Energetic constraints on precipitation under climate change

Energetic constraints on precipitation are useful for understanding the response of the hydrological cycle to ongoing climate change, its response to possible geoengineering schemes, and the limits on precipitation in very warm climates of the past. Much recent progress has been made in quantifying the different forcings and feedbacks on precipitation and in understanding how the transient responses of precipitation and temperature might differ qualitatively. Here, we introduce the basic ideas and review recent progress. We also examine the extent to which energetic constraints on precipitation may be viewed as radiative constraints and the extent to which they are confirmed by available observations. Challenges remain, including the need to better demonstrate the link between energetics and precipitation in observations and to better understand energetic constraints on precipitation at sub-global length scales.

Effect of high temperature and water stress on groundnuts under field conditions

Groundnuts cultivated in the semiarid tropics are often exposed to water stress (mid-season and end season) and high temperature (> 34 °C) during the critical stages of flowering and pod development. This study evaluated the effects of both water stress and high temperature under field conditions at ICRISAT, India. Treatments included two irrigations (full irrigation, 100 % of crop evapotranspiration; and water stress, 40 % of crop evapotranspiration), four temperature treatments from a combination of two sowing dates and heat tunnels with mean temperatures from sowing to maturity of 26.3° (T1), 27.3° (T2), 29.0° (T3) and 29.7 °C (T4) and two genotypes TMV2 and ICGS 11. The heat tunnels were capable of raising the day temperature by > 10 °C compared to ambient. During the 20-day high-temperature treatment at flowering, mean temperatures were 33.8° (T1), 41.6° (T2), 38.7° (T3) and 43.5°C (T4). The effects of water stress and high temperature were additive and temporary for both vegetative and pod yield, and disappeared as soon as high-temperature stress was removed. Water use efficiency was significantly affected by the main effects of temperature and cultivar and not by water stress treatments. Genotypic differences for tolerance to high temperature can be attributed to differences in flowering pattern, flower number, peg-set and harvest index. It can be inferred from this study that genotypes that are tolerant to water stress are also tolerant to high temperature under field conditions. In addition, genotypes with an ability to establish greater biomass and with a significantly greater partitioning of biomass to pod yield would be suitable for sustaining higher yields in semiarid tropics with high temperature and water stress.

The development and contribution of surface charge by crop residues in two Malawian acid soils

The effects of maize and soya bean residues on the pH and charge of a loamy sand (Kawalazi) and a sandy clay loam (Naming'omba) from Malawi were measured to determine both the indirect effect of the residues on soil charge through the changes in pH, and the direct contribution of charge carried on the residue surfaces. The soils had pH values (10 mM CaCl2) of 4.3 and 5.0 and organic matter contents were 1.4% and 2.7%, respectively. The clay fractions were dominated by kaolinite and goethite, and mica was present in both samples. The soils were incubated for 28 days with maize (Zea mays) and soya bean (Glycine max) residues. The maximum addition of residue (12.0%) in the Kawalazi and Naming'omba soils increased the pH from 4.3 and 5.0 to 4.8 and 5.3 (maize) and to 9.0 and 8.8 (soya bean), respectively. Negative charge increased from 2.1 and 4.7 cmol(c) kg(-1) to 3.8 and 7.5 (maize) and to 5.3 and 9.3 cmol(c) kg(-1) (soya bean). Positive charge increased from 0.72 and 0.62 to 0.87 and 0.85 cmol(c) kg(-1) (maize) and to 0.75 and 0.68 (soya bean). The charge contribution by the residues was calculated by difference between the charge on a sample incubated with residue and the charge on a soil without residue limed to the same pH value. Up to 100 cmolc negative charge and 10 cmol(c) of positive charge per kg of residue were directly contributed to the soil-residue mixture, the amounts depending on the type of residue, the extent to which the residue was decomposed in the soil and the pH of the mixture. The Anderson and Sposito method [Soil Sci. Soc. Am. J. 55 (1991) 1569] was used to partition the permanent negative charge (holding Cs+) from variable negative charge (holding Li+). In the pH range 3.7-6.5 the maize residue contributed between 3 and 26 cmol(c) of variable charge per kg of residue in the Kawalazi soil and between 6 and 25 cmol(c) per kg of residue in the Naming'omba soil. For soya bean the values were between I and 28 and between 4 and 68 cmolc per kg of residue, respectively. At a given pH value, the charge tended to increase with time of incubation and for a given addition of residue, pH decreased during incubation. Addition of residues contributed no permanent negative charge and the charge on the soil measured by Cs adsorption was independent of pH change caused by the residue showing that the method is valid for soil-residue mixtures. With time there was a decrease in the amount of permanent charge probably due to masking as humic material become adsorbed on mineral surfaces. (C) 2003 Elsevier Science B.V. All rights reserved.

