Effects of clay amendment on adsorption and desorption of copper in water repellent soils

Copper is an important micronutrient and trace amounts are essential for crop growth. However, high concentrations of copper will produce toxic effects. Australia is increasingly developing production of crops in water repellent soils. Clay amendment, a common amelioration techniques used in Australia, has demonstrated agronomic benefits in increased crop or pasture production. The sorption and desorption of copper and the effect of clay treatment on copper behaviour in a water repellent soil collected from an experimental farm in South Australia is studied. We found that the water repellent soils amended with clay have an increased adsorption capacity of copper. Also the clay-amended soils had an increased ratio of specific sorption to total sorption of copper. The implications of this study to the sustainable agro-environmental management of water repellent soils is discussed.

Absorption and desorption characteristics of fluoride in the calcareous and siliceous sand sheet aquifers of south-west Victoria, Australia

This study assessed the sustainability of utilising groundwater systems to
manage an aluminium smelter's fluoridated trade wastewater stream. Replacing ocean discharge of the wastewater with land irrigation is one option. Using a groundwater model (developed using MODFLOW incorporating parameter estimation software (PEST-ASP)), we found that most of the groundwater flow takes place through surface sands. Fluoride is adsorbed in these sands during the drier summer months, but desorption is rapid when winter rain flushes the aquifer. Underlying clays and other layers prevent significant contamination of the deeper aquifer.

The effect of concentrations and properties of phenanthrene, pyrene, and benzo(a)pyrene on desorption in contaminated soil aged for 1 year

Purpose : The choice and timing of microorganisms added to soils for bioremediation is affected by the dominant bioavailable contaminants in the soil. However, changes to the concentration of bioavailable PAHs in soil are not clear, especially when several PAHs coexist. This study investigated the effects of PAH concentration and chemical properties on desorption in meadow brown soil after a 1-year aging period, which could reflect changes of PAH bioavailability during bioremediation. Materials and methods : Based on the percentage of different molecular weights in a field investigation, high-level contaminated soil (HCS) and low-level contaminated soil (LCS) were prepared by adding phenanthrene (PHE), pyrene (PYR) and benzo(a)pyrene (BaP) to uncontaminated meadow brown soil. The concentrations of HCS and LCS were 250 mg kg−1 (PHE, PYR, and BaP: 100, 100, and 50 mg kg−1) and 50 mg kg−1 (PHE, PYR, and BaP: 20, 20, and 10 mg kg−1) respectively. The soils were aged for 1 year, after which desorption was induced by means of a XAD-2 adsorption technique over a 96-h period. Results and discussion : The range of the rapidly desorbing fraction (F rap) for PHE, PYR, and BaP in HCS and LCS was from 1.9 to 27.8 %. In HCS, desorption of PYR was most difficult, and the rate constant of very slow desorption (K vs) of PYR was 8 orders of magnitude lower than that of BaP, which had similar very slow desorbing fractions (49.8 and 50.5 %, respectively). However, in LCS, desorption of PYR was the easiest; the Kvs of PYR was 8–10 orders of magnitude higher than those of PHE and BaP. In HCS, the time scale for release of 50 % of the PAHs was ranked as BaP > PYR > PHE, while in LCS this was BaP > PHE > PYR. Conclusions : The combined effect of PAH concentrations and properties should be taken into account during desorption. The desorption of PAH did not always decrease with increasing molecular weight, and the desorption of four-ring PAHs might be special. These results are useful for screening biodegrading microbes and determining when they should be added to soils based on the dominant contaminants present during different periods, thus improving the efficiency of soil bioremediation.

Adsorption and desorption characteristics of fluoride in the calcareous and siliceous sand sheet aquifers of south-west Victoria, Australia

This study assessed the sustainability of utilising groundwater systems to manage an aluminium smelters fluoridated trade wastewater stream. Replacing ocean discharge of the wastewater with land irrigation is one option. Using a groundwater model (developed using MODFLOW incorporating parameter estimation software (PEST-ASP)), we found that most of the groundwater flow takes place through surface sands. Fluoride is adsorbed in these sands during the drier summer months, but desorption is rapid when winter rain flushes the aquifer. Underlying clays and other layers prevent significant contamination of the deeper aquifer.

