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We describe the energy and sequence of phase transformations in multilayered Al/Zr foils with atomic ratios of 3 Al:1 Zr during low temperature (<350 °C) heat treatments in a differential scanning calorimeter. The initial phase formed is an Al-rich amorphous phase that appears to grow by Zr diffusion through the amorphous phase. The subsequent nucleation and growth of tetragonal Al3Zr along the Al/amorphous layer interface is mediated by Al diffusion through the crystalline intermetallic phase. Diffusion coefficients associated with these processes are higher than expected from reports of diffusivities measured at higher temperatures. The inferred heat of formation of the tetragonal Al3Zr phase is 1240 ± 40 J/g (53 ± 2 kJ/mol atom). No anomalous variation in the energy or sequence of phase transformations is found with bilayer thickness for samples with bilayer thickness in the range of 17 nm to 90 nm despite anomalies in the bilayer dependence of self-propagating reaction velocities in the same foils. [ABSTRACT FROM AUTHOR]

High temperature, self-propagating reactions are observed in vapor-deposited Al/Zr multilayered foils of overall atomic ratios 3 Al:1 Zr and 2 Al:1 Zr and nanoscale layer thicknesses; however, the reaction velocities do not exhibit the inverse dependence on bilayer thickness that is expected based on changes in the average diffusion distance. Instead, for bilayer thicknesses of 20-30 nm, the velocity is essentially constant at ∼7.7 m/s. We explore several possible explanations for this anomalous behavior, including microstructural factors, changes in the phase evolution, and phase transformations in the reactant layers, but find no conclusive explanations. We determine that the phase evolution during self-propagating reactions in foils with a 3 Al:1 Zr stoichiometry is a rapid transformation from Al/Zr multilayers to the equilibrium intermetallic Al3Zr compound with no intermediate crystalline phases. This phase evolution is the same for foils of 90 nm bilayer thicknesses and foils of bilayer thicknesses in the range of 27 nm to 35 nm. Further, for foils with a bilayer thickness of 90 nm and a 3 Al:1 Zr overall chemistry, the propagation front is planar and steady, in contrast to unsteady reaction fronts in foils with 1 Al:1 Zr overall chemistry and similar bilayer thicknesses. [ABSTRACT FROM AUTHOR]

Materials with the pyrochlore/fluorite structure have diverse technological applications, from magnetism to nuclear waste disposal. Here we report the observation of structural instability present in the pyrochlores A2Zr2O6O' (A = Pr, La) and Yb2Ti2O6O', that exists despite ideal stoichiometry, ideal cation-ordering, the absence of lone pair effects, and a lack of magnetic order. Though these materials appear to have good long-range order, local structure probes find displacements, of the order of 0.01 nm, within the pyrochlore framework. The pattern of displacements of the A2O' sublattice mimics the entropically-driven fluxional motions characteristic of and well-known in the silica mineral β-cristobalite. The universality of such displacements within the pyrochlore structure adds to the known structural diversity and explains the extreme sensitivity to composition found in quantum spin ices and the lack of ferroelectric behavior in pyrochlores. [ABSTRACT FROM AUTHOR]

Here we report that a self-sustaining oxidation of a multilayer foil can be ignited by an intermetallic formation reaction, releasing ∼4× the energy of the formation reaction. We examine foils with overall chemistries of 3Al:2Ni, 3Al:Zr, and Al:Zr and find that only the latter experiences significant oxidation. The Al:Zr samples initially react to form intermetallics and reach ∼1500 K in <10 ms. The samples then oxidize in air, absorbing ∼30 at. % O and remaining at ∼1400 K for >2.0 s. The phases within the Al:Zr foils are characterized and temperature-time profiles are examined to predict the heat generated by the oxidation reaction. [ABSTRACT FROM AUTHOR]