Correlation between regioselectivity and site charge in propene polymerisation catalysed by metallocene

The reactions of propene with [Zr(cyclopentadienyl)(2)Me](+) have been investigated using density functional theory in order to study the correlation between regioselectivity and site charge in propene polymerisation. The reaction paths of the 1,2 and 2,1 additions of the methyl group to propene have been established. The geometries and energies of the reactants, transition states and products have been obtained using both PBEPBE/LANL2DZ and B3LYP/LANL2DZ methodologies. The results with both density functionals show that the activation energy for 1,2-insertion is lower than that for 2,1-insertion (Fig. 5) and this is consistent with the experiment results. Also for both density functionals, the difference of the thermal dynamic driving forces between the 2,1 product named 2-21 and the 1,2 product named 2-12 is significantly lower than the difference between the energy barriers. It is noted that in the reactants, the Mulliken partial charge on the central carbon atom C2 is positive and it can be concluded that 1,2-insertion is favoured because it can proceed via a cationic reaction.

Surface chemistry of glycine on Pt{111} in different aqueous environments

Adsorption of glycine on Ptf111g under UHV conditions and in different aqueous environments was studied by XPS (UHV and ambient pressure) and NEXAFS. Under UHV conditions, glycine adsorbs in its neutral molecular state up to about 0.15 ML. Further deposition leads to the formation of an additional zwitterionic species, which is in direct contact with the substrate surface, followed by the growth of multilayers, which also consist of zwitterions. The neutral surface species is most stable and decomposes at 360 K through a multi-step process which includes the formation of methylamine and carbon monoxide. When glycine and water are co-adsorbed in UHV at low temperatures (< 170 K) inter-layer diffusion is inhibited and the surface composition depends on the adsorption sequence. Water adsorbed on top of a glycine layer does not lead to significant changes in its chemical state. When glycine is adsorbed on top of a pre-adsorbed chemisorbed water layer or thick ice layer, however, it is found in its zwitterionic state, even at low coverage. No difference is seen in the chemical state of glycine when the layers are exposed to ambient water vapor pressure up to 0.2 Torr at temperatures above 300 K. Also the decomposition temperature stays the same, 360 K, irrespective of the water vapor pressure. Only the reaction path of the decomposition products is affected by ambient water vapor.

Both black and symbolically white: The 'Bajan-Brit' return migrant as post-colonial hybrid

The research presented in this article centres on an under-researched demographic group of young return migrants, namely, second-generation Barbadians, or 'Bajan-Brits', who have decided to 'return' to the birthplace of their parents. Based on 51 in-depth interviews, the essay examines the experiences of second-generation return migrants from an interpretative perspective framed within post-colonial discourse. The article first considers the Bajan-Brits and issues of race in the UK before their decision to migrate. It is then demonstrated that on 'return', in certain respects, these young, black English migrants occupy a liminal position of cultural, racial and economic privilege, based on their 'symbolic' or 'token' whiteness within the post-colonial context of Barbados. But this very hybridity and inbetweeness means that they also face difficulties and associated feelings of social alienation and discrimination. The ambivalent status of this transnational group of migrants serves to challenge traditional notions of Barbadian racial identity.

