29 resultados para SUPERCRITICAL FLUID EXTRACTION WITH CO2


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Under increasing greenhouse gas concentrations, ocean heat uptake moderates the rate of climate change, and thermal expansion makes a substantial contribution to sea level rise. In this paper we quantify the differences in projections among atmosphere-ocean general circulation models of the Coupled Model Intercomparison Project in terms of transient climate response, ocean heat uptake efficiency and expansion efficiency of heat. The CMIP3 and CMIP5 ensembles have statistically indistinguishable distributions in these parameters. The ocean heat uptake efficiency varies by a factor of two across the models, explaining about 50% of the spread in ocean heat uptake in CMIP5 models with CO2 increasing at 1%/year. It correlates with the ocean global-mean vertical profiles both of temperature and of temperature change, and comparison with observations suggests the models may overestimate ocean heat uptake and underestimate surface warming, because their stratification is too weak. The models agree on the location of maxima of shallow ocean heat uptake (above 700 m) in the Southern Ocean and the North Atlantic, and on deep ocean heat uptake (below 2000 m) in areas of the Southern Ocean, in some places amounting to 40% of the top-to-bottom integral in the CMIP3 SRES A1B scenario. The Southern Ocean dominates global ocean heat uptake; consequently the eddy-induced thickness diffusivity parameter, which is particularly influential in the Southern Ocean, correlates with the ocean heat uptake efficiency. The thermal expansion produced by ocean heat uptake is 0.12 m YJ−1, with an uncertainty of about 10% (1 YJ = 1024 J).

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Projections of climate change impacts on crop yields are inherently uncertain1. Uncertainty is often quantified when projecting future greenhouse gas emissions and their influence on climate2. However, multi-model uncertainty analysis of crop responses to climate change is rare because systematic and objective comparisons among process-based crop simulation models1, 3 are difficult4. Here we present the largest standardized model intercomparison for climate change impacts so far. We found that individual crop models are able to simulate measured wheat grain yields accurately under a range of environments, particularly if the input information is sufficient. However, simulated climate change impacts vary across models owing to differences in model structures and parameter values. A greater proportion of the uncertainty in climate change impact projections was due to variations among crop models than to variations among downscaled general circulation models. Uncertainties in simulated impacts increased with CO2 concentrations and associated warming. These impact uncertainties can be reduced by improving temperature and CO2 relationships in models and better quantified through use of multi-model ensembles. Less uncertainty in describing how climate change may affect agricultural productivity will aid adaptation strategy development andpolicymaking.

