Changes in the global sulfate burden due to perturbations in global CO2 concentrations

A large ensemble of general circulation model (GCM) integrations coupled to a fully interactive sulfur cycle scheme were run on the climateprediction.net platform to investigate the uncertainty in the climate response to sulfate aerosol and carbon dioxide (CO2) forcing. The sulfate burden within the model (and the atmosphere) depends on the balance between formation processes and deposition (wet and dry). The wet removal processes for sulfate aerosol are much faster than dry removal and so any changes in atmospheric circulation, cloud cover, and precipitation will feed back on the sulfate burden. When CO2 is doubled in the Hadley Centre Slab Ocean Model (HadSM3), global mean precipitation increased by 5%; however, the global mean sulfate burden increased by 10%. Despite the global mean increase in precipitation, there were large areas of the model showing decreases in precipitation (and cloud cover) in the Northern Hemisphere during June–August, which reduced wet deposition and allowed the sulfate burden to increase. Further experiments were also undertaken with and without doubling CO2 while including a future anthropogenic sulfur emissions scenario. Doubling CO2 further enhanced the increases in sulfate burden associated with increased anthropogenic sulfur emissions as observed in the doubled CO2-only experiment. The implications are that the climate response to doubling CO2 can influence the amount of sulfate within the atmosphere and, despite increases in global mean precipitation, may act to increase it.

Use of a crop model ensemble to quantify CO2 stimulation of water-stressed and well-watered crops

Increased atmospheric concentrations of carbon dioxide (CO2) will benefit the yield of most crops. Two free air CO2 enrichment (FACE) meta-analyses have shown increases in yield of between 0 and 73% for C3 crops. Despite this large range, few crop modelling studies quantify the uncertainty inherent in the parameterisation of crop growth and development. We present a novel perturbed-parameter method of crop model simulation, which uses some constraints from observations, that does this. The model used is the groundnut (i.e. peanut; Arachis hypogaea L.) version of the general large-area model for annual crops (GLAM). The conclusions are of relevance to C3 crops in general. The increases in yield simulated by GLAM for doubled CO2 were between 16 and 62%. The difference in mean percentage increase between well-watered and water-stressed simulations was 6.8. These results were compared to FACE and controlled environment studies, and to sensitivity tests on two other crop models of differing levels of complexity: CROPGRO, and the groundnut model of Hammer et al. [Hammer, G.L., Sinclair, T.R., Boote, K.J., Wright, G.C., Meinke, H., Bell, M.J., 1995. A peanut simulation model. I. Model development and testing. Agron. J. 87, 1085-1093]. The relationship between CO2 and water stress in the experiments and in the models was examined. From a physiological perspective, water-stressed crops are expected to show greater CO2 stimulation than well-watered crops. This expectation has been cited in literature. However, this result is not seen consistently in either the FACE studies or in the crop models. In contrast, leaf-level models of assimilation do consistently show this result. An analysis of the evidence from these models and from the data suggests that scale (canopy versus leaf), model calibration, and model complexity are factors in determining the sign and magnitude of the interaction between CO2 and water stress. We conclude from our study that the statement that 'water-stressed crops show greater CO2 stimulation than well-watered crops' cannot be held to be universally true. We also conclude, preliminarily, that the relationship between water stress and assimilation varies with scale. Accordingly, we provide some suggestions on how studies of a similar nature, using crop models of a range of complexity, could contribute further to understanding the roles of model calibration, model complexity and scale. (C) 2008 Elsevier B.V. All rights reserved.

Quantification of physical and biological uncertainty in the simulation of the yield of a tropical crop using present-day and doubled CO2 climates

The impacts of climate change on crop productivity are often assessed using simulations from a numerical climate model as an input to a crop simulation model. The precision of these predictions reflects the uncertainty in both models. We examined how uncertainty in a climate (HadAM3) and crop General Large-Area Model (GLAM) for annual crops model affects the mean and standard deviation of crop yield simulations in present and doubled carbon dioxide (CO2) climates by perturbation of parameters in each model. The climate sensitivity parameter (lambda, the equilibrium response of global mean surface temperature to doubled CO2) was used to define the control climate. Observed 1966-1989 mean yields of groundnut (Arachis hypogaea L.) in India were simulated well by the crop model using the control climate and climates with values of lambda near the control value. The simulations were used to measure the contribution to uncertainty of key crop and climate model parameters. The standard deviation of yield was more affected by perturbation of climate parameters than crop model parameters in both the present-day and doubled CO2 climates. Climate uncertainty was higher in the doubled CO2 climate than in the present-day climate. Crop transpiration efficiency was key to crop model uncertainty in both present-day and doubled CO2 climates. The response of crop development to mean temperature contributed little uncertainty in the present-day simulations but was among the largest contributors under doubled CO2. The ensemble methods used here to quantify physical and biological uncertainty offer a method to improve model estimates of the impacts of climate change.