Hydrothermal synthesis and structural characterization of novel alpha-Keggin unit-supported Cu(II)- and Mn(II)-bipyridine complexes from a tri-lacunary precursor

Blue [{Cu(2,2'-bipy)(2)}(2){alpha-SiW12O40}] (bipy = bipyridyl) (1) and pale yellow [Mn(2,2'-bipy)(3)](2)[alpha-SiW12O40] (2) have been synthesized hydrothermally and characterized by IR spectroscopy and single crystal X-ray structure analysis. In 1, the [alpha-SiW12O40](4-) ion acts as a bridge between the two [{Cu(2,2'-bipy)(2)](2+) moieties via coordination through the terminal oxygen atoms, while in 2, the [Mn(2,2'-bipy)(3)](2+) ion balances the charge on the polyoxo anion without forming any covalent bond. To the best of our knowledge, this is the first example of transition metal-mediated transformation of [alpha-SiW9O34](10-) to [alpha-SiW12O40](4-).

Self-assembly of a modified amyloid peptide fragment: pH-responsiveness and nematic phase formation

The self-assembly of peptide YYKLVFFC based on a fragment of the amyloid beta (A) peptide, A beta 16-20, KLVFF has been studied in aqueous solution. The peptide is designed with multiple functional residues to examine the interplay between aromatic interactions and charge on the self-assembly, as well as specific transformations such as the pH-induced phenol-phenolate transition of the tyrosine residue. Circular dichroism (CD) and Fourier-transform infrared (FTIR) spectroscopies are used to investigate the conditions for beta-sheet self-assembly and the role of aromatic interactions in the CD spectrum as a function of pH and concentration. The formation of well-defined fibrils at pH 4.7 is confirmed by cryo-TEM (transmission electron microscope) and negative stain TEM. The morphology changes at higher pH, and aggregates of short twisted fibrils are observed at pH 11. Polarized optical microscopy shows birefringence at a low concentration (1 wt.-%) of YYKLVFFC in aqueous solution, and small-angle X-ray scattering was used to probe nematic phase formation in more detail. A pH-induced transition from nematic to isotropic phases is observed on increasing pH that appears to be correlated to a reduction in aggregate anisotropy upon increasing pH.

Self-assembly and hydrogelation of an amyloid peptide fragment

The self-assembly of a fragment of the amyloid beta peptide that has been shown to be critical in amyloid fibrillization has been studied in aqueous solution. There are conflicting reports in the literature on the fibrillization of A beta (16-20), i.e., KLVFF, and our results shed light on this. In dilute solution, self-assembly of NH2-KLVFF-COOH is strongly influenced by aromatic interactions between phenylalanine units, as revealed by UV spectroscopy and circular dichroism. Fourier transform infrared (FTIR) spectroscopy reveals beta-sheet features in spectra taken for more concentrated solutions and also dried films. X-ray diffraction and cryo-transmission electron microscopy (cryo-TEM) provide further support for beta-sheet amyloid fibril formation. A comparison of cryo-TEM images with those from conventional dried and negatively stained TEM specimens highlights the pronounced effects of sample preparation on the morphology. A comparison of FTIR data for samples in solution and dried samples also highlights the strong effect of drying on the self-assembled structure. In more concentrated phosphate-buffered saline (PBS) solution, gelation of NH2-KLVFF-COOH is observed. This is believed to be caused by screening of the electrostatic charge on the peptide, which enables beta sheets to aggregate into a fibrillar gel network. The rheology of the hydrogel is probed, and the structure is investigated by light scattering and small-angle X-ray scattering.

