, 200 and 300bar, performed with pure CO(2) and with a co-solvent. The extracts were evaluated with respect to fatty acid composition (FAC), fractionated chemical profile (FCP) and total phenolic content (TPC). The Sox total yields were generally higher than those obtained by SFE. The crossover pressure for SFE was between 260 and 280bar. The FAC results show oleic and linoleic acids as main components, especially for Sox and SFE extracts. The FCP for samples obtained by Sox and Mac indicated the presence of benzaldehyde and benzyl alcohol, components responsible for almond flavor and with important industrial uses, whereas the SFE extracts present a high content of a possible flavonoid. The higher TPC values were obtained by Sox and Mac with ethanol. In general, the maximum pressure in SFE produced the highest yield, TPC and oleic acid content. The use of ethanol at 5% as co-solvent in SFE did not result in a significant effect on any evaluated parameter. The production of peach almond oil through all techniques is substantially adequate and SFE presented advantages, with respect to the quality of the extracts due to the high oleic acid content, as presented by some Sox samples.

Supercritical carbon dioxide extraction of capsaicinoids from malagueta pepper (Capsicum frutescens L.) assisted by ultrasound.

Extracts from malagueta pepper (Capsicum frutescens L.) were obtained using supercritical fluid extraction (SFE) assisted by ultrasound, with carbon dioxide as solvent at 15MPa and 40°C. The SFE global yield increased up to 77% when ultrasound waves were applied, and the best condition of ultrasound-assisted extraction was ultrasound power of 360W applied during 60min. Four capsaicinoids were identified in the extracts and quantified by high performance liquid chromatography. The use of ultrasonic waves did not influence significantly the capsaicinoid profiles and the phenolic content of the extracts. However, ultrasound has enhanced the SFE rate. A model based on the broken and intact cell concept was adequate to represent the extraction kinetics and estimate the mass transfer coefficients, which were increased with ultrasound. Images obtained by field emission scanning electron microscopy showed that the action of ultrasonic waves did not cause cracks on the cell wall surface. On the other hand, ultrasound promoted disturbances in the vegetable matrix, leading to the release of extractable material on the solid surface. The effects of ultrasound were more significant on SFE from larger solid particles.

Fundamentals of Microwave Extraction

Microwave-assisted extraction (MAE) is a process that removes solutes from a solid matrix into a solvent. Phenomena such as electromagnetic transfer, heat transfer, mass transfer, and momentum transfer make the process complex. For developing process engineering, the characteristics of heat and mass transfer are extremely significant. Accurate and controlled heat is possible because of the capacity of microwave radiation to penetrate and combine with a substrate. Therefore, the microwave procedure can be designed to transport electromagnetic energy with specific power to the location of the compounds of interest in the substrate. The energy-saving factors and short processing times lead to a reduction in manufacturing costs, and improvement of product uniformity and yields, resulting in products with high quality compared with other extraction techniques. This chapter provides a general review of heat and mass transfer and gives a brief discussion on the factors influencing the extraction efficiency of MAE. The performance of MAE is also compared to other classical methods, thus explaining the advantages of MAE technology as applied to plant extraction research.

Extraction of Clove and Vetiver Oils with Supercritical Carbon Dioxide: Modeling and Simulation

The kinetics of supercritical fluid extraction (SFE) of clove and vetiver oils using carbon dioxide as solvent was studied, in order to establish an efficient method to predict extraction curves on large scale. The mass transfer model of Sovova was used to adjust the experimental SFE data, which were obtained at 100 bar and 35 °C for clove and 200 bar and 40 °C for vetiver, using extraction columns of different geometry and solvent flow rates. Some other process parame- ters, such as bed density and porosity, solvent to feed ratio and solvent velocity were kept constant from one experiment to another, in order to verify if the mass transfer coefficients adjusted by the model varied. The results show that the model of Sovova was able to predict an overall extraction curve for clove from data obtained with twenty times less raw material, since the mass transfer coefficients remained the same and the predicted curves were similar to the observed ones. For vetiver, the simulation was not as effective, probably due to the effects of transport properties on the process.