Long-term response of the nematode community to elevated atmospheric CO2 in a temperate dry grassland soil

Long-term effects of the elevated atmospheric CO2 on biosphere have been in focus of research since the last few decades. In this experiment undisturbed soil monoliths of loess grassland were exposed to an elevated CO2 environment (two-times the ambient CO2 level) for a period of six years with the aid of the open top chamber method. Control without a chamber and CO2 elevation was applied as well. Elevated CO2 level had very little impact oil soil food web. It did not influence either root and microbial biomass or microbial and nematode community structure. The only significant response was that density of the bacterial feeder genus Heterocephalobus increased in the chamber with elevated CO2 concentration. Application of the open top chambers initiated more changes on nematodes than the elevated CO2 level. Open top chamber (OTC) method decreased nematode density (total and plant feeder as well) to less than half of the original level. Negative effect was found on the genus level in the case of fungal feeder Aphelenchoides, plant feeder Helicotylenchus and Paratylenchus. It is very likely that the significantly lower belowground root biomass and partly its decreased quality reflected by the increased C/N ratio are the main responsible factors for the lower density of the plant feeder nematodes in the plots of chambers. According to diversity profiles, MI and MI(2-15) parameters, nematode communities in the open top chambers (both on ambient and elevated CO2 level) seem to be more structured than those under normal circumstances six years after start of the experiment.

Acclimation of photosynthesis to elevated CO2 in onion (Allium cepa) grown at a range of temperatures

Onion (Allium cepa) was grown in the field within temperature gradient tunnels (providing about -2.5degreesC to +2.5degreesC from outside temperatures) maintained at either 374 or 532 mumol mol(-1) CO2. Plant leaf area was determined non-destructively at 7 day intervals until the time of bulbing in 12 combinations of temperature and CO2 concentration. Gas exchange was measured in each plot at the time of bulbing, and the carbohydrate content of the leaf (source) and bulb (sink) was determined. Maximum rate of leaf area expansion increased with mean temperature. Leaf area duration and maximum rate of leaf area expansion were not significantly affected by CO2. The light-saturated rates of leaf photosynthesis (A(sat)) were greater in plants grown at normal than at elevated CO2 concentrations at the same measurement CO2 concentration. Acclimation of photosynthesis decreased with an increase in growth temperature, and with an increase in leaf nitrogen content at elevated CO2. The ratio of intercellular to atmospheric CO2 (C-i/C-a ratio) was 7.4% less for plants grown at elevated compared with normal CO2. A(sat) in plants grown at elevated CO2 was less than in plants grown at normal CO2 when compared at the same C-i Hence, acclimation of photosynthesis was due both to stomatal acclimation and to limitations to biochemical CO2 fixation. Carbohydrate content of the onion bulbs was greater at elevated than at normal CO2. In contrast, carbohydrate content was less at elevated compared with normal CO2 in the leaf sections in which CO2 exchange was measured at the same developmental stage. Therefore, acclimation of photosynthesis in fully expanded onion leaves was detected despite the absence of localised carbohydrate accumulation in these field-grown crops.

Water use of a bioenergy plantation increases in a future high CO2 world

Fast-growing poplar trees may in future be used as a source of renewable energy for heat, electricity and biofuels such as bioethanol. Water use in Populus x euramericana (clone I214), following long-term exposure to elevated CO2 in the POPFACE (poplar free-air carbon dioxide enrichment) experiment, is quantified here. Stomatal conductance was measured and, during two measurement campaigns made before and after coppicing, whole-tree water use was determined using heat-balance sap-flow gauges, first validated using eddy covariance measurements of latent heat flux. Water use was determined by the balance between leaf-level reductions in stomatal conductance and tree-level stimulations in transpiration. Reductions in stomatal conductance were found that varied between 16 and 39% relative to ambient air. Whole-tree sap flow was increased in plants growing under elevated CO2, on average, by 12 and 23%, respectively, in the first and in the second measurement campaigns. These results suggest that future CO2 concentrations may result in an increase in seasonal water use in fast-growing, short-rotation Populus plantations.