Fair trade and European public procurement: legal principles and governance dynamics

Purpose The article examines principles of Fair Trade in public procurement in Europe, focusing on legal dimensions related to the European Public Procurement Directives. Design/methodology/approach The article situates public procurement of Fair Trade products in relation to the rise of non-state regulatory initiatives, highlighting how they have entered into new governance dynamics in the public sector and play a part in changing practices in sustainable procurement. A review of legal position on Fair Trade in procurement law is informed by academic research and campaigning experience from the Fair Trade Advocacy Office. Findings Key findings are that the introduction of Fair Trade products into European public procurement has been marked by legal ambiguity, having developed outside comprehensive policy or legal guidelines. Following a 2012 ruling by the Court of Justice of the European Union, it is suggested that the legal position for Fair Trade in procurement has become clearer, and that forthcoming change to the Public Procurement Directives may facilitate the uptake of fair trade products by public authorities. However potential for future expansion of the public sector ‘market’ for Fair Trade is approached with caution: purchasing Fair Trade products as a marker of sustainability, which started to be embedded within procurement practice in the 2000s, is challenged by current European public austerity measures. Research limitations/implications Suggestions for future research include the need for systematic cross-institutional and multi-country comparison of the legal and governance dimensions of procurement practice with regard to Fair Trade. Practical implications A clarification of current state-of-play with regard to legal aspects of fair trade in public procurement of utility for policy and advocacy discussion. Originality/value The article provides needed elaboration on an under researched topic area of value to academia and policy makers.

A lightweight balloon-carried cloud charge sensor

Despite the importance of microphysical cloud processes on the climate system, some topics are under-explored. For example, few measurements of droplet charges in nonthunderstorm clouds exist. Balloon carried charge sensors can be used to provide new measurements. A charge sensor is described for use with meteorological balloons, which has been tested over a range of atmospheric temperatures from -60 to 20 degrees C, in cloudy and clear air. The rapid time response of the sensor (to >10 V s(-1)) permits charge densities from 100 fC m(-3) to 1 nC m(-3) to be determined, which is sufficient for it to act as a cloud edge charge detector at weakly charged horizontal cloud boundaries.

Microbe-associated molecular pattern (MAMP) signatures, synergy, size and charge: influences on perception or mobility and host defence responses

Triggering of defences by microbes has mainly been investigated using single elicitors or microbe-associated molecular patterns (MAMPs), but MAMPs are released in planta as complex mixtures together with endogenous oligogalacturonan (OGA) elicitor. We investigated the early responses in Arabidopsis of calcium influx and oxidative burst induced by non-saturating concentrations of bacterial MAMPs, used singly and in combination: flagellin peptide (flg22), elongation factor peptide (elf18), peptidoglycan (PGN) and component muropeptides, lipo-oligosaccharide (LOS) and core oligosaccharides. This revealed that some MAMPs have additive (e.g. flg22 with elf18) and even synergistic (flg22 and LOS) effects, whereas others mutually interfere (flg22 with OGA). OGA suppression of flg22-induced defences was not a result of the interference with the binding of flg22 to its receptor flagellin-sensitive 2 (FLS2). MAMPs induce different calcium influx signatures, but these are concentration dependent and unlikely to explain the differential induction of defence genes [pathogenesis-related gene 1 (PR1), plant defensin gene 1.2 (PDF1.2) and phenylalanine ammonia lyase gene 1 (PAL1)] by flg22, elf18 and OGA. The peptide MAMPs are potent elicitors at subnanomolar levels, whereas PGN and LOS at high concentrations induce low and late host responses. This difference might be a result of the restricted access by plant cell walls of MAMPs to their putative cellular receptors. flg22 is restricted by ionic effects, yet rapidly permeates a cell wall matrix, whereas LOS, which forms supramolecular aggregates, is severely constrained, presumably by molecular sieving. Thus, MAMPs can interact with each other, whether directly or indirectly, and with the host wall matrix. These phenomena, which have not been considered in detail previously, are likely to influence the speed, magnitude, versatility and composition of plant defences.