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The global mean temperature in 2008 was slightly cooler than that in 2007; however, it still ranks within the 10 warmest years on record. Annual mean temperatures were generally well above average in South America, northern and southern Africa, Iceland, Europe, Russia, South Asia, and Australia. In contrast, an exceptional cold outbreak occurred during January across Eurasia and over southern European Russia and southern western Siberia. There has been a general increase in land-surface temperatures and in permafrost temperatures during the last several decades throughout the Arctic region, including increases of 1° to 2°C in the last 30 to 35 years in Russia. Record setting warm summer (JJA) air temperatures were observed throughout Greenland. The year 2008 was also characterized by heavy precipitation in a number of regions of northern South America, Africa, and South Asia. In contrast, a prolonged and intense drought occurred during most of 2008 in northern Argentina, Paraguay, Uruguay, and southern Brazil, causing severe impacts to agriculture and affecting many communities. The year began with a strong La Niña episode that ended in June. Eastward surface current anomalies in the tropical Pacific Ocean in early 2008 played a major role in adjusting the basin from strong La Niña conditions to ENSO-neutral conditions by July–August, followed by a return to La Niña conditions late in December. The La Niña conditions resulted in far-reaching anomalies such as a cooling in the central tropical Pacific, Arctic Ocean, and the regions extending from the Gulf of Alaska to the west coast of North America; changes in the sea surface salinity and heat content anomalies in the tropics; and total column water vapor, cloud cover, tropospheric temperature, and precipitation patterns typical of a La Niña. Anomalously salty ocean surface salinity values in climatologically drier locations and anomalously fresh values in rainier locations observed in recent years generally persisted in 2008, suggesting an increase in the hydrological cycle. The 2008 Atlantic hurricane season was the 14th busiest on record and the only season ever recorded with major hurricanes each month from July through November. Conversely, activity in the northwest Pacific was considerably below normal during 2008. While activity in the north Indian Ocean was only slightly above average, the season was punctuated by Cyclone Nargis, which killed over 145,000 people; in addition, it was the seventh-strongest cyclone ever in the basin and the most devastating to hit Asia since 1991. Greenhouse gas concentrations continued to rise, increasing by more than expected based on with CO2 the 1979 to 2007 trend. In the oceans, the global mean uptake for 2007 is estimated to be 1.67 Pg-C, about CO2 0.07 Pg-C lower than the long-term average, making it the third-largest anomaly determined with this method since 1983, with the largest uptake of carbon over the past decade coming from the eastern Indian Ocean. Global phytoplankton chlorophyll concentrations were slightly elevated in 2008 relative to 2007, but regional changes were substantial (ranging to about 50%) and followed long-term patterns of net decreases in chlorophyll with increasing sea surface temperature. Ozone-depleting gas concentrations continued to fall globally to about 4% below the peak levels of the 2000–02 period. Total column ozone concentrations remain well below pre-1980, levels and the 2008 ozone hole was unusually large (sixth worst on record) and persistent, with low ozone values extending into the late December period. In fact the polar vortex in 2008 persisted longer than for any previous year since 1979. Northern Hemisphere snow cover extent for the year was well below average due in large part to the record-low ice extent in March and despite the record-maximum coverage in January and the shortest snow cover duration on record (which started in 1966) in the North American Arctic. Limited preliminary data imply that in 2008 glaciers continued to lose mass, and full data for 2007 show it was the 17th consecutive year of loss. The northern region of Greenland and adjacent areas of Arctic Canada experienced a particularly intense melt season, even though there was an abnormally cold winter across Greenland's southern half. One of the most dramatic signals of the general warming trend was the continued significant reduction in the extent of the summer sea-ice cover and, importantly, the decrease in the amount of relatively older, thicker ice. The extent of the 2008 summer sea-ice cover was the second-lowest value of the satellite record (which started in 1979) and 36% below the 1979–2000 average. Significant losses in the mass of ice sheets and the area of ice shelves continued, with several fjords on the northern coast of Ellesmere Island being ice free for the first time in 3,000–5,500 years. In Antarctica, the positive phase of the SAM led to record-high total sea ice extent for much of early 2008 through enhanced equatorward Ekman transport. With colder continental temperatures at this time, the 2007–08 austral summer snowmelt season was dramatically weakened, making it the second shortest melt season since 1978 (when the record began). There was strong warming and increased precipitation along the Antarctic Peninsula and west Antarctica in 2008, and also pockets of warming along coastal east Antarctica, in concert with continued declines in sea-ice concentration in the Amundsen/Bellingshausen Seas. One significant event indicative of this warming was the disintegration and retreat of the Wilkins Ice Shelf in the southwest peninsula area of Antarctica.

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Dynamic viscoelasticity of electrorheological fluids based on microcrystalline cellulose/castor oil suspensions was experimentally investigated in squeeze flow. The dependence of storage modulus G' and loss modulus G" parallel to external electric field on electric fields and strain amplitudes is presented. The experiments show that, when external electric field is higher than the critical field, the viscoelasticity of the ER fluids converts from linear to nonlinear, and the ER fluids transfer from solid-like state to fluid state with the growth of strain amplitude. The influences of strain amplitude and oscillatory frequency on the nonlinearity of viscoelasticity were also studied.

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Experiments with CO2 instantaneously quadrupled and then held constant are used to show that the relationship between the global-mean net heat input to the climate system and the global-mean surface-air-temperature change is nonlinear in Coupled Model Intercomparison Project phase 5 (CMIP5) Atmosphere-Ocean General Circulation Models (AOGCMs). The nonlinearity is shown to arise from a change in strength of climate feedbacks driven by an evolving pattern of surface warming. In 23 out of the 27 AOGCMs examined the climate feedback parameter becomes significantly (95% confidence) less negative – i.e. the effective climate sensitivity increases – as time passes. Cloud feedback parameters show the largest changes. In the AOGCM-mean approximately 60% of the change in feedback parameter comes from the topics (30N-30S). An important region involved is the tropical Pacific where the surface warming intensifies in the east after a few decades. The dependence of climate feedbacks on an evolving pattern of surface warming is confirmed using the HadGEM2 and HadCM3 atmosphere GCMs (AGCMs). With monthly evolving sea-surface-temperatures and sea-ice prescribed from its AOGCM counterpart each AGCM reproduces the time-varying feedbacks, but when a fixed pattern of warming is prescribed the radiative response is linear with global temperature change or nearly so. We also demonstrate that the regression and fixed-SST methods for evaluating effective radiative forcing are in principle different, because rapid SST adjustment when CO2 is changed can produce a pattern of surface temperature change with zero global mean but non-zero change in net radiation at the top of the atmosphere (~ -0.5 Wm-2 in HadCM3).

