Evaluation of fe oxide-coated granular activated carbon for removal and recovery of Cu(II) and Cr(VI) from aqueous solution /

"April 1994."--Cover.

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation, in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter-rich black shales rather than in sandstones, siltstones and organic matter-poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity-permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity-permeability and organic matter alteration, suitable for subsequent mineral precipitation. K-Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 +/- 150 (2sigma) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity-permeability creation. Those rocks lacking sufficient porosity-permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.

Coal ash conversion into effective adsorbents for removal of heavy metals and dyes from wastewater

Fly ash was modified by hydrothermal treatment using NaOH solutions under various conditions for zeolite synthesis. The XRD patterns are presented. The results indicated that the samples obtained after treatment are much different. The XRD profiles revealed a number of new reflexes, suggesting a phase transformation probably occurred. Both heat treatment and chemical treatment increased the surface area and pore volume. It was found that zeolite P would be formed at the conditions of higher NaOH concentration and temperature. The treated fly ash was tested for adsorption of heavy metal ions and dyes in aqueous solution. It was shown that fly ash and the modified forms could effectively absorb heavy metals and methylene blue but not effectively adsorb rhodamine B. Modifying fly ash with NaOH solution would significantly enhance the adsorption capacity depending on the treatment temperature, time, and base concentration. The adsorption capacity of methylene blue would increases with pH of the dye solution and the sorption capacity of FA-NaOH could reach 5 x 10(-5) mol/g. The adsorption isotherm could be described by the Langmuir and Freundlich isotherm equations. Removal of copper and nickel ions could also be achieved on those treated fly ash. The removal efficiency for copper and nickel ions could be from 30% to 90% depending on the initial concentrations. The increase in adsorption temperature will enhance the adsorption efficiency for both heavy metals. The pseudo second-order kinetics would be better for fitting the dynamic adsorption of Cu and Ni ions. (c) 2005 Elsevier B.V. All rights reserved.

Hydrogen generation from liquid phase catalytic reforming of sugar solutions using metal-supported catalysts

Most of the hydrogen production processes are designed for large-scale industrial uses and are not suitable for a compact hydrogen device to be used in systems like solid polymer fuel cells. Integrating the reaction step, the gas purification and the heat supply can lead to small-scale hydrogen production systems. The aim of this research is to study the influence of several reaction parameters on hydrogen production using liquid phase reforming of sugar solution over Pt, Pd, and Ni supported on nanostructured supports. It was found that the desired catalytic pathway for H-2 production involves cleavage of C-C, C-H and O-H bonds that adsorb on the catalyst surface. Thus a good catalyst for production of H2 by liquid-phase reforming must facilitate C-C bond cleavage and promote removal of adsorbed CO species by the water-gas shift reaction, but the catalyst must not facilitate C-O bond cleavage and hydrogenation of CO or CO2. Apart from studying various catalysts, a commercial Pt/gamma-alumina catalyst was used to study the effect of temperature at three different temperatures of 458, 473 and 493 K. Some of the spent catalysts were characterised using TGA, SEM and XRD to study coke deposition. The amorphous and organised form of coke was found on the surface of the catalyst. (C) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Characterization of metal ion-induced [3H]inositol hexakisphosphate binding to rat cerebellar membranes

The binding of [3H]inositol hexakisphosphate ([3H] InsP6) to rat cerebellar membranes has been characterized with the objective of establishing the role, if any, of a membrane protein receptor. In the presence of EDTA, we have previously identified an InsP6-binding site with a capacity of approximately 20 pmol/mg protein (Hawkins, P. T., Reynolds, D. J. M., Poyner, D. R., and Hanley, M. R. (1990) Biochem. Biophys. Res. Commun. 167, 819-827). However, in the presence of 1 mM Mg2+, the capacity of [3H]InsP6 binding to membranes was increased approximately 9-fold. This enhancing effect of Mg2+ was reversed by addition of 10 microM of several cation chelators, suggesting that the increased binding required trace quantities of other metal cations. This is supported by experiments where it was possible to saturate binding by addition of excess membranes, despite not significantly depleting radioligand, pointing to removal of some other factor. Removal of endogenous cations from the binding assay by pretreatment with chelex resin also prevents the Mg(2+)-induced potentiation. Consideration of the specificity of the chelators able to abolish this potentiation suggested involvement of Fe3+ or Al3+. Both these ions (but not several others) were able to increase [3H]InsP6 binding to chelex-pretreated membranes at concentrations of 1 microM. It is possible to demonstrate synergy between Fe3+ and Mg2+ under these conditions. We propose that [3H]InsP6 may interact with membranes through non-protein recognition possibly via phospholipids, in a manner dependent upon trace metals. The implications of this for InsP6 biology are considered.