Fitting the Sovová's supercritical fluid extraction model by means of a global optimization tool

Abstract The estimation of parameters of the Sovova’s model for supercritical fluid extraction is addressed in the present work. A global optimization approach is employed. Reasons for this decision are given as a consequence of more general modeling objectives. The way of dealing with different objective functions and constraints is described. Real-life experiments are given.

Recovery of anthocyanins from residues of Rubus fruticosus, Vaccinium myrtillus and Eugenia brasiliensis by ultrasound assisted extraction, pressurized liquid extraction and their combination

This work investigated the extraction efficiency of polyphenols (anthocyanins) from blackberry, blueberry and grumixama residues using combined ultrasonic assisted extraction (UAE) and pressurized liquid extraction (PLE) (UAE+PLE). The performance of UAE+PLE was compared to those achieved by the isolated PLE and UAE methods and conventional Soxhlet extraction. The effects of the extraction methods and solvents (acidified water pH 2.0, ethanol+water 50% v/v and ethanol+water 70% ethanol v/v) on total phenolics content, anthocyanin composition and antioxidant capacity of extracts were investigated by a full factorial design. The extraction efficiency for total phenolics and antioxidant capacity in decreasing order was: UAE+PLE>PLE≈Soxhlet>UAE, and for anthocyanins it was: Soxhlet≈UAE>UAE+PLE>PLE, using hydroethanolic mixtures as solvents. Extractions with acidified water and ultrasound were not effective to recover phenolics. Two, four and fourteen anthocyanins were identified in the extracts from grumixama, blackberry and blueberry, respectively.

Sequential high pressure extractions applied to recover piceatannol and scirpusin B from passion fruit bagasse

Passion fruit seeds are currently discarded on the pulp processing but are known for their high piceatannol and scirpusin B contents. Using pressurized liquid extraction (PLE), these highly valuable phenolic compounds were efficiently extracted from defatted passion fruit bagasse (DPFB). PLE was performed using mixtures of ethanol and water (50 to 100% ethanol, w/w) as solvent, temperatures from 50 to 70°C and pressure at 10MPa. The extraction methods were compared in terms of the global yield, total phenolic content (TPC), piceatannol content and the antioxidant capacity of the extracts. The DPFB extracts were also compared with those from non-defatted passion fruit bagasse (nDPFB). Identification and quantification of piceatannol were performed using UHPLC-MS/MS. The results showed that high TPC and piceatannol content were achieved for the extracts obtained from DPFB through PLE at 70°C and using 50 and 75% ethanol as the solvent. The best PLE conditions for TPC (70°C, 75% ethanol) resulted in 55.237mgGAE/g dried and defatted bagasse, whereas PLE at 70°C and 50% ethanol achieved 18.590mg of piceatannol/g dried and defatted bagasse, and such yields were significantly higher than those obtained using conventional extraction techniques. The antioxidant capacity assays showed high correlation with the TPC (r>0.886) and piceatannol (r>0.772). The passion fruit bagasse has therefore proved to be a rich source of piceatannol and PLE showed high efficiency to recover phenolic compounds from defatted passion fruit bagasse.

SUPERCRITICAL EXTRACTION OF LINSEED OIL: ECONOMICAL VIABILITY AND MODELING EXTRACTION CURVES

The aim of the present study was to use supercritical technology to recover linseed oil (Linum usitatissimum L.) using carbon dioxide (alone or modified with ethanol as solvent) to determine the influence of the technique on the chemical composition of the oil obtained, model the kinetic curves of extraction, and estimate the manufacturing cost of the process. The experiments were conducted at 323 K, pressure of 25 MPa, constant solvent flow of 1.7 × 10−5 kg/s, and extraction time of 5 h. The highest yield was obtained with the addition of cosolvent (28.8%). The SFE process of linseed oil manufacture proved to be economically viable, resulting in a product with a specific cost of 13.21 US