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We report the first examples of hydrophilic 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands, and their applications as actinide(III) selective aqueous complexing agents. The combination of a hydrophobic diamide ligand in the organic phase and a hydrophilic tetrasulfonated bis-triazine ligand in the aqueous phase is able to separate Am(III) from Eu(III) by selective Am(III) complex formation across a range of nitric acid concentrations with very high selectivities, and without the use of buffers. In contrast, disulfonated bis-triazine ligands are unable to separate Am(III) from Eu(III) in this system. The greater ability of the tetrasulfonated ligands to retain Am(III) selectively in the aqueous phase than the corresponding disulfonated ligands appears to be due to the higher aqueous solubilities of the complexes of the tetrasulfonated ligands with Am(III). The selectivities for Am(III) complexation observed with hydrophilic tetrasulfonated bis-triazine ligands are in many cases far higher than those found with the polyaminocarboxylate ligands previously used as actinide-selective complexing agents, and are comparable to those found with the parent hydrophobic bis-triazine ligands. Thus we demonstrate a feasible alternative method to separate actinides from lanthanides than the widely studied approach of selective actinide extraction with hydrophobic bis-1,2,4-triazine ligands such as CyMe4-BTBP and CyMe4-BTPhen.

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In the Coupled Model Intercomparison Project Phase 5 (CMIP5), the model-mean increase in global mean surface air temperature T under the 1pctCO2 scenario (atmospheric CO2 increasing at 1% yr−1) during the second doubling of CO2 is 40% larger than the transient climate response (TCR), i.e. the increase in T during the first doubling. We identify four possible contributory effects. First, the surface climate system loses heat less readily into the ocean beneath as the latter warms. The model spread in the thermal coupling between the upper and deep ocean largely explains the model spread in ocean heat uptake efficiency. Second, CO2 radiative forcing may rise more rapidly than logarithmically with CO2 concentration. Third, the climate feedback parameter may decline as the CO2 concentration rises. With CMIP5 data, we cannot distinguish the second and third possibilities. Fourth, the climate feedback parameter declines as time passes or T rises; in 1pctCO2, this effect is less important than the others. We find that T projected for the end of the twenty-first century correlates more highly with T at the time of quadrupled CO2 in 1pctCO2 than with the TCR, and we suggest that the TCR may be underestimated from observed climate change.

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Lowland heath is an internationally important habitat type that has greatly declined in abundance throughout Western Europe. In recent years this has led to a growing interest in the restoration of heathland on agricultural land. This generally requires the use of chemical treatments to return soil chemical conditions to those appropriate for the support of heathland ecosystems. However, the potential for negative impacts on the environment due to the potential of these treatments to increase the availability of trace metals via raised soil acidity requires investigation. A large-scale field study investigated the effect of two chemical treatments used in heathland restoration, elemental sulphur and ferrous sulphate, on soil acidity and whether it is possible to predict the effect of the treatments on availability of two potentially toxic cations (Al and Cd) in the soil along with their subsequent accumulation in the shoots of the grass Agrostis capillaris. Results showed that both treatments decreased soil pH, but that only elemental sulphur produced a pH similar to heathland soil. The availability of Al, measured by extraction with 1 M ammonium nitrate, could not be predicted by soil pH, depth in the soil and total Al concentration in the soil. By contrast, availability of Cd could be predicted from these three variables. Concentrations of both Al and Cd in the shoots of A. capillaris showed no significant relationship with the extractable concentration in the soil. Results are discussed in light of the possible environmental impacts of the chemical restoration techniques.

