A systematic and feasible method for computing nuclear contributions to electrical properties of polyatomic molecules

An analytic method to evaluate nuclear contributions to electrical properties of polyatomic molecules is presented. Such contributions control changes induced by an electric field on equilibrium geometry (nuclear relaxation contribution) and vibrational motion (vibrational contribution) of a molecular system. Expressions to compute the nuclear contributions have been derived from a power series expansion of the potential energy. These contributions to the electrical properties are given in terms of energy derivatives with respect to normal coordinates, electric field intensity or both. Only one calculation of such derivatives at the field-free equilibrium geometry is required. To show the useful efficiency of the analytical evaluation of electrical properties (the so-called AEEP method), results for calculations on water and pyridine at the SCF/TZ2P and the MP2/TZ2P levels of theory are reported. The results obtained are compared with previous theoretical calculations and with experimental values

Impact of mass lumping on gravity and Rossby waves in 2D finite-element shallow-water models

The goal of this study is to evaluate the effect of mass lumping on the dispersion properties of four finite-element velocity/surface-elevation pairs that are used to approximate the linear shallow-water equations. For each pair, the dispersion relation, obtained using the mass lumping technique, is computed and analysed for both gravity and Rossby waves. The dispersion relations are compared with those obtained for the consistent schemes (without lumping) and the continuous case. The P0-P1, RT0 and P-P1 pairs are shown to preserve good dispersive properties when the mass matrix is lumped. Test problems to simulate fast gravity and slow Rossby waves are in good agreement with the analytical results.

Spatial covariation of Azotobacter abundance and soil properties: A case study using the wavelet transform

The soil microflora is very heterogeneous in its spatial distribution. The origins of this heterogeneity and its significance for soil function are not well understood. A problem for understanding spatial variation better is the assumption of statistical stationarity that is made in most of the statistical methods used to assess it. These assumptions are made explicit in geostatistical methods that have been increasingly used by soil biologists in recent years. Geostatistical methods are powerful, particularly for local prediction, but they require the assumption that the variability of a property of interest is spatially uniform, which is not always plausible given what is known about the complexity of the soil microflora and the soil environment. We have used the wavelet transform, a relatively new innovation in mathematical analysis, to investigate the spatial variation of abundance of Azotobacter in the soil of a typical agricultural landscape. The wavelet transform entails no assumptions of stationarity and is well suited to the analysis of variables that show intermittent or transient features at different spatial scales. In this study, we computed cross-variograms of Azotobacter abundance with the pH, water content and loss on ignition of the soil. These revealed scale-dependent covariation in all cases. The wavelet transform also showed that the correlation of Azotobacter abundance with all three soil properties depended on spatial scale, the correlation generally increased with spatial scale and was only significantly different from zero at some scales. However, the wavelet analysis also allowed us to show how the correlation changed across the landscape. For example, at one scale Azotobacter abundance was strongly correlated with pH in part of the transect, and not with soil water content, but this was reversed elsewhere on the transect. The results show how scale-dependent variation of potentially limiting environmental factors can induce a complex spatial pattern of abundance in a soil organism. The geostatistical methods that we used here make assumptions that are not consistent with the spatial changes in the covariation of these properties that our wavelet analysis has shown. This suggests that the wavelet transform is a powerful tool for future investigation of the spatial structure and function of soil biota. (c) 2006 Elsevier Ltd. All rights reserved.

Exploring the spatial relations between soil physical properties and apparent electrical conductivity

Relations between the apparent electrical conductivity of the soil (ECa) and top- and sub-soil physical properties were examined for two arable fields in southern England (Crowmarsh Battle Farms and the Yattendon Estate). The spatial variation of ECa and the soil properties was explored geostatistically. The variogram ranges showed that ECa varied on a similar spatial scale to many of the soil physical properties in both fields. Several features in the map of kriged predictions of ECa were also evident in maps of the soil properties. In addition, the correlation coefficients showed a strong relation between ECa and several soil properties. A moving correlation analysis enabled differences in the relations between ECa and the soil properties to be examined within the fields. The results indicated that relations were inconsistent; they were stronger in some areas than others. A regression of ECa on the principal component scores of the leading components for both fields showed that the first two components accounted for a large proportion of the variance in ECa, whereas the others accounted for little or none. For Crowmarsh topsoil sand and clay, loss on ignition and volumetric water measured in the autumn had large correlations on the first component, and for Yattendon they were large for topsoil sand and clay, and autumn and spring volumetric water. The cross-variograms suggested strong coregionalization between ECa and several soil physical properties; in particular subsoil sand and silt at Crowmarsh, and subsoil sand and clay at Yattendon. The structural correlations from the linear model of coregionalization confirmed the strength of the relations between ECa and the subsoil properties. Nevertheless, no one property was consistently important for both fields. Although a map of ECa can indicate the general patterns of spatial variation in the soil, it is not a substitute for information on soil properties obtained by sampling and analysing the soil. Nevertheless, it could be used to guide further sampling. (c) 2005 Elsevier B.V. All rights reserved.

Monitoring and modelling the three-dimensional flow of water under drip irrigation

The interpretation of soil water dynamics under drip irrigation systems is relevant for crop production as well as on water use and management. In this study a three-dimensional representation of the flow of water under drip irrigation is presented. The work includes analysis of the water balance at point scale as well as area-average, exploring uncertainties in water balance estimations depending on the number of locations sampled. The water flow was monitored by detailed profile water content measurements before irrigation, after irrigation and 24 h later with a dense array of soil moisture access tubes radially distributed around selected drippers. The objective was to develop a methodology that could be used on selected occasions to obtain 'snap shots' of the detailed three-dimensional patterns of soil moisture. Such patterns are likely to be very complex, as spatial variability will be induced for a number of reasons, such as strong horizontal gradients in soil moisture, variations between individual sources in the amount of water applied and spatial variability is soil hydraulic properties. Results are compared with a widely used numerical model, Hydrus-2D. The observed dynamic of the water content distribution is in good agreement with model simulations, although some discrepancies concerning the horizontal distribution of the irrigation bulb are noted due to soil heterogeneity. (c) 2006 Elsevier B.V. All rights reserved.

Exploring the spatial relations between soil properties and electro-magnetic induction (EMI) and the implications for management

The relations between soil electrical conductivity (ECa) and top- and sub-soil physical properties were examined for an arable field in England. The correlation coefficients between ECa and the soil particle size fractions were large and their cross variograms showed that the coregionalization was also strong. The coregionalization was stronger for the subsoil properties than for the topsoil, the reverse to the correlation coefficients. The relations between ECa and some soil properties, such as clay and water content, appear complex and emphasize that a map of ECa cannot substitute for sampling the soil.

Effect of manure application on crop yield and soil chemical properties in a long-term field trial of semi-arid Kenya

The sustainability of cereal/legume intercropping was assessed by monitoring trends in grain yield, soil organic C (SOC) and soil extractable P (Olsen method) measured over 13 years at a long-term field trial on a P-deficient soil in semi-arid Kenya. Goat manure was applied annually for 13 years at 0, 5 and 10 t ha(-1) and trends in grain yield were not identifiable because of season-to-season variations. SOC and Olsen P increased for the first seven years of manure application and then remained constant. The residual effect of manure applied for four years only lasted another seven to eight years when assessed by yield, SOC and Olsen P. Mineral fertilizers provided the same annual rates of N and P as in 5 t ha(-1) manure and initially ,gave the same yield as manure, declining after nine years to about 80%. Therefore, manure applications could be made intermittently and nutrient requirements topped-up with fertilizers. Grain yields for sorghum with continuous manure were described well by correlations with rainfall and manure input only, if data were excluded for seasons with over 500 mm rainfall. A comprehensive simulation model should correctly describe crop losses caused by excess water.

Plant roots release phospholipid surfactants that modify the physical and chemical properties of soil

Plant root mucilages contain powerful surfactants that will alter the interaction of soil solids with water and ions, and the rates of microbial processes. The lipid composition of maize, lupin and wheat root mucilages was analysed by thin layer chromatography and gas chromatography-mass spectrometry. A commercially available phosphatidylcholine (lecithin), chemically similar to the phospholipid surfactants identified in the mucilages, was then used to evaluate its effects on selected soil properties. The lipids found in the mucilages were principally phosphatidylcholines, composed mainly of saturated fatty acids, in contrast to the lipids extracted from root tissues. In soil at low tension, lecithin reduced the water content at any particular tension by as much as 10 and 50% in soil and acid-washed sand, respectively. Lecithin decreased the amount of phosphate adsorption in soil and increased the phosphate concentration in solution by 10%. The surfactant also reduced net rates of ammonium consumption and nitrate production in soil. These experiments provide the first evidence we are aware of that plant-released surfactants will significantly modify the biophysical environment of the rhizosphere.

A 3D stochastic cloud model for investigating the radiative properties of inhomogeneous cirrus clouds

(From author). Comments: First 3D stochastic/fractal model of cirrus; first detailed analysis & explanation of power spectra of ice water content, including first observations of 50-km scale break and mixing-induced steepening of spectrum; first demonstration of the potential effect of wind shear on radiative fluxes by changing fall-streak orientation. Has spawned work on the effect of 3D photon transport on the radiative effects of cirrus clouds.

Independent evaluation of the ability of spaceborne radar and lidar to retrieve the microphysical and radiative properties of ice clouds

The combination of radar and lidar in space offers the unique potential to retrieve vertical profiles of ice water content and particle size globally, and two algorithms developed recently claim to have overcome the principal difficulty with this approach-that of correcting the lidar signal for extinction. In this paper "blind tests" of these algorithms are carried out, using realistic 94-GHz radar and 355-nm lidar backscatter profiles simulated from aircraft-measured size spectra, and including the effects of molecular scattering, multiple scattering, and instrument noise. Radiation calculations are performed on the true and retrieved microphysical profiles to estimate the accuracy with which radiative flux profiles could be inferred remotely. It is found that the visible extinction profile can be retrieved independent of assumptions on the nature of the size distribution, the habit of the particles, the mean extinction-to-backscatter ratio, or errors in instrument calibration. Local errors in retrieved extinction can occur in proportion to local fluctuations in the extinction-to-backscatter ratio, but down to 400 m above the height of the lowest lidar return, optical depth is typically retrieved to better than 0.2. Retrieval uncertainties are greater at the far end of the profile, and errors in total optical depth can exceed 1, which changes the shortwave radiative effect of the cloud by around 20%. Longwave fluxes are much less sensitive to errors in total optical depth, and may generally be calculated to better than 2 W m(-2) throughout the profile. It is important for retrieval algorithms to account for the effects of lidar multiple scattering, because if this is neglected, then optical depth is underestimated by approximately 35%, resulting in cloud radiative effects being underestimated by around 30% in the shortwave and 15% in the longwave. Unlike the extinction coefficient, the inferred ice water content and particle size can vary by 30%, depending on the assumed mass-size relationship (a problem common to all remote retrieval algorithms). However, radiative fluxes are almost completely determined by the extinction profile, and if this is correct, then errors in these other parameters have only a small effect in the shortwave (around 6%, compared to that of clear sky) and a negligible effect in the longwave.

Temperature-responsive properties and drug solubilization capacity of amphiphilic copolymers based on N-vinylpyrrolidone and vinyl propyl ether

A series of amphiphilic copolymers were synthesized by free-radical copolymerization of N-vinylpyrrolidone (NVP) with vinyl propyl ether (VPE), and the structure of the copolymers was characterized by elemental analysis and gel permeation chromatography. The reactivity of VPE in copolymerization was found to be significantly lower than the reactivity of NVP, which resulted in a decrease of copolymers’ yields and molecular weights with higher content of VPE in the feed mixture. An investigation of the behavior of the copolymers in aqueous solutions at different temperatures by dynamic light scattering revealed the presence of lower critical solution temperature, which depending on the content of VPE ranged within 23−38 °C. Aqueous solutions of these copolymers were studied by fluorescent spectroscopy with pyrene as a polarity probe to reveal the formation of hydrophobic domains. The copolymers were found to be useful for enhancing the solubility of riboflavin in water.

Global estimates of snow water equivalent from passive microwave instruments: history, challenges and future developments

Snow properties have been retrieved from satellite data for many decades. While snow extent is generally felt to be obtained reliably from visible-band data, there is less confidence in the measurements of snow mass or water equivalent derived from passive microwave instruments. This paper briefly reviews historical passive microwave instruments and products, and compares the large-scale patterns from these sources to those of general circulation models and leading reanalysis products. Differences are seen to be large between the datasets, particularly over Siberia. A better understanding of the errors in both the model-based and measurement-based datasets is required to exploit both fully. Techniques to apply to the satellite measurements for improved large-scale snow data are suggested.

Correlations between microphysical properties of large-scale semi-transparent cirrus and the state of the atmosphere

By making use of TOVS Path-B satellite retrievals and ECMWF reanalyses, correlations between bulk microphysical properties of large-scale semi-transparent cirrus (visible optical thickness between 0.7 and 3.8) and thermodynamic and dynamic properties of the surrounding atmosphere have been studied on a global scale. These clouds constitute about half of all high clouds. The global averages (from 60°N to 60°S) of mean ice crystal diameter, De, and ice water path (IWP) of these clouds are 55 μm and 30 g m−2, respectively. IWP of these cirrus is slightly increasing with cloud-top temperature, whereas De of cold cirrus does not depend on this parameter. Correlations between De and IWp of large-scale cirrus seem to be different in the midlatitudes and in the tropics. However, we observe in general stronger correlations between De and IWP and atmospheric humidity and winds deduced from the ECMWF reanalyses: De and IWP increase both with increasing atmospheric water vapour. There is also a good distinction between different dynamical situations: In humid situations, IWP is on average about 10 gm−2 larger in regions with strong large-scale vertical updraft only that in regions with strong large-scale horizontal winds only, whereas the mean De of cold large-scale cirrus decreases by about 10 μm if both strong large-scale updraft and horizontal winds are present.

Single amino acid substitutions in puroindoline-b mutants influence lipid binding properties

External reflectance Fourier transform infrared (ER-FTIR) spectroscopy and surface pressure measurements have been used to characterize the interaction of wild-type puroindoline-b (Pin-b) and two mutant forms featuring single residue substitutions-namely, Gly-46 to Ser-46 (Pin-bH) and Trp-44 to Arg-44 (Pin-bS)-with condensed-phase monolayers of zwitterionic (L-alpha-dipalmitoylphosphatidylcholine, DPPC) and anionic (L-alpha-dipalmitoylphosphatidyl-dl-glycerol, DPPG) phospholipids. The interaction with anionic DPPG monolayers, monitored by surface pressure isotherms, was influenced significantly by mutations in Pin-b (p < 0.05); wild-type Pin-b showed the highest surface pressure change of 10.6 +/- 1.0 mN m(-1), followed by Pin-bH (7.9 +/- 1.6 mN m(-1)) and Pin-bS (6.3 +/- 1.0 mN m(-1)), and the surface pressure isotherm kinetics were also different in each case. Integrated Amide I peak areas from corresponding ER-FTIR spectra confirmed the differences in adsorption kinetics, but also showed that differences in adsorbed amount were less significant, suggesting that mutations influence the degree of penetration into DPPG films. All Pin-b types showed evidence of interaction with DPPC films, detected as changes in surface pressure (5.6 +/- 1.1 mN m(-1)); however, no protein peaks were detected in the ER-FTIR spectra, which indicated that the interaction was via penetration with limited adsorption at the lipid/water interface. The expression of Pin-b mutants is linked to wheat endosperm hardness; therefore, the data presented here suggest that the lipid binding properties may be pivotal within the mechanism for this quality trait. In addition, the data suggest antimicrobial activities of Pin-b mutants would be lower than those of the wild-type Pin-b, because of decreased selectivity toward anionic phospholipids.

Physical properties of Hydropsyche siltalai (Trichoptera) net silk

Most suspension-feeding trichopterans spin a fine-silk capture net that is used to remove suspended matter from the water. The efficiency of these nets has previously been studied by considering the geometry of the web structure but the material from which the nets is constructed has received little attention. We report measurements of the tensile strength and extensibility of net silk from Hydropsyche siltalai. These measurements place caddisfly silk as one of the weakest natural silks so far reported, with a mean tensile strength of 221 +/- 22 megaNewtons (MN)/m(2). We also show that H. siltalai silk can more than double in length before catastrophic breakage, and that the silk is at least 2 orders of magnitude stronger than the maximum force estimated to act upon it in situ. Possible reasons for this disparity include constraints of evolutionary history and safety margins to prevent net failure or performance reduction.