Intercropping with pulses to concentrate nitrogen and sulphur in wheat

The effects of intercropping wheat with faba bean (Denmark, Germany, Italy and UK) and wheat with pea (France), in additive and replacement designs on grain nitrogen and sulphur concentrations were studied in field experiments in the 2002/03, 2003/04 and 2004/05 growing seasons. Intercropping wheat with grain legumes regularly increased the nitrogen concentration of the cereal grain, irrespective of design or location. Sulphur concentration of the cereal was also increased by intercropping, but less regularly and to a lesser extent compared with effects on nitrogen concentration. Nitrogen concentration (g/kg) in wheat additively intercropped with faba bean was increased by 8% across all sites (weighted for inverse of variance), but sulphur concentration was only increased by 4%, so N:S ratio was also increased by 4%. Intercropping wheat with grain legumes increased sodium dodecyl sulphate (SDS)-sedimentation volume. The effect of intercropping on wheat nitrogen concentration was greatest when intercropping had the most deleterious effect on wheat yield and the least deleterious effect on pulse yield. Over all sites and seasons, and irrespective of whether the design was additive or replacement, increases in crude protein concentration in the wheat of 10 g/kg by intercropping with faba bean were associated with 25-30% yield reduction of the wheat, compared with sole-cropped wheat. It was concluded that the increase in protein concentration of wheat grain in intercrops could be of economic benefit when selling wheat for breadmaking, but only if the bean crop was also marketed effectively.

Delaying senescence of wheat with fungicides has interacting effects with cultivar on grain sulphur concentration but not with sulphur yield or nitrogen: sulphur ratios

Winter wheat was grown in three field experiments, each repeated over two or three seasons, to investigate effects of extending flag leaf life by fungicide application on the concentration, kg ha(-1) and mg grain(-1) of nitrogen (N) and sulphur (S) as well as N:S ratio and sodium dodecyl sulphate (SDS) sedimentation volume. The experiments involved up to six cultivars and different application rates, timings and frequencies of azoxystrobin and epoxiconazole. For every day the duration to 37 % green flag leaf area (m) was extended, N yield was increased by 2.58 kg ha(-1), N per grain by 0.00957 mg, S yield by 0.186 kg ha(-1) and S per grain by 0.000718 mg. The N:S ratio decreased by 0.0135 per day. There was no evidence that these responses varied with cultivar. In contrast, the relationship between flag leaf life and N or S concentration interacted with cultivar. The N and S concentrations of Shamrock, the cultivar that suffered most from brown rust (Puccinia rccondita), increased with the extension of flag leaf life whereas the concentrations of N and S in Malacca, a cultivar more susceptible to Septoria tritici, decreased as flag leaf senescence was delayed. This was because the relationships between m and N and S yields were much better conserved over cultivars than those between m and thousand grain weight (TGW) and grain yield ha(-1). (c) 2004 Elsevier B.V. All rights reserved.

4,4 '-Dipyridyl-N,N '-dioxide complexes of metal-thiocyanate/selenocyanate: pi-stacked molecular rods as three-dimensional support for two-dimensional polymeric sheets and intra/interchain S center dot center dot center dot S interaction dependent architecture of the R-2(2)(8) synthon driven assembly of one-dimensional polymeric chains

Three supramolecular complexes of Co(II) using SCN-/SeCN- in combination with 4,4'-dipyridyl-N,N'-dioxide (dpyo), i.e., {[Co(SCN)(2)(dpyo)(2)].(dpyo)}(n) ( 1), {[Co(SCN)(2)(dpyo)(H2O)(2)].(H2O)}(n) ( 2), {[Co(SeCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 3), have been synthesized and characterized by single-crystal X-ray analysis. Complex 1 is a rare example of a dpyo bridged two-dimensional (2D) coordination polymer, and pi-stacked dpyo supramolecular rods are generated by the lattice dpyo, passing through the rhombic grid of stacked layers, resulting in a three-dimensional (3D) superstructure. Complexes 2 and 3 are isomorphous one-dimensional (1D) coordination polymers [-Co-dpyo-Co-] that undergo self-assembly leading to a bilayer architecture derived through an R-2(2)(8) H-bonding synthon between coordinated water and dpyo oxygen. A reinvestigation of coordination polymers [Mn(SCN)(2)(dpyo)( H2O)(MeOH)](n) ( 4) and {[Fe(SCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 5) reported recently by our group [ Manna et al. Indian J. Chem. 2006, 45A, 1813] reveals brick wall topology rather than bilayer architecture is due to the decisive role of S center dot center dot center dot S/Se center dot center dot center dot Se interactions in determining the helical nature in 4 and 5 as compared to zigzag polymeric chains in 2 and 3, although the same R-2(2)(8) synthon is responsible for supramolecular assembly in these complexes.