Surface morphologies and internal fine structures of bast fibers

Fiber surface morphologies and associated internal structures are closely related to its properties. Unlike other fibers including cotton, bast fibers possess transverse nodes and fissures in cross-sectional and longitudinal directions. Their morphologies and associated internal structures were anatomically examined under the scanning electron microscope. The results showed that the morphologies of the nodes and the fissures of bast fibers varied depending on the construction of the inner fibril cellular layers. The transverse nodes and fissures were formed by the folding and spiralling of the cellular layers during plant growth. The dimensions of nodes and fissures were determined by the dislocations of the cellular layers. There were also many longitudinal fissures in bast fibers. Some deep longitudinal fissures even opened the fiber lumen for a short way along the fiber. In addition, the lumen channel of the bast fibers could be disturbed or disrupted by the nodes and the spirals of the internal cellular layers. The existence of the transverse nodes and fissures in the bast fibers could degrade the fiber mechanical properties, whereas the longitudinal fissures may contribute to the very rapid moisture absorption and desorption.

Enhanced degradation efficiency of toluene using titania/silica photocatalysis as a regeneration process

Three kinds of titania/silica pellets were prepared using the sol-gel method with surface areas of 50.4m² g-1, 421.1m².g^-1 and 89.1m².g^-1. An annular reactor was designed and built to determine the degradation efficiency of toluene and to investigate the relationship between the adsorption and desorption-photocatalytic processes. Surface area is an important factor influencing the adsorption-photocatalytic efficiency. Higher surface areas of pellets contribute to high rates of conversion of toluene. Un-reacted toluene and reaction intermediates accumulating on their surface deactivated the titania/silica catalyst. To overcome this problem, the adsorption and regeneration process were alternated in a dual reactor system. Connecting or disconnecting the toluene feed gas enabled one reactor to adsorb toluene, while the second reactor was regenerated by photocatalysis. Using UV irradiation and titania/silica pellets with high BET surface area (421.1 m².g^-1), the alternating adsorption/regeneration processes kept the degradation efficiency of toluene at 90% after 8 hours operation. By improving the adsorption-photocatalysis efficiency, and minimising the generation and accumulation of intermediate on the surface of pellets, the method extended catalyst life and maintained a high degradation efficiency of toluene.

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.

Thermodynamics of lipophilic drug binding to intestinal fatty acid binding protein and permeation across membranes

Intestinal fatty acid binding protein (I-FABP) is present at high levels in the absorptive cells of the intestine (enterocytes), where it plays a role in the intracellular solubilization of fatty acids (FA). However, I-FABP has also been shown to bind to a range of non-FA ligands, including some lipophilic drug molecules. Thus, in addition to its central role in FA trafficking, I-FABP potentially serves as an important intracellular carrier of lipophilic drugs. In this study we provide a detailed thermodynamic analysis of the binding and stability properties of I-FABP in complex with a series of fibrate and fenamate drugs to provide an insight into the forces driving drug binding to I-FABP. Drug binding and selectivity for I-FABP are driven by the interplay of protein−ligand interactions and solvent processes. The Gibbs free energies (ΔG°) determined from dissociation constants at 25 °C ranged from −6.2 to −10 kcal/mol. The reaction energetics indicate that drug binding to I-FABP is an enthalpy−entropy driven process. The relationship between I-FABP stability and drug binding affinity was examined by pulse proteolysis. There is a strong coupling between drug binding and I-FABP stability. The effect of an I-FABP protein sink on the kinetics and thermodynamics of tolfenamic acid permeation across an artificial phospholipid membrane were investigated. I-FABP significantly decreased the energy barrier for desorption of tolfenamic acid from the membrane into the acceptor compartment. Taken together, these data suggest that the formation of stable drug−I-FABP complexes is thermodynamically viable under conditions simulating the reactant concentrations likely observed in vivo and maybe a significant biochemical process that serves as a driving force for passive intestinal absorption of lipophilic drugs.

Zinc and DHA have opposing effects on the expression levels of histones H3 and H4 in human neuronal cells