Effects of cultural system (organic and conventional) on growth, photosynthesis and yield components of sweet corn (zea mays L.) under semi-arid environment

Organic sweet maize consists of a new industrial crop product. Field experiment was conducted to determine the effects of cultural systems on growth, photosynthesis and yield components of sweet maize crop (Zea mays L. F-1 hybrid 'Midas'). A randomized complete block design was employed with four replicates per treatment (organic fertilization: cow manure (5, 10 and 20 t ha(-1)), poultry manure (5, 10 and 20 t ha(-1)) and barley mulch (5, 10 and 20 t ha(-1)), synthetic fertilizer (240 kg N ha(-1)): 21-0-0 and control). The lowest dry weight, height and leaf area index and sod organic matter were measured in the control treatment. Organic matter content was proportionate to the amount of manure applied. The control plots had the lowest yield (1593 kg ha(-1)) and the double rate cow manure plots the had,greatest one. (6104 kg ha(-1)). High correlation between sweet corn yield and organic matter was registered. Moreover, the lowest values of 1000-grain weight were obtained with control plot. The fertilizer plot gave values which were similar to the full rate cow manure treatment. The photosynthetic race of the untreated control was significantly lower than that of the other treatments. The phorosynthetic rate increased as poultry manure and barley mulch ram decreased and as cow manure increased. Furthermore the untreated control had the lowest stomatal conductance and chlorophyll content. Our results indicated that sweet corn growth and yield in the organic plots was significantly higher than those in the conventional plots.

UV irradiance as a major influence on growth, development and secondary products of commercial importance in Lollo Rosso lettuce 'Revolution' grown under polyethylene films

The growth and production of anthocyanin, flavonoid and phenolic compounds were evaluated in Lollo Rosso lettuce 'Revolution' grown continuously under films varying in their ability to transmit LTV radiation (completely transparent to IN, transparent above 320, 350, 370 and 3 80 nm and completely opaque to LTV radiation). Plants were grown from seed under UV transparent and UV blocking films and destructively harvested 3-4 weeks after transplanting. Plants under a complete UV blocking film (UV400) produced up to 2.2 times more total above ground dry weight than plants under the UV transparent film. In contrast, anthocyanin content in plants under the UV blocking film was approximately eight times lower than in plants under a UV transparent film. Furthermore, there was a curvilinear relationship between the anthocyanin content and LTV wavelength cutoff such that above 370 run there was no further reduction in anthocyanin content. Fluorescence measurements indicated that photosynthetic performance index was 15% higher under the presence of UVB and UVA (UV280) than under the presence of UVA (UV320) and 53% higher than in the absence of UV radiation suggesting protection of the photosynthetic apparatus possibly by phenolic compounds. These findings are of particular importance as the potential of UV transmitting films to increase secondary compounds may offer the opportunity to produce plants commercially with increased health benefits compared to those grown under conventional films.

Effects of fungicide dose and mixtures on selection for triazole resistance in Mycosphaerella graminicola under field conditions

The effects of varying doses of fungicides, alone or in mixtures, on selection for triazole resistance were examined under field conditions. Two experiments were conducted using the triazole fungicide fluquinconazole with the strobilurin fungicide azoxystrobin as a mixture partner. Inoculated wheat plots with a known ratio of more sensitive to less sensitive isolates of the leaf blotch fungus Mycosphaerella graminicola were sprayed with fungicide and sampled once symptoms had appeared. Selection for fluquinconazole resistance increased in proportion to the dose, up to one-half of the full dose (the maximum tested) in both experiments. At the higher doses of fluquinconazole, the addition of azoxystrobin was associated with a decrease in selection (nonsignificant in the first experiment) for triazole resistance. Control by low doses of fluquinconazole was increased by mixture with azoxystrobin, but at higher doses mixture with azoxystrobin sometimes decreased control, so that reduced selection was obtained at the cost of some reduction in control. The effects on resistance are not necessarily general consequences of mixing fungicides, and suggest that the properties of any specific mixture may need to be demonstrated experimentally. Selection was inversely related to control in the unmixed treatments in both experiments, but the relationship was weaker in the mixtures with azoxystrobin.