Competitive sorption of intermixed heavy metals in water repellent soil in Southern Australia

In water repellent soil, Cr, Pb and Cu showed higher adsorption intensities than Zn, Cd and Ni did. Soil water repellency is much more widespread than formerly thought. In order to promote fertility and productivity, the irrigation of recycled water onto water repellent soil may be an applied technology to be used in some areas of Southern Australia. Therefore, heavy metals in recycled water potentially enter into the soil. The competitive sorption and retention capacity of heavy metals in soil are important to be determined, especially considering the special geochemical origin of water repellent soil that was caused by waxes on or between the soil particles. Batch equilibrium sorption experiments on Cd, Cr, Cu, Ni, Pb and Zn in their typical proportion in recycled water were conducted in water repellent soil. The sorption intensity, sorption isotherm in the experiments together showed that Cr, Pb and Cu have higher sorption intensity than those of Zn, Ni and Cd in the competitive system. The risk assessment for the application of recycled water onto water repellent soil is definitely necessary, especially for the metal cations with relatively weak sorption.

Baseline assessment of metals and hydrocarbons in the sediments of Lake Mulwala, Australia

An assessment of hydrocarbon and metal/metalloids (arsenic, cadmium, copper, lead, mercury, selenium, zinc) contamination in sediments from Lake Mulwala, Australia, was undertaken. The objectives of the study were: (i) to determine the extent of contamination in the lake sediments, compared to Australian and international sediment quality guidelines, and (ii) to attempt to identify the contaminant sources to the lake. With the exception of a few samples containing elevated levels of arsenic and/or mercury, the levels of all contaminants in the sediment samples taken from the lake were below the 'lower trigger' of the Australian Sediment Quality Guidelines that would warrant further investigation. High molecular weight hydrocarbons (up to 700 mg kg−1) were found in most sediment samples. Non-metric statistical analysis indicated that the contaminant distribution was different in different parts of the lake, with the lowest concentrations generally found at the influent to the lake. No definitive source(s) of contamination could be identified for either metalloids or hydrocarbons.

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate ligand with bivalent metals: a new 2D-layered phenylphosphinate zinc(II) complex

By reaction of Zn(CH₃COO)₂ with p,p′-diphenylmethylenediphosphinic acid in water a new inorganic–organic polymeric hybrid of formula [Zn(CH₂(P(Ph)O₂)₂)] has been synthesized and completely characterized. The X-ray analysis established that the structure consists of 2D-layered polymeric array, the 2D-sheets being built up through strong covalent linkages between the zinc metal and the oxygen donors of the phenylphosphinate ligand. The 2D-layers, which are featuring a mesh-net fashion, present voids of various dimensionality, up to 24-membered rings. The organic parts of the hybrid ligand, namely the phenyl rings, are shielding the inorganic skeleton of the layers, preventing the propagation of the polymer in the third dimension. No water molecules are present in the lattice, both of coordination and crystallization. Crystal data are: monoclinic, P2₁Ic, a=11.840(2), b=9.646(9), c=12.516(5) Å, β=95.03(2), V=1423.9(15) ų, Z=4. The solid material has been characterized by ³¹P MAS NMR spectroscopy and thermogravimetric analysis.

Competitive sorbtion of metals in water repellent soils: implications for irrigation recycled water