• The nickel (Ni) hyperaccumulator Alyssum murale has been developed as a commercial crop for phytoremediation/phytomining Ni from metal-enriched soils. Here, metal co-tolerance, accumulation and localization were investigated for A. murale exposed to metal co-contaminants. • A. murale was irrigated with Ni-enriched nutrient solutions containing basal or elevated concentrations of cobalt (Co) or zinc (Zn). Metal localization and elemental associations were investigated in situ with synchrotron X-ray microfluorescence (SXRF) and computed-microtomography (CMT). • A. murale hyperaccumulated Ni and Co (> 1000 µg g−1 dry weight) from mixed-metal systems. Zinc was not hyperaccumulated. Elevated Co or Zn concentrations did not alter Ni accumulation or localization. SXRF images showed uniform Ni distribution in leaves and preferential localization of Co near leaf tips/margins. CMT images revealed that leaf epidermal tissue was enriched with Ni but devoid of Co, that Co was localized in the apoplasm of leaf ground tissue and that Co was sequestered on leaf surfaces near the tips/margins. • Cobalt-rich mineral precipitate(s) form on leaves of Co-treated A. murale. Specialized biochemical processes linked with Ni (hyper)tolerance in A. murale do not confer (hyper)tolerance to Co. A. murale relies on a different metal storage mechanism for Co (exocellular sequestration) than for Ni (vacuolar sequestration). [ABSTRACT FROM AUTHOR]

Eutrophication caused by dissolved P from poultry litter (PL)amended agricultural soils has been a serious environmental concern in the Delaware-Maryland-Virginia Peninsula (Delmarva), USA. To evaluate state and federal nutrient management strategies for reducing the environmental impact of soluble P from long-term PL-amended Delaware (DE) soils, we investigated (i) inorganic P speciation; (ii) P adsorption capacity; and (iii) the extent of P desorption. Although thc electron microprobe (EMP) analyses showed a strong correlation betwcen P and Al/Fe, crystalline Al/Fe-P precipitates were not detected by x-ray diffraction (XRD). Instead, the inorganic P fractionation analyses showed high levels of oxalate extractable P, Al, and Fe fractions (615-858,1215-1478, and 337-752 mg kg-1, respectively), which were susceptible lo slow release during the long-term (30-d) P desorption experiments at a moderately acidic soil pHwater. The labile P in the short-term (24-h) desorption studies was significantly associated with oxalate and F extractable Fe and Al, respectively. This was evident in an 80% reduction maximum in total desorbable P from NH4 oxalate/F pretreated soils. In the adsorption experiments, P was strongly retained in soils at near targeted pH of lime (≈6.0), but P adsorption gradually decreased with decreasing pH near the soil pHwater (≈5.0). Thc overall findings suggest that P losses from the can be suppressed by an increase in the P retention capacity of soils via (i) an increase in the number of lime applications to maintain soil pHwater at near targeted pH values, and/or (ii) alum/iron sulfate amendments to provide additional Al- and Fe-based adsorbents. [ABSTRACT FROM AUTHOR]

The six week eruption of Eyjafjallajökull volcano in 2010 produced heavy ash fall in a sparsely populated area of southern and south eastern Iceland and disrupted European commercial flights for at least 6 days. We adopted a protocol for the rapid analysis of volcanic ash particles, for the purpose of informing respiratory health risk assessments. Ash collected from deposits underwent a multi-laboratory physicochemical and toxicological investigation of their mineralogical parameters associated with bio-reactivity, and selected in vitro toxicology assays related to pulmonary inflammatory responses. Ash from the eruption of Grímsvötn, Iceland, in 2011 was also studied. The results were benchmarked against ash from Soufrière Hills volcano, Montserrat, which has been extensively studied since the onset of eruptive activity in 1995. For Eyjafjallajökull, the grain size distributions were variable: 2-13 vol% of the bulk samples were <4 µm, with the most explosive phases of the eruption generating abundant respirable particulate matter. In contrast, the Grímsvötn ash was almost uniformly coarse (<3.5 vol%<4 µm material). Surface area ranged from 0.3 to 7.7 m2 g(-1) for Eyjafjallajökull but was very low for Grímsvötn (<0.6 m2 g(-1)). There were few fibre-like particles (which were unrelated to asbestos) and the crystalline silica content was negligible in both eruptions, whereas Soufrière Hills ash was cristobalite-rich with a known potential to cause silicosis. All samples displayed a low ability to deplete lung antioxidant defences, showed little haemolysis and low acute cytotoxicity in human alveolar type-1 like epithelial cells (TT1). However, cell-free tests showed substantial hydroxyl radical generation in the presence of hydrogen peroxide for Grímsvötn samples, as expected for basaltic, Fe-rich ash. Cellular mediators MCP-1, IL-6, and IL-8 showed chronic pro-inflammatory responses in Eyjafjallajökull, Grímsvötn and Soufrière Hills samples, despite substantial differences in the sample mineralogy and eruptive styles. The value of the pro-inflammatory profiles in differentiating the potential respiratory health hazard of volcanic ashes remains uncertain in a protocol designed to inform public health risk assessment, and further research on their role in volcanic crises is warranted., (Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.)