Acclimation of photosynthesis to elevated CO2 in onion (allium cepa) grown at a range of temperatures

Onion (Allium cepa) was grown in the field within temperature gradient tunnels (providing about -2.5 degrees C to +2.5 degrees C from outside temperatures) maintained at either 374 or 532 mumol mol (-1) CO2. Plant leaf area was determined non-destructively at 7 day intervals until the time of bulbing in 12 combinations of temperature and CO2 concentration. Gas exchange was measured in each plot at the time of bulbing, and the carbohydrate content of the leaf (source) and bulb (sink) was determined. Maximum rate of leaf area expansion increased with mean temperature. Leaf area duration and maximum rate of leaf area expansion were not significantly affected by CO2. The light-saturated rates of leaf photosynthesis (A(sat)) were greater in plants grown at normal than at elevated CO2 concentrations at the same measurement CO2 concentration. Acclimation of photosynthesis decreased with an increase in growth temperature, and with an increase in leaf nitrogen content at elevated CO2. The ratio of intercellular to atmospheric CO2 (C-i/C-a ratio) was 7.4% less for plants grown at elevated compared with normal CO2. A(sat) in plants grown at elevated CO2 was less than in plants grown at normal CO2 when compared at the same C-i Hence, acclimation of photosynthesis was due both to stomatal acclimation and to limitations to biochemical CO2 fixation. Carbohydrate content of the onion bulbs was greater at elevated than at normal CO2. In contrast, carbohydrate content was less at elevated compared with normal CO2 in the leaf sections in which CO2 exchange was measured at the same developmental stage. Therefore, acclimation of photosynthesis in fully expanded onion leaves was detected despite the absence of localised carbohydrate accumulation in these field-grown crops.

Molecular guided catalytic hydrogenation by micelle-hosted Pd nanoparticle in supercritical CO2

Homogeneous dispersion of microemulsion containing palladium nanoparticles in scCO(2) is, for the first time, observed via sapphire window reactor and these particles show an unusual reluctance for double bond hydrogenation of citral aldehyde at hydrophobic end rather than hydrophilic end (high regioselectivity) owing to the unique micelle environment in supercritical carbon dioxide that guide a head-on attack of the molecule.

Coordination-driven self-assembly of a novel carbonato-bridged heteromolecular neutral nickel(II) triangle by atmospheric CO2 fixation

Formation of a quasi-symmetrical mu(3)-carbonato-bridged self-assembled heteromolecular triangle of Ni(II), [(mu(3)-CO3){Ni-2(salmeNH)(2)(NCS)(2)}[Ni(salmeNH(2))(2)]center dot Et2O center dot H2O (HsalmeNH = 2-[(3-methylamino-propylimino)-methyl]-phenol) involves atmospheric CO2 uptake in a neutral medium, by spontaneous self-reorganization of the starting mononuclear Ni(II)-Schiff-base complex, [Ni(salmeNH)(2)]. The environment around Ni(II) in two of the subunits is different from the third one. The starting complex, (Ni(salmeNH)(2)], and one of the possible intermediate species, [Ni(salmeNH(2))(2)(NCS)(2)], which has a very similar coordination environment to that in the third Ni(II) center, have been characterized structurally. A plausible mechanism for the formation of such a triangle has also been proposed. The compound shows a very strong antiferromagnetic coupling. Fit as a regular triangular arrangement gave J = -53.1, g = 2.24, and R = 1.5 x 10(-4).

Occurrence of ribbons of cyclic water pentamers in a metallo-organic framework formed by spontaneous fixation of CO2

In the reaction of equimolar amounts of copper(II) acetate with 2,2'-dipyridylamine (DPA) in aqueous tetrahydrofuran, in presence of KOH, aerial CO2 is spontaneously fixed to the carbonate anion yielding [Cu(DPA)(CO3)] . 3H(2)O (1). X-ray crystallography shows the presence of zigzag ribbons of cyclic water pentamers in the channels of a chain-like metallo-organic framework. The water ribbons are stabilised by hydrogen bonds to the metallo-organic backbone. Each (H2O)(5) pentamer is approximately planar.

Selective catalytic oxidation of alkylaromatic molecules by nanosize water droplets containing Co2+ species in supercritical carbon dioxide fluid

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.

Micelle-hosted bimetallic Pd-Ru nanoparticle for in situ catalytic hydrogenation in supercritical CO2

Bimetallic Pd-Ru nanoparticles of different elemental ratios are prepared via in situ reduction of their simple salts in reverse micelles in supercritical carbon dioxide (scCO(2)). The optimised Pd:Ru (1: 1) nanoparticle shows the highest activity for hydrogenation of functionalised alkene under mild conditions, which can be easily recycled under the reaction conditions without use of organic solvent. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis of well-dispersed nanoparticles within porous solid structures using surface-tethered surfactants in supercritical CO2

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.

Micellar catalysis for partial oxidation of toluene to benzoic acid in supercritical CO2: effects of fluorinated surfactants

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.