Zn and DHA have putative neuroprotective effects and these two essential nutrients are known to interact biochemically. We aimed to identify novel protein candidates that are differentially expressed in human neuronal cell line M17 in response to Zn and DHA that would explain the molecular basis of this interaction. Two-dimensional gel electrophoresis and MS were applied to identify major protein expression changes in the protein lysates of human Ml7 neuronal cells that had been grown in the presence and absence of Zn and DHA. Proteomic findings were further investigated using Western immunoblot and real-time PCR analyses. Four protein spots, which had significant differential expression, were identified and selected for in-gel trypsin digestion followed by matrix-assisted laser desorption ionisation MS analysis. The resultant peptide mass fingerprint for each spot allowed their respective identities to be deduced. Two human histone variants H3 and H4 were identified. Both H3 and H4 were downregulated by Zn in the absence of DHA (Zn effect) and upregulated by DHA (DHA effect) in the presence of Zn (physiological condition). These proteomic findings were further supported by Western immunoblot and real-time PCR analyses using H3- and H4-specific monoclonal antibodies and oligonucleotide primers, respectively. We propose that dietary Zn and DHA cause a global effect on gene expression, which is mediated by histones. Such novel information provides possible clues to the molecular basis of neuroprotection by Zn and DHA that may contribute to the future treatment, prevention and management of neurodegenerative diseases such as Alzheimer's disease.

Deployment of DGT units in marine waters to assess the environmental risk from a deep sea tailings outfall

Measurements of total, filterable and DGT-labile concentrations of nine metals (Al, Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn) have been made at five sites up to 4.2km from a deep sea tailings outfall operated by Lihir Gold Ltd. at Lihir Island, Papua New Guinea. At each site, pairs of DGT units (one containing a 0.4mm and the other a 0.8mm diffusive gel layer) were deployed at three depths (50–70; 105–130; 135–155m) for 4–7 days. Comparison of predicted water column DGT-labile metal concentrations in field deployments showed the 0.8mm DGT units were relatively enriched in metals, with the effect being greatest closer to the outfall for Pb and Mn and least for Fe, Cr, Ni and Zn. The most likely explanation for this is that in addition to simple ion diffusion, kinetic factors associated with ageing or desorption processes govern release of metals from iron and aluminium oxyhydroxide colloids which diffuse through the gels. The thicker gels have a longer residence time over which metals can be released for adsorption. This model explains why enrichment is most pronounced near the outfall; more distant sites have lower colloid concentrations because of the longer time for coagulation to increase particle sizes to the extent they cannot enter the gels. Total and filterable metal (FM) concentrations were frequently below the limits of detection (LOD) achievable by conventional ICP-AES (1–52gL⁻¹) and this limited their usefulness for assessing environmental risk and for metal speciation determination. Because of its pre-concentration step DGT gave metal concentrations above their LODs and these decreased exponentially with distance from the outfall. Concentrations of DGT–labile metal fell below Australian water quality guidelines for protection of 99% of marine organisms within 0.13km of the outfall for Cd, Cr and Ni and below that for protection of 95% of marine organisms within 0.4, 0.7 and 3.6km for lead, zinc and copper, respectively.

Synthesis and characterization of silver nanoparticles and titanium oxide nanofibers : toward multifibrous nanocomposites

A new method was investigated to produce new multiscale fibrous nanocomposites comprised of titanium oxide (TiO₂) nanofibers and silver (Ag) nanoparticles (NPs). The process involved electrospinning TiO₂ precursor solution containing colloidal solution of Ag NPs, and organic solvent (dimethyl-n′n-formamide) to fabricate a porous, nonwoven, free-standing nanofiber mesh. Postprocess heating of the electrospun nanofibers entailed calcination in air environment at 500°C for 3 h. Microemulsion processing was used to generate NPs of Ag in a monodispersed distribution throughout the colloidal solution. X-ray diffraction data were consistent with the anatase phase of TiO2, while transmission electron microscopy and hydrogen desorption measurements revealed a very porous microstructure. It was demonstrated that NP colloidal stability is solvent dependent. It is anticipated that incorporation of metal particles in nanofibers will lead to enhanced photocurrent generation, when used in functional devices.

Characterisation of gold electrodes modified with self-assembled monolayers of l-cysteine for the adsorptive stripping analysis of copper

Electrochemical sensors for copper ions in environmental samples were prepared by modifying gold electrodes with l-cysteine by self-assembly. The adsorption of l-cysteine on gold electrodes was studied by electrochemical reductive desorption in 0.5 M KOH, and the interaction of l-cysteine with copper ions was investigated by cyclic voltammetry, chronoamperometry and X-ray photoelectron spectroscopy. At low concentrations the ratio of l-cysteine to bound Cu(II) is 2:1. At higher concentrations (0.1 M) copper reacts with adsorbed cysteine forming copper sulfide on the electrode surface. On a modified l-cysteine gold electrode, Osteryoung square wave voltammetric determination of Cu(II) with a detection limit below 5 ppb has been demonstrated.

Phase-structure effects of electrospun TiO2 nanofiber membranes on As(III) adsorption

TiO2 nanofibers (NFs) with different phases such as amorphous, anatase, mixed anatase?rutile, and rutile have been prepared by combining the electrospinning technique with the subsequent process of heat treatment or acidic-dissolution method. The obtained NFs are characterized by a Fourier transform infrared spectrometer (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption?desorption isotherm measurements. Phase structure effects of electrospun TiO2 NFs on As(III) adsorption behaviors have been investigated. The results showed a significant effect of the phase structures of TiO2 NFs on As(III) adsorption rates and capacities. Amorphous TiO2 NFs have the highest As(III) adsorption rate and capacity in the investigated samples, which can be attributed to its higher surface area and porous volume. This research provides a simple and low-cost method for phasecontrolled fabrication of TiO2 NFs and application for effective removal of arsenic from aqueous solution.

Synthesis and biological evaluation of novel folic acid receptor-targeted, β-cyclodextrin-based drug complexes for cancer treatment

Drug targeting is an active area of research and nano-scaled drug delivery systems hold tremendous potential for the treatment of neoplasms. In this study, a novel cyclodextrin (CD)-based nanoparticle drug delivery system has been assembled and characterized for the therapy of folate receptor-positive [FR(+)] cancer. Water-soluble folic acid (FA)-conjugated CD carriers (FACDs) were successfully synthesized and their structures were confirmed by 1D/2D nuclear magnetic resonance (NMR), matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOF-MS), high performance liquid chromatography (HPLC), Fourier transform infrared spectroscopy (FTIR), and circular dichroism. Drug complexes of adamatane (Ada) and cytotoxic doxorubicin (Dox) with FACD were readily obtained by mixed solvent precipitation. The average size of FACD-Ada-Dox was 1.5-2.5 nm. The host-guest association constant Ka was 1,639 M-1 as determined by induced circular dichroism and the hydrophilicity of the FACDs was greatly enhanced compared to unmodified CD. Cellular uptake and FR binding competitive experiments demonstrated an efficient and preferentially targeted delivery of Dox into FR-positive tumor cells and a sustained drug release profile was seen in vitro. The delivery of Dox into FR(+) cancer cells via endocytosis was observed by confocal microscopy and drug uptake of the targeted nanoparticles was 8-fold greater than that of non-targeted drug complexes. Our docking results suggest that FA, FACD and FACD-Ada-Dox could bind human hedgehog interacting protein that contains a FR domain. Mouse cardiomyocytes as well as fibroblast treated with FACD-Ada-Dox had significantly lower levels of reactive oxygen species, with increased content of glutathione and glutathione peroxidase activity, indicating a reduced potential for Dox-induced cardiotoxicity. These results indicate that the targeted drug complex possesses high drug association and sustained drug release properties with good biocompatibility and physiological stability. The novel FA-conjugated β-CD based drug complex might be promising as an anti-tumor treatment for FR(+) cancer.

Anti-metastatic and differential effects on protein expression of epigallocatechin-3-gallate in HCCLM6 hepatocellular carcinoma cells

Hepatocellular carcinoma (HCC) is the fifth most common cancer worldwide and the third highest cause of cancer-related mortality in humans. Epigallocatechin-3-gallate (EGCG) has been shown to inhibit the metastatic activity of certain cancer cells. The aim of this study was to determine the effects and molecular mechanism(s) of action of EGCG in human HCC cells. A migration and invasion assay for the metastatic behavior of HCCLM6 cells was performed. The anti-metastatic effects of EGCG were investigated by RT-PCR and gelatin zymography. A total cellular protein profile was obtained using 2-dimensional gel electrophoresis (2-DE), followed by matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS) analyses of proteins with significant differences in expression following treatment with EGCG. The results revealed that EGCG induced apoptosis and inhibited the metastasis of HCCLM6 cells. The anti-metastatic effects of EGCG were associated with the inhibition of matrix metalloproteinase (MMP)-2 and MMP-9 activity. The expression levels of far upstream element (FUSE) binding protein 1 (FUBP1), heat shock protein beta 1 (HSPB1), heat shock 60 kDa protein 1 (chaperonin) (CH60) and nucleophosmin (NPM) proteins, which are associated with metastasis, were significantly altered in the EGCG-treated HCCLM6 cells. The data from the present study suggest that EGCG has potential as a therapeutic agent for the treatment of HCC.