Synthesis, structure, and high-temperature thermoelectric properties of boron-doped Ba_8Al_(14)Si_(31) clathrate I phases

Single crystals of boron-doped Ba_8Al_(14)Si_(31) clathrate I phase were prepared using Al flux growth. The structure and elemental composition of the samples were characterized by single-crystal and powder X-ray diffraction; elemental analysis; and multinuclear ^(27)Al, ^(11)B, and ^(29)Si solid-state NMR. The samples' compositions of Ba_8B_(0.17)Al_(14)Si_(31), Ba_8B_(0.19)Al_(15)Si_(31), and Ba_8B_(0.32)Al_(14)Si_(310) were consistent with the framework-deficient clathrate I structure Ba_8Al_xSi_(42-3/4x)□_(4-1/4x) (X = 14, □ = lattice defect). Solid-state NMR provides further evidence for boron doped into the framework structure. Temperature-dependent resistivity indicates metallic behavior, and the negative Seebeck coefficient indicates that transport processes are dominated by electrons. Thermal conductivity is low, but not significantly lower than that observed in the undoped Ba_8Al_(14)Si_(31) prepared in the same manner

A neutron scattering study of the interplay between structure and magnetism in Ba(Fe1−x_{1-x}Cox_{x})2_2As2_2

Single crystal neutron diffraction is used to investigate the magnetic and structural phase diagram of the electron doped superconductor Ba(Fe$_{1-x}$Co$_x$)$_2$As$_2$. Heat capacity and resistivity measurements have demonstrated that Co doping this system splits the combined antiferromagnetic and structural transition present in BaFe$_2$As$_2$ into two distinct transitions. For $x$=0.025, we find that the upper transition is between the high-temperature tetragonal and low-temperature orthorhombic structures with ($T_{\mathrm{TO}}=99 \pm 0.5$ K) and the antiferromagnetic transition occurs at $T_{\mathrm{AF}}=93 \pm 0.5$ K. We find that doping rapidly suppresses the antiferromagnetism, with antiferromagnetic order disappearing at $x \approx 0.055$. However, there is a region of co-existence of antiferromagnetism and superconductivity. The effect of the antiferromagnetic transition can be seen in the temperature dependence of the structural Bragg peaks from both neutron scattering and x-ray diffraction. We infer from this that there is strong coupling between the antiferromagnetism and the crystal lattice

Role of Nanoclays in Carbon stabilization in Andisols and Cambisols

Greenhouse gas (GHG) emissions and their consequent effect on global warming are an issue of global environmental concern. Increased carbon (C) stabilization and sequestration in soil organic matter (SOM) is one of the ways to mitigate these emissions. Here we evaluated the role of nanoclays isolated from soil on C stabilization in both a C rich Andisols and C depleted Cambisols. Nanoclays were analyzed for size and morphology by transmission electron microscopy, for elemental composition and molecular composition using pyrolysis-GC/MS. Moreover, nanoclays were treated with H2O2 to isolate stable SOM associated with them. Our result showed better nanoclay extraction efficiency and higher nanoclay yield for Cambisol compared to Andisols, probably related to their low organic matter content. Nanoclay fractions from both soils were different in size, morphology, surface reactivity and SOM content. Nanoclays in Andisols sequester around 5-times more C than Cambisols, and stabilized 6 to 8-times more C than Cambisols nanoclay after SOM chemical oxidation. Isoelectric points and surface charge of nanoclays extracted from the two soils was very different. However, the chemical reactivity of the nanoclay SOM was similar, illustrating their importance for C sequestration. Generally, the precise C stabilization mechanisms of both soils may be different, with nanoscale aggregation being more important in Andisols. We can conclude that independent of the soil type and mineralogy the nanoclay fraction may play an important role in C sequestration and stabilization in soil-plant systems

Using organic phosphorus to sustain pasture productivity: A perspective

Organic phosphorus (P) in grazed pastures/grasslands could sustain production systems that historically relied on inorganic P fertiliser. Interactions between inorganic P, plants and soils have been studied extensively. However, less is known about the transformation of organic P to inorganic orthophosphate. This paper investigates what is known about organic P in pasture/grassland soils used for agriculture, as well as the research needed to utilise organic P for sustainable plant production. Organic P comprises > 50% of total soil P in agricultural systems depending on location, soil type and land use. Organic P hydrolysis and release of orthophosphate by phosphatase enzymatic activity is affected by a range of factors including: (a) the chemical nature of the organic P and its ability to interact with the soil matrix; (b) microorganisms that facilitate mineralisation; (c) soil mineralogy; (d) soil water electrolytes; and (e) soil physicochemical properties. Current biogeochemical knowledge of organic P processing in soil limits our ability to develop management strategies that promote the use of organic P in plant production. Information is particularly needed on the types and sources of organic P in grassland systems and the factors affecting the activity of enzymes that mineralise organic P. Integrated approaches analysing the soil matrix, soil water and soil biology are suggested to address this knowledge gap

Effects of Different Phosphate Fertilizers on Pasture Nutrition and Soil Phosphorus in Canterbury, New Zealand

A field trial was conducted over 6 years to assess the relative performance of three phosphate (P) fertilisers of differing solubility (single superphosphate, ‘longlife’ superphosphate, ‘reactive’ phosphate rock) on a permanent pasture at Methven in Canterbury, New Zealand. Plant P uptake data showed that while the overall relative effectiveness of the fertilisers was closely related to their water-soluble P content (single superphosphate \u3e ‘longlife’ superphosphate \u3e ‘reactive’ phosphate rock), the agronomic efficiency of the sparingly soluble phosphate rock fertiliser improved markedly with time. Soil P analysis demonstrated that significant dissolution of phosphate rock had occurred in the soil, and the findings of this trial confirm that phosphate rock is an appropriate P fertiliser for use in pastoral agriculture in New Zealand

Sensitivity of the soil-borne pathogen Phytophthora agathidicida, the causal agent of kauri dieback, to the anti-oomycete fungicides ethaboxam, fluopicolide, mandipropamid, and oxathiapiprolin

The oomycete Phytophthora agathidicida is the causal agent of kauri dieback, which threatens the survival of endemic kauri (Agathis australis) forests in Aotearoa|New Zealand. Current chemical control of P. agathidicida involves the application of either a mixture of halogenated tertiary amines or phosphite salts with some success, but neither treatment cures the disease. Recently, four anti-oomycete fungicides, all with different modes of action, have become commercially available. Here, we determined the inhibition potential of these fungicides on three P. agathidicida isolates, using agar dilution assays. The average concentration required to inhibit mycelial growth by 50% (EC₅₀) for ethaboxam, fluopicolide, and mandipropamid was 0.0916, 0.372, and 0.0196 µg/mL, respectively. Inhibition of P. agathidicida mycelia by oxathiapiprolin and its commercial formulation, Zorvec® Enicade®, was 0.000152 and 0.000309 µg/mL, respectively. Based on the EC₅₀ values reported in this study, these fungicides are the most effective inhibitors of P. agathidicida mycelia when compared to previously screened fungicides, natural products, and plant extracts. Thus, their performance in this initial screening supports further research into their potential use as a kauri dieback management tool