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Wheat Distillers’ Dried Grains with Solubles (DDGS) and in-process samples were used for protein extraction. Prolamins were the predominant protein components in the samples. The absence of extractable α- and γ-gliadins in DDGS indicated protein aggregation during the drum drying processing stage. Prolamin extraction was performed using 70% (v/v) ethanol or alkaline-ethanol solution in the presence of reducing agent. DDGS extracts had relatively low protein contents (14-44.9%, w/w), regardless of the condition applied. The wet solids were the most suitable raw material for protein extraction, with recovery yields of ~ 55% (w/w) and protein content of ~58% (w/w) in 70% (v/v) ethanol. Protein extracts from wet solids were significantly rich in glutamic acid and proline. Mass balance calculations demonstrated the high carbohydrate content (~ 50%, w/w) of solid residues. Overall, the feasibility of utilising in-process samples of DDGS for protein extraction with commercial potential was demonstrated.

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In analysis of complex nuclear forensic samples containing lanthanides, actinides and matrix elements, rapid selective extraction of Am/Cm for quantification is challenging, in particular due the difficult separation of Am/Cm from lanthanides. Here we present a separation process for Am/Cm(III) which is achieved using a combination of AG1-X8 chromatography followed by Am/Cm extraction with a triazine ligand. The ligands tested in our process were CyMe4-BTPhen, CyMe4- BTBP, CA-BTP and CA-BTPhen. Our process allows for purification and quantification of Am and Cm (recoveries 80%–100%) and other major actinides in < 2d without the use of multiple columns or thiocyanate. The process is unaffected by high level Ca(II)/Fe(III)/Al(III) (10mg mL−1) and thus requires little pre-treatment of samples.

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Stabilized nano-sized water droplet carrying water-soluble Co2+ species is employed as a new catalyst system for the oxidation of the alkyl aromatics in the presence of a fluorinated surfactant. This stable system contains no labile C-H structure and can facilitate excellent mixing of catalytic Co(II)/NaBr species, hydrocarbon substrates and oxygen in supercritical carbon dioxide fluid, which is demonstrated to be an excellent alternative solvent system to acetic acid or nitric acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions. As a result, potential advantages of this 'greener' catalytic method including safer operation, easier separation and purification, higher catalytic activity with selectivity and without using corrosive or oxidation unstable solvent are therefore envisaged.

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We have developed a new method for the synthesis of Pd nanoparticles with controllable sizes within a silica matrix using solid-supported surfactants in supercritical CO2. XRD, HRTEM and CO chemisorption data show that unformly sized Pd nanoparticles are evenly distributed within the porous silica and are chemically tethered by surfactant molecules [poly(oxyethylene stearyl ether) and fluorinated poly(oxyethylene)]. It is postulated that tiny solid-supported surfactant assemblies act as nano-reactors for the template synthesis of nanoparticles or clusters from the soluble precursors therein.

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One of the key hindrances on development of solid catalysts containing cobalt species for partial oxidation of organic molecules at mild conditions in conventional liquid phase is the severe metal leaching. The leached soluble Co species with a higher degree of freedom always out-performs those of solid supported Co species in oxidation catalysis. However, the homogeneous Co species concomitantly introduces separation problems. We have recently reponed for the first time, a new oxidation catalyst system for the oxidation of organic molecules in supercritical CO2 using the principle of micellar catalysis. [CF3(CF2)(8)COO](2)Co.xH(2)O (the fluorinated anionic moiety forms aqueous reverse micelles carrying water-soluble Co2+ cations in scCO(2)) was previously shown to be extremely active for the oxidation of toluene in the presence of sodium bromide in water-CO2 mixture, giving 98% conversion and 99% selectivity to benzoic acid at 120 degreesC. In this study, we show that the effects of varying the type of surfactant counterions and the length of the surfactant chains on catalysis. It is found that the use of [CF3(CF2)(8)COO](2)Mg.yH(2)O/Co(II) acetate is as effective as the [CF3(CF2)(8)COO](2)Co.xH(2)O and the fluorinated chain length used has a subtle effect on the catalytic rate measured. It is also demonstrated that this new type of micellar catalyst in scCO(2) can be easily separated via CO2 depressurisation and be reused without noticeable deactivation. (C) 2003 Elsevier B.V. All rights reserved.