Complexes of the uranyl ion with bis(diphenylphosphino)methane dioxide

Bis(diphenylphosphino)methane dioxide compounds of uranyl nitrate and uranyl bis(beta-diketonates) have been synthesized and characterized by spectroscopic and X-ray diffraction methods. Monodentate, bidentate chelate and bridging bidentate modes of coordination for this ligand have been established from the single-crystal X-ray diffraction studies of its compounds, [UO2(DBM)(2)DPPMO], [UO2(NO3)(2)DPPNO] and [{UO2(DBM)(2)}(2)DPPMO], respectively. (C) 2004 Elsevier Ltd. All rights reserved.

Temperature dependent high-resolution infrared photoabsorption cross-sections of trifluoromethyl sulphur pentafluoride

Absolute infrared photoabsorption cross-sections have been measured over the range 600-1500 cm(-1) for the powerful greenhouse gas SF5CF3 at high resolution (0.03 cm(-1)) and at temperatures between 203 and 298 K. Our data indicate that the integrated absorption intensity shows a weak negative dependence on temperature. It is concluded therefore that previous calculations of radiative forcings and global warming potentials based on room-temperature data are reasonable estimates for the atmosphere, but may be low by a few percent. (C) 2002 Elsevier Science B.V. All rights reserved.

The adsorption geometry of sulphur on Ir{100}: a quantitative LEED study

A quantitative low energy electron diffraction (LEED) analysis has been performed for the p(2 x 2)-S and c(2 x 2)-S surface structures formed by exposing the (1 x 1) phase of Ir{100} to H2S at 750 K. S is found to adsorb on the fourfold hollow sites in both structures leading to Pendry R-factor values of 0.17 for the p(2 x 2)-S and 0.16 for the c(2 x 2)-S structures. The distances between S and the nearest and next-nearest Ir atoms were found to be similar in both structures: 2.36 +/- 0.01 angstrom and 3.33 +/- 0.01 angstrom, respectively. The buckling in the second substrate layer is consistent with other structural studies for S adsorption on fcc{100} transition metal surfaces: 0.09 angstrom for p(2 x 2)-S and 0.02 angstrom for c(2 x 2)-S structures. The (1 x 5) reconstruction, which is the most stable phase for clean Ir{100}, is completely lifted and a c(2 x 2)-S overlayer is formed after exposure to H,S at 300 K followed by annealing to 520 K. CO temperature-programmed desorption (TPD) experiments indicate that the major factor in the poisoning of Ir by S is site blocking. (c) 2005 Elsevier B.V. All rights reserved.

Pressure-dependent product distribution of citral hydrogenation over micelle-hosted Pd and Ru nanoparticles in supercritical carbon dioxide

In situ synthesis and testing of Ru and Pd nanoparticles as catalysts in the presence of ammonium perfluorohydrocarbo-carboxylate surfactant in supercritical carbon dioxide were carried out in a stainless steel batch reactor at 40 degrees C over a pressure range of 80-150 bar CO2/H-2. Direct Visualization of the formation of a supercritical phase at above 80 bar, followed by the formation of homogeneous microemulsions containing dispersed Ru nanoparticles and Pd nanoparticles in scCO(2) at above 95-100 bar, were conducted through a sapphire window reactor using a W-0 (molar water to surfactant ratio) of 30. The synthesised RU and Pd nanoparticles showed interesting product distributions in the selective hydrogenation of organic molecules, depending critically oil the density and polarity of the fluid (which ill turn depends on the pressure applied). Thus, selective hydrogenation of the citral molecule, which contains three reducible groups (aldehydes and double bonds at the 23 and 6,7 positions), is feasible Lis a chemical probe. (c) 2005 Elsevier Inc. All rights reserved.

Micelle-hosted palladium nanoparticles catalyze citral molecule hydrogenation in supercritical carbon dioxide

A new approach of employing metal particles in micelles for the hydrogenation of organic molecules in the presence of fluorinated surfactant and water in supercritical carbon dioxide has very recently been introduced. This is allegedly to deliver many advantages for carrying out catalysis including the use of supercritical carbon dioxide (scCO(2)) as a greener solvent. Following this preliminary account, the present work aims to provide direct visual evidence on the formation of metal microemulsions and to investigate whether metal located in the soft micellar assemblies could affect reaction selectivity. Synthesis of Pd nanoparticles in perfluorohydrocarboxylate anionic micelles in scCO(2) is therefore carried out in a stainless steel batch reactor at 40 degreesC and in a 150 bar CO2/H-2 mixture. Homogeneous dispersion of the microemulsion containing Pd nanoparticles in scCO(2) is observed through a sapphire window reactor at W-0 ratios (molar water-to-surfactant ratios) ranging from 2 to 30. It is also evidenced that the use of micelle assemblies as new metal catalyst nanocarriers could indeed exert a great influence on product selectivity. The hydrogenation of a citral molecule that contains three reducible groups (aldehyde, double bonds at the 2,3-position and the 6,7-position) is studied. An unusually high selectivity toward citronellal (a high regioselectivity toward the reduction of the 2,3-unsaturation) is observed in supercritical carbon dioxide. On the other hand, when the catalysis is carried out in the conventional liquid or vapor phase over the same reaction time, total hydrogenation of the two double bonds is achieved. It is thought that the high kinetic reluctance for double bond hydrogenation of the citral molecule at the hydrophobic end (the 6,7-position) is due to the unique micelle environment that is in close proximity to the metal surface in supercritical carbon dioxide that guides a head-on attack of the molecule toward the core metal particle.

Partial aerial oxidation of nonpolar alcohols over Teflon-modified noble metal catalysts in supercritical carbon dioxide

We have reported earlier that modification of commercial graphite Pt-supported catalysts with Teflon fluorinated polymeric coating of a very strong hydrophobic nature can significantly improve catalytic activity for aerial oxidation of water-insoluble alcohols such as anthracene methanol in supercritical carbon dioxide (scCO(2)). Thus, this paper presents some further characterization of these new catalyst materials and the working fluid phase during the catalysis. Using the same Teflon-modified metal catalysts, this paper addresses the oxidation of another water-insoluble alcohol molecule, m-hydrobenzoin in scCO(2). It is found that conversion and product distribution of this diol oxidation critically depend on the temperature and pressure of the scCO(2) used, which suggest the remarkable solvent properties of the scCO(2) under these unconventional oxidation conditions. (C) 2004 Elsevier Inc. All rights reserved.

A new oxidation catalyst system using fluorous cobalt(II) species in water-supercritical carbon dioxide (C-H free environment)

Stabilized water droplet dispersed in supercritical carbon dioxide fluid is demonstrated to be an excellent alternative solvent system to acetic acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions.

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.

An integrated assessment of carbon dioxide capture and storage in the UK

Geological carbon dioxide storage (CCS) has the potential to make a significant contribution to the decarbonisation of the UK. Amid concerns over maintaining security, and hence diversity, of supply, CCS could allow the continued use of coal, oil and gas whilst avoiding the CO2 emissions currently associated with fossil fuel use. This project has explored some of the geological, environmental, technical, economic and social implications of this technology. The UK is well placed to exploit CCS with a large offshore storage capacity, both in disused oil and gas fields and saline aquifers. This capacity should be sufficient to store CO2 from the power sector (at current levels) for a least one century, using well understood and therefore likely to be lower-risk, depleted hydrocarbon fields and contained parts of aquifers. It is very difficult to produce reliable estimates of the (potentially much larger) storage capacity of the less well understood geological reservoirs such as non-confined parts of aquifers. With the majority of its large coal fired power stations due to be retired during the next 15 to 20 years, the UK is at a natural decision point with respect to the future of power generation from coal; the existence of both national reserves and the infrastructure for receiving imported coal makes clean coal technology a realistic option. The notion of CCS as a ‘bridging’ or ‘stop-gap’ technology (i.e. whilst we develop ‘genuinely’ sustainable renewable energy technologies) needs to be examined somewhat critically, especially given the scale of global coal reserves. If CCS plant is built, then it is likely that technological innovation will bring down the costs of CO2 capture, such that it could become increasingly attractive. As with any capitalintensive option, there is a danger of becoming ‘locked-in’ to a CCS system. The costs of CCS in our model for UK power stations in the East Midlands and Yorkshire to reservoirs in the North Sea are between £25 and £60 per tonne of CO2 captured, transported and stored. This is between about 2 and 4 times the current traded price of a tonne of CO2 in the EU Emissions Trading Scheme. In addition to the technical and economic requirements of the CCS technology, it should also be socially and environmentally acceptable. Our research has shown that, given an acceptance of the severity and urgency of addressing climate change, CCS is viewed favourably by members of the public, provided it is adopted within a portfolio of other measures. The most commonly voiced concern from the public is that of leakage and this remains perhaps the greatest uncertainty with CCS. It is not possible to make general statements concerning storage security; assessments must be site specific. The impacts of any potential leakage are also somewhat uncertain but should be balanced against the deleterious effects of increased acidification in the oceans due to uptake of elevated atmospheric CO2 that have already been observed. Provided adequate long term monitoring can be ensured, any leakage of CO2 from a storage site is likely to have minimal localised impacts as long as leaks are rapidly repaired. A regulatory framework for CCS will need to include risk assessment of potential environmental and health and safety impacts, accounting and monitoring and liability for the long term. In summary, although there remain uncertainties to be resolved through research and demonstration projects, our assessment demonstrates that CCS holds great potential for significant cuts in CO2 emissions as we develop long term alternatives to fossil fuel use. CCS can contribute to reducing emissions of CO2 into the atmosphere in the near term (i.e. peak-shaving the future atmospheric concentration of CO2), with the potential to continue to deliver significant CO2 reductions over the long term.