The role of oxidation in the protection of sliding metal surfaces

This study is concerned with the mechanisms of growth and wear of protective oxide films formed under various tribological conditions. In the study three different tribological systems are examined in each of which oxidational wear is the dominant equilibrium mode. These are an unlubricated steel on steel system sliding at low and elevated temperatures, a boundary lubricated aluminium bronze on steel system and an unlubricated reciprocating sliding 9% Cr steel system operated at elevated temperature, in an atmosphere of carbon dioxide. The results of mechanical measurements of wear and friction are presented for a range of conditions of load, speed and temper.ature for the systems, together with the results of extensive examinations of the surfaces and sub­ surfaces by various physical methods of analysis. The major part of the thesis, however, is devoted to the development and application of surface models and theoretical quantative expressions in order to explain the observed oxidational wear phenomena. In this work, the mechanisms of formation of load bearing ox ide plateaux are described and are found to be dependent on system geometry and environment. The relative importance of ''in contact" and "out of contact" oxidation is identified together with growth rate constants appropriate to the two situations. Hypotheses are presented to explain the mechanisms of removal of plateaux to form wear debris. The latter hypotheses include the effects of cyclic stressing and dislocation accumulation, together with effects associated with the kinetics of growth and physical properties of the various oxides. The proposed surf ace mode1s have led to the develop­ ment of quantitative expressions for contact temperature, unlubricated wear rates, boundary lubricated wear rates and the wear of rna ter ial during the transition from severe to mild wear. In general theoretical predictions from these expressions are in very good agreement with experimental values.

A study in the reduction of efficiency of nitrogen oxide removal catalysts for automobiles

Automotive catalysts are the most effective short-term answer to air pollution from automobiles. Since strict control of exhaust emissions is, or will be,covered by legislation in most developed countries in the world, catalytic devices will be increasingly fitted to cars. There is consequently an urgent need for the development of catalysts that will not compete for scarce precious metal resources. A number of problems have already been identified in connection with base metal catalysts but quantitative investigations are lacking. The base metal reduction catalysts developed by Imperial Chemical Industries Limited, catalysts and Chemical Group, in collaboration with the Air Pollution Control Laboratory, B L Cars Limited for automotive emission control, are susceptible to de-activation by three major mechanisms. These are: physical loss of the wash-coat (a high surface area coating which supports the active species), aggregation of the active species and poisoning by fuel and engine oil additives. This thesis is especially concerned with the first two of these and attempts to indicate the relative magnitude .of their effect on the activity of. the catalysts. Aggregation of the active species or sintering, as it is loosely called, was studied by using impregnated granules to overcome effects due to the loss of the wash-coat. Samples were aged in a synthetic exhaust gas, free from poisons, and metal crystallite sizes were measured by scanning-electron microscopy. The increase in particle size was correlated with the loss in catalytic activity. In order to maintain a link with the real conditions of service a number of monolithic catalysts were tested in an engine-dynamometer and several previously tested endurance catalysts were examined. A mechanism is proposed for the break-up and subsequent 10s.5 of the wash-coat and suggestions for improved resistance to loss of the' coating and active species are proposed.

A comparative study on the pyrolysis of metal- and ash-enriched wood and the combustion properties of the gained char

This study aims to investigate the pyrolysis behaviour of metal-contaminated wood and the combustion properties of char derived from wood pyrolysis. Seven metals (Na, Mg, Ca, Zn, Cd, Pb and Fe(III)) were introduced to willow in cation form by ion-exchange and the thermal behaviour of demineralised samples and samples with additional ash were also investigated. The results show that the char yield increased from 21% to 24-28% and levoglucosan yield in vapour phase decreased from 88% to 62-29% after the addition of inorganic compounds, even though the metal binding capacity of wood varied from one metal ion to another. While char yield seems to be effected mainly by the concentration of the metal ions, levoglucosan yield was more dependent on the ionic species especially when sodium ions were present. When combustion experiments were carried out with char made of the metal enriched wood, two consecutive steps were observed, both effected by the presence of inorganic compounds. The first step was identified as the release and combustion of volatiles, while the second peak of the burning profile is the actual combustion of the fixed carbon. The burnout temperatures, estimated ignition indices and the conversion indicate that the type and not the amount of metal ions were the determining factors during the second step of combustion. © 2012 Published by Elsevier B.V.

A structural investigation of the alkali metal site distribution within bioactive glass using neutron diffraction and multinuclear solid state NMR

The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2 metal ions bonded either to bridging or to non-bridging oxygen atoms. 23Na triple quantum MAS (3QMAS) NMR data corroborates the split Na-O correlations. The structural sites present will be intimately related to the release properties of the glass system in physiological fluids such as plasma and saliva, and hence to the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimizing material design.

Design, synthesis and RAFT polymerisation of a quinoline-based monomer for use in metal-binding composite microfibres

Metal-binding polymer fibres have attracted major attention for diverse applications in membranes for metal sequestration from waste waters, non-woven wound dressings, matrices for photocatalysis, and many more. This paper reports the design and synthesis of an 8-hydroxyquinoline-based zinc-binding styrenic monomer, QuiBoc. Its subsequent polymerisation by reversible addition–fragmentation chain transfer (RAFT) yielded well-defined polymers, PQuiBoc, of controllable molar masses (6 and 12 kg mol−1) with low dispersities (Đ, Mw/Mn < 1.3). Protected (PQuiBoc) and deprotected (PQuiOH) derivatives of the polymer exhibited a high zinc-binding capacity, as determined by semi-quantitative SEM/EDXA analyses, allowing the electrospinning of microfibres from a PQuiBoc/polystyrene (PS) blend without the need for removal of the protecting group. Simple “dip-coating” of the fibrous mats into ZnO suspensions showed that PQuiBoc/PS microfibres with only 20% PQuiBoc content had almost three-fold higher loadings of ZnO (29%) in comparison to neat PS microfibres (11%).

Multi-media filtration for removal of petroleum contamination

A pilot scale multi-media filtration system was used to evaluate the effectiveness of filtration in removing petroleum hydrocarbons from a source water contaminated with diesel fuel. Source water was artificially prepared by mixing bentonite clay and tap water to produce a turbidity range of 10-15 NTU. Diesel fuel concentrations of 150 ppm or 750 ppm were used to contaminate the source water. The coagulants used included Cat Floc K-10 and Cat Floc T-2. The experimental phase was conducted under direct filtration conditions at constant head and constant rate filtration at 8.0 gpm. Filtration experiments were run until the filter reached its clogging point as noted by a measured peak pressure loss of 10 psi. The experimental variables include type of coagulant, oil concentration and source water. Filtration results were evaluated based on turbidity removal and petroleum hydrocarbon (PHC) removal efficiency as measured by gas chromatography. Experiments indicated that clogging was controlled by the clay loading on the filter and that inadequate destabilization of the contaminated water by the coagulant limited the PHC removal. ^

Development of calix[4]arene-functionalized microcantilever array sensing system for the rapid, sensitive and simultaneous detection of metal ions in aqueous solutions

The work described in this thesis was conducted with the aim of: 1) investigating the binding capabilities of calix[4]arene-functionalized microcantilevers towards specific metal ions and 2) developing a new16-microcantilever array sensing system for the rapid, and simultaneous detection of metal ions in fresh water. Part I of this thesis reports on the use of three new bimodal calix[4]arenes (methoxy, ethoxy and crown) as potential host/guest sensing layers for detecting selected ions in dilute aqueous solutions using single microcantilever experimental system. In this work it was shown that modifying the upper rim of the calix[4]arenes with a thioacetate end group allow calix[4]arenes to self-assemble on Au(111) forming complete highly ordered monolayers. It was also found that incubating the microcantilevers coated with 5 nm of Inconel and 40 nm of Au for 1 h in a 1.0 M solution of calix[4]arene produced the highest sensitivity. Methoxy-functionalized microcantilevers showed a definite preference for Ca²⁺ ions over other cationic guests and were able to detect trace concentration as low as 10⁻¹² M in aqueous solutions. Microcantilevers modified with ethoxy calix[4]arene displayed their highest sensitivity towards Sr²⁺ and to a lesser extent Ca²⁺ ions. Crown calix[4]arene-modified microcantilevers were however found to bind selectively towards Cs⁺ ions. In addition, the counter anion was also found to contribute to the deflection. For example methoxy calix[4]arene-modified microcantilever was found to be more sensitive to CaCl₂ over other water-soluble calcium salts such as Ca(NO₃)₂ , CaBr₂ and CaI₂. These findings suggest that the response of calix[4]arene-modified microcantilevers should be attributed to the target ionic species as a whole instead of only considering the specific cation and/or anion. Part II presents the development of a 16-microcantilever sensor setup. The implementation of this system involved the creation of data analysis software that incorporates data from the motorized actuator and a two-axis photosensitive detector to obtain the deflection signal originating from each individual microcantilever in the array. The system was shown to be capable of simultaneous measurements of multiple microcantilevers with different coatings. A functionalization unit was also developed that allows four microcantilevers in the array to be coated with an individual sensing layer one at the time. Because of the variability of the spring constants of different cantilevers within the array, results presented were quoted in units of surface stress unit in order to compare values between the microcantilevers in the array.

Assessing hydrothermal liquefaction for the production of bio-oil and enhanced metal recovery from microalgae cultivated on acid mine drainage

The hydrothermal liquefaction(HTL) of algal biomass is a promising route to viable second generation biofuels. In this investigation HTL was assessed for the valorisation of algae used in the remediation of acid mine drainage (AMD). Initially the HTL process was evaluated using Arthrospira platensis (Spirulina) with additional metal sulphates to simulate metal remediation. Optimised conditions were then used to process a natural algal community (predominantly Chlamydomonas sp.) cultivated under two scenarios: high uptake and low uptake of metals from AMD. High metal concentrations appear to catalyse the conversion to bio-oil, and do not significantly affect the heteroatom content or higher heating value of the bio-oil produced. The associated metals were found to partition almost exclusively into the solid residue, favourable for potential metal recovery. High metal loadings also caused partitioning of phosphates from the aqueous phase to the solid phase, potentially compromising attempts to recycle process water as a growth supplement. HTL was therefore found to be a suitable method of processing algae used in AMD remediation, producing a crude oil suitable for upgrading into hydrocarbon fuels, an aqueous and gