Defoliation and patchy nutrient return drive grazing effects on plant and soil properties in a dairy cow pasture

Large herbivores can influence plant and soil properties in grassland ecosystems, but especially for belowground biota and processes, the mechanisms that explain these effects are not fully understood. Here, we examine the capability of three grazing mechanisms-plant defoliation, dung and urine return, and physical presence of animals (causing trampling and excreta return in patches)-to explain grazing effects in Phleum pratense-Festuca pratensis dairy cow pasture in Finland. Comparison of control plots and plots grazed by cows showed that grazing maintained original plant-community structure, decreased shoot mass and root N and P concentrations, increased shoot N and P concentrations, and had an inconsistent effect on root mass. Among soil fauna, grazing increased the abundance of fungivorous nematodes and Aporrectodea earthworms and decreased the abundance of detritivorous enchytraeids and Lumbricus earthworms. Grazing also increased soil density and pH but did not affect average soil inorganic-N concentration. To reveal the mechanisms behind these effects, we analyzed results from mowed plots and plots that were both mowed and treated with a dung and urine mixture. This comparison revealed that grazing effects on plant attributes were almost entirely explained by defoliation, with only one partly explained by excreta return. Among belowground attributes, however, the mechanisms were more mixed, with effects explained by defoliation, patchy excreta return, and cow trampling. Average soil inorganic-N concentration was not affected by grazing because it was simultaneously decreased by defoliation and increased by cow presence. Presence of cows created great spatial heterogeneity in soil N availability and abundance of fungivorous nematodes. A greenhouse trial revealed a grazing-induced soil feedback on plant growth, which was explained by patchiness in N availability rather than changes in soil biota. Our results show that grazing effects on plant attributes can be satisfactorily predicted using the effects of defoliation, whereas those on soil fauna and soil N availability need understanding of other mechanisms as well. The results indicate that defoliation-induced changes in plant ecophysiology and the great spatial variation in N availability created by grazers are the two key mechanisms through which large herbivores can control grassland ecosystems.

Suppression of charge order, disappearance of antiferromagnetism, and emergence of ferromagnetism in Nd0.5Ca0.5MnO3 nanoparticles

Nd0.5Ca0.5MnO3 nanoparticles (average diameter similar to 20 and 40 nm) are synthesized by the polymeric precursor sol-gel method and characterized by various physico-chemical techniques. Quite strikingly, in the 20 nm particles, the charge-ordered (CO) and the antiferromagnetic phases observed in the bulk below 250 K and 160 K, respectively, are completely absent. Instead, a ferromagnetic (FM) transition is observed at 95 K followed by an insulator-to-metal transition at 75 K. The 40 nm particles show a residual CO phase but a transition to the FM state also occurs, at a slightly higher temperature of 110 K.

Simulation of magnetovolume effects in Fe65Ni35 nanoparticles

We compare magnetovolume effects in bulk and nanoparticles by performing Monte Carlo simulations of a spin-analogous model with coupled spatial and magnetic degrees of freedom and chemical disorder. We find that correlations between surface and bulk atoms lead with decreasing particle size to a substantial modification of the magnetic and elastic behavior at low temperatures.

In situ surface modification of molybdenum-doped organic-inorganic hybrid TiO2 nanoparticles under hydrothermal conditions and treatment of pharmaceutical effluent

Molybdenum-doped TiO2 organic-inorganic hybrid nanoparticles were synthesized under mild hydrothermal conditions by in situ surface modification using n-butylamine. This was carried out at 150 degrees C at autogeneous pressure over 18 h. n-Butylamine was selected as a surfactant since it produced nanoparticles of the desired size and shape. The products were characterized using powder X-ray diffraction, Fourier transform infrared spectrometry, dynamic light-scattering spectroscopy, UV-Vis spectroscopy and transmission electron microscopy. Chemical oxygen demand was estimated in order to determine the photodegradation efficiency of the molybdenum-doped TiO2 hybrid nanoparticles in the treatment of pharmaceutical effluents. It was found that molybdenum-doped TiO2 hybrid nanoparticles showed higher photocatalytic efficiency than untreated TiO2 nanoparticles.

Technique for Using Fine-Grained Soil in Reinforced Earth

The performance of reinforced earth structures depends on the mobilization of interfacial shearing resistance between soil and reinforcement. This criterion typically eliminates the use of fine-grained soil as a backfill material in reinforced earth structures. Considering the distribution of induced interfacial shear stress in soil around the surface of the reinforcement, it has been shown that only a thin zone of frictional material around the reinforcement is required to mobilize almost full interfacial shearing resistance of sand. Six series of pullout tests have been conducted, with different types of reinforcement, to study the effect of thickness of sand (frictional material) around the reinforcement on the pullout resistance. Sawdust and kaolin clay have been used as bulk backfill material, providing the soil with negligible friction. With low-friction-strength soil as bulk material, a 15-mm thickness of sand around the reinforcement is required to increase the interfacial shearing resistance to that with sand as the bulk material. With this new technique, low-frictional fine-grained soils can be used as bulk backfill material in reinforced earth constructions.

Spectrally broadened excitonic absorption and enhanced optical nonlinearities in Dy3+-doped ZnO nanoparticles

We have synthesized Dy3+-doped ZnO nanoparticles at room temperature through the sol-gel method. X-ray diffraction and Scanning electron microscopic studies confirm the crystalline nature of the particles. Excitonic absorption of ZnO shows three different bands, and we observe that incorporation of Dy3+ results in the shifting and broadening of the n=1 absorption band of ZnO. Photoluminescence studies done at the excitation wavelength of 335 nm show broad emission containing five different bands. Open-aperture z-scan studies done at 532 nm using 5 ns laser pulses show an optical limiting behavior, which numerically fits to a three-photon type absorption process. The nonlinearity is essentially resonant, as it is found to increase consistently with Dy3+ concentration. This feature makes Dy3+-doped ZnO a flexible optical limiter for potential device applications.

Effect of substrate on particle arrangement in arrays formed by self-assembly of polymer grafted nanoparticles

We show that the substrate affects the interparticle spacing in monolayer arrays with hexagonal order formed by self-assembly of polymer grafted nanoparticles. Remarkably, arrays with square packing were formed due to convective shearing at a liquid surface induced by miscibility of colloidal solution with the substrate.

Enhanced lithium-ion transport in PEG-based composite polymer electrolyte with Mn0.03Zn0.97Al2O4 nanoparticles

The ion conduction and thermal properties of composite solid polymer electrolyte (SPE) comprising Poly(ethylene) Glycol (PEG, mol wt. 2000), lithium perchlorate (LiClO4) and insulating Mn0.03Zn0.97Al2O4 nanoparticle fillers were studied by complex impedance analysis and DSC techniques. The average size of the nanoparticles was determined by powder X-ray diffraction (XRD) using Scherrer's equation and was found to be similar to 8 nm. The same was also determined by TEM imaging and found to be similar to 12 nm. The glass transition temperature T, as measured by differential scanning calorimeter (DSC), showed a minimum at 5 mol% of narroparticles. Fractional crystallinity was determined using DSC. NMR was used to deter-mine crystallinity of a pure PEG sample, which was then used as the standard. Fractional crystallinity X. was the lowest for 5 mol% and beyond. The ionic conductivity of the composite polymer electrolyte containing 5 mol% Mn0.03Zn0.97Al2O4 nanoparticles was found to be 1.82 x 10(-5) S/cm, while for the pristine one, it was 7.27 x 10(-7) S/cm at room temperature. As a function of nanoparticle content, conductivity was observed to go through two maxima, one at around 5 mol% and another shallower one at around 12 mol%. The temperature dependence of conductivity could be divided into two regions, one consistent with Arrhenius behaviour and the other with VTF. We conclude that the enhancement of ionic conductivity on the addition of Mn0.03Zn0.97Al2O4 nanoparticles is a result of reduction in both the T, and the crystallinity. (C) 2002 Elsevier Science B.V. All rights reserved.

Spatial confinement of exciton transfer and the role of conformational order in organic nanoparticles

Organic nanoparticles consisting of single conjugated polymer chains were investigated as a function of degree of conjugation by means of single-molecule spectroscopy. The degree of conjugation was synthetically controlled. For highly conjugated chains, singlet excitons are efficiently funneled over nanometer distances to a small number of sites. In contrast, chains with less conjugation and a high number of saturated bonds do not exhibit energy funneling due to a highly disordered conformation.

Monodisperse sub-10 nm gold nanoparticles by reversing the order of addition in Turkevich method - The role of chloroauric acid

The Turkevich method for synthesizing gold nanoparticles, using sodium citrate as the reducing agent, is renowned for its ability to produce biocompatible colloids with mean size >10 nm. Here we show that monodisperse gold nanoparticles in the 5-10 nm size range can be synthesized by simply reversing the order of addition of reactants, i.e. adding chloroauric acid to citrate solution. Kinetic studies and electron microscopic characterization revealed that the reactivity of chloroauric acid, initial molar ratio of citrate to chloroauric acid (MR), and reaction mixture pH play an important role in producing monodisperse gold nanoparticles. Reversing the order of addition also enhanced the stabilization of nanoparticles at high MR values. Remarkably, the system exhibits a `memory' of the order of addition, even when the timescale of mixing is much shorter than the timescale of synthesis. (C) 2011 Elsevier Inc. All rights reserved.

Mitigation of Alkali Induced Heave in Rectorite Soil with Fly Ash

Mechanisms that control the volume changes behavior of foundation soils are well understood. The changes that occur in the behavior of soil due to migration of pollutants are not well understood. The extent of changes that occur in the presence of small concentration of contaminants can be predicted based on changes in the thickness of double layer and associated fabric changes. Interactions that occur with strong contaminants depends on the type of soil, type and concentration of contamination and duration of interaction etc It has been shown that different concentrations (1N and 4N) of sodium hydroxide solution causes abnormal changes on volume change behaviour of soil due to mineralogical changes. An attempt is made in this paper to stabilize contaminated soil using fly ash, after establishing its stability in alkali solutions. It was found that the effectiveness of fly ash to control the alkali induced heave increases with fly ash content incorporated into the soil. X-ray diffraction studies reveal that the mineralogical changes that occur in soil due to alkali interaction are inhibited by the presence of fly ash.

Onset of sphalerite to wurtzite transformation in ZnS nanoparticles

In this work, the incubation period for the onset of sphalerite to wurtzite transformation in isolated ZnS nanoparticles 2 to 7 nm in size was determined via the in situ isothermal annealing of as-synthesized sphalerite nanoparticles in a transmission electron microscope (TEM). Nanoparticles sitting on the TEM grid were well separated from each other in order to minimize particle sintering during the annealing operation. The phase transformation onset was observed at 300 degrees C, 350 degrees C, and 400 degrees C after 90, 10, and 4 min, respectively. These time-temperature data for the phase transformation onset were then used to calculate the activation energy for the nucleation of the wurtzite phase in 2 to 7 nm sphalerite particles. The activation energy determined was 24 Kcal/mol. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3622625]

Exfoliation of copper hydroxysalt in water and the conversion of the exfoliated layers to cupric and cuprous oxide nanoparticles

P-aminobenzoate- intercalated copper hydroxysalt was prepared by coprecipitation at high pH (similar to 12). As the pH was reduced to similar to 7 on washing with water, the development of partial positive charge on the amine end of the intercalated anion caused repulsion between the layers leading to delamination and colloidal dispersion of monolayers of copper hydroxysalt in water. The dispersed copper hydroxysalt monolayers were used as precursors for the synthesis of copper(I)/(II) oxide nanoparticles at room temperature. While the hydroxysalt layers yielded spindle-shaped CuO particles when left to stand, they formed hollow spherical nanoparticles of Cu(2)O when treated with an alkaline solution of ascorbic acid.

Colloidal calcium nanoparticles: digestive ripening in the presence of a capping agent and coalescence of particles under an electron beam

The nanochemistry of calcium remains unexplored, which is largely due to the inaccessibility of calcium nanoparticles in an easy to handle form by conventional methods of synthesis as well as its highly reactive and pyrophoric nature. The synthesis of colloidal Ca nanoparticles by the solvated metal atom dispersion (SMAD) method is described. The as-prepared Ca-THF nanoparticles, which are polydisperse, undergo digestive ripening in the presence of a capping agent, hexadecyl amine (HDA) to afford highly monodisperse colloids consisting of 2-3 nm sized Ca-HDA nanoparticles. These are quite stable towards precipitation for long periods of time, thereby providing access to the study of the nanochemistry of Ca. Particles synthesized in this manner were characterized by UV-visible spectroscopy, high resolution electron microscopy, and powder X-ray diffraction methods. Under an electron beam, two adjacent Ca nanoparticles undergo coalescence to form a larger particle.

Gas-phase synthesis of size-classified polyhedral In(2)O(3) nanoparticles

Monodisperse polyhedral In(2)O(3) nanoparticles were synthesized by differential mobility classification of a polydisperse aerosol formed by evaporation of indium at atmospheric pressure. When free molten indium particles oxidize, oxygen is absorbed preferentially on certain planes leading to the formation of polyhedral In(2)O(3) nanoparticles. It is shown that the position of oxygen addition, its concentration, the annealing temperature and the type of carrier gas are crucial for the resulting particle shape and crystalline quality. Semiconducting nanopolyhedrals, especially nanocubes used for sensors, are expected to offer enhanced sensitivity and improved response time due to the higher surface area as compared to spherical particles.