Australia is a water-stressed nation and demand on potable water supply is increasing. Consequently water conservation and reuse are increasingly becoming important. Irrigation of recycled wastewater on water repellent soils is a technology that is being trialled as a means of improving crop production and conserving potable supply. However, recycled water contains potentially harmful heavy metals. This paper reports the competitive sorption and desorption of several common heavy metals found in soils collected from a farm located in the south-east of South Australia. The soil from this location is severely water repellent, but some sites were amended with kaolinite clay (Si₄Al₄O₁₀(OH)₈) about 7 and 15 years ago. The metals studied were Cu, Pb, Cd, Cr, Ni, and Zn. Competitive sorption of the metals was distinctly observed. For all heavy metals, the quantity of metal sorbed was higher in amended soil, and there was a strong correlation between the specific sorption to total sorption ratio and the amount of clay in the soil. The sorption intensities varied with metal, Cr, Pb, and Cu having a high sorption tendencies and Zn, Cd, and Ni having comparatively low sorption tendencies. The total sorption capacity for all metals increased in clay-treated soils compared with non-treated soils. On average, clay-amended water repellent soils had a 20–40% increased capacity to adsorb total metals; however, this increase was largely caused by the increased capacities to adsorb Zn, Cd, and Ni. The effect of clay treatment largely enhanced the sorption capacity of relatively weakly adsorbing heavy metals. The implications for using recycled wastewater on the long-term sustainable agro-environmental management of these soils are discussed.

In vitro bioactivity evaluation of titanium and niobium metals with different surface morphologies

Current orthopaedic biomaterials research mainly focuses on designing implants that could induce controlled, guided and rapid healing. In the present study, the surface morphologies of titanium (Ti) and niobium (Nb) metals were tailored to form nanoporous, nanoplate and nanofibre-like structures through adjustment of the temperature in the alkali-heat treatment. The in vitro bioactivity of these structures was then evaluated by soaking the treated samples in simulated body fluid (SBF). It was found that the morphology of the modified surface significantly influenced the apatite-inducing ability. The Ti surface with a nanofibre-like structure showed better apatite-inducing ability than the nanoporous or nanoplate surface structures. A thick dense apatite layer formed on the Ti surface with nanofibre-like structure after 1 week of soaking in SBF. It is expected that the nanofibre-like surface could achieve good apatite formation in vivo and subsequently enhance osteoblast cell adhesion and bone formation.

Effects of pore morphology on the compressive behaviour of porous metals

In the present study, porous nickel foams with three different porosities (i.e. 50 %, 60 % and 70 %) were fabricated using the space-holding sintering method. Ammonium bicarbonate particles with sizes ranging from 1- 2 mm were chosen as the space-holding material. The anisotropic behaviours of the nickel foam samples were investigated by compressive testing loading at different directions, i.e., in both directions of the major and minor axis of ellipsoidal cells. Electron scanning microscopy (SEM) and Image-Pro Plus was used to characterise the morphological characteristics of the porous nickel foam samples. Results indicated that the porous nickel foam samples exhibited obvious anisotropic mechanical properties. The foam sample shows significantly higher nominal stress for loading in the direction of the major axis of the pores than loading in the direction of the minor axis of pores. The nominal stress increases with the decreasing of the porosity.

Photocatalytic activity of manganese-doped ZnO nanocrystalline powders

ZnO nanocrystalline powders doped with up to 5 at% manganese were synthesized and their photocatalytic activity was studied. Doped ZnO powders were prepared using a sol-gel process. The crystal structure and grain size of the particles were characterized by X-ray diffractometry and optical properties were studied using UV-Vis spectroscopy. The photoactivity of undoped and doped ZnO nanocrystalline powders was evaluated by monitoring the photo-bleaching of the aqueous solutions of Rhodamine B dye in the presence of ZnO under simulated sunlight. The results showed that up to 3 at% manganese were successfully doped into the nanocrystalline ZnO and that manganese-doping reduced the photocatalytic activity of ZnO.

Secondary emission of nanocrystalline zinc oxide

The Raman and photoluminescence (PL) spectra of nanocrystalline zinc oxide produced by mechanochemical synthesis were measured using a pulsed nitrogen laser (337.1 nm) and xenon lamp (360 nm) as excitation sources in PL measurements and a cw Nd:YAG laser in Raman measurements. PL was observed in the range 400–800 nm. The Raman spectrum of nanocrystalline (90 nm) ZnO was compared to that of coarsegrained ZnO. The Raman bands of nanocrystalline zinc oxide were found to be shifted to lower frequencies and broadened. Laser radiation was shown to cause local heating of zinc oxide up to 1000 K, resulting in photoinduced formation of zinc nanoclusters. Mixtures of zinc oxide and sodium chloride powders are heated to substantially lower temperatures. Under nitrogen laser excitation, the green PL band (535 nm), characteristic of bulk ZnO, is shifted to longer wavelengths by 85 nm. The results are interpreted in terms of light confinement in zinc oxide microclusters consisting of large number of nanocrystallites. The photoinduced processes in question may be a viable approach to producing metal-insulator structures in globular photonic crystals, opals, filled with zinc oxide.

Optical and photocatalytic properties of nanocrystalline TiO2 synthesised by solid-state chemical reaction

Nanoparticulate TiO₂ is of interest for a variety of technological applications, including optically transparent UV-filters and photocatalysts for the destruction of chemical waste. The successful use of nanoparticulate TiO₂ in such applications requires an understanding of how the synthesis conditions effect the optical and photocatalytic properties. In this study, we have investigated the effect of heat treatment temperature on the properties of nanoparticulate TiO₂ powders that were synthesised by solid-state chemical reaction of anhydrous TiOSO₄ with Na₂CO₃. It was found that the photocatalytic activity increased with the heat treatment temperature up to a maximum at 600 °C and thereafter declined. In contrast, the optical transparency decreased monotonically with the heat treatment temperature. These results indicate that solid-state chemical reaction can be used to prepare powders of nanoparticulate TiO₂ with properties that are optimised for use as either optically transparent UV-filters or photocatalysts.

Mechanochemical synthesis of nanocrystalline SnO2-ZnO photocatalysts

Mechanochemical processing of anhydrous chloride precursors with Na₂CO₃ has been investigated as a means of manufacturing nanocrystalline SnO₂ doped ZnO photocatalysts. High-energy milling and heat-treatment of a 0.1SnCl₂+0.9ZnCl₂+Na₂CO₃+4NaCl reactant mixture was found to result in the formation of a composite powder consisting of oxide grains embedded within a matrix of NaCl. Subsequent washing with deionized water resulted in removal of the NaCl matrix phase and partial hydration of the oxide reaction product with the consequent formation of ZnSn(OH)₆. The extent of this hydration reaction was found to decrease in a linear fashion with the temperature of the post-milling heat-treatment over the range of 400–700 °C. For a heat-treatment temperature of 700 °C, the SnO₂ doped ZnO powder was found to exhibit significantly higher photocatalytic activity than either single-phase SnO₂ or ZnO powders that were synthesized using similar processing conditions. The heightened photocatalytic activity of the SnO₂ doped ZnO was attributed to its higher specific surface area and the enhanced charge separation arising from the coupling of ZnO with SnO₂.

Nanocrystalline zirconia powders synthesised by mechanochemical processing

Mechanochemical processing of zirconium and yttrium chloride precursors with lithium hydroxide has been used to synthesise ultrafine powders of yttria-stabilised zirconia. The precursors reacted during milling to form a composite consisting of nanocrystalline oxide grains embedded within a matrix of lithium chloride. The ultrafine powder was recovered subsequently by removing the lithium chloride through washing with deionised water and methanol. The powders were characterised using X-ray diffraction (XRD), transmission electron microscopy (TEM), and BET gas adsorption. The sintering behaviour of cold pressed pellets was examined by dilatometry.

Cobblestone mesotexture in a nanocrystalline Ni–20Fe electrodeposit

A distinct mesotexture seen in a nanocrystalline Ni–20Fe electrodeposit is described. The texture is characterized by a ^⟨0 0 1^⟩fibre axis perpendicular to the local curvature of the nodule growth surface. Each nodule contains of the order of 10⁸ grains over its growth interface. The texture shows some similarity to traditional cobblestone patterns. Similar forms of mesotextures are likely to be ubiquitous in nanocrystalline electrodeposits and can be expected to affect the homogeneity and, possibly, anisotropy of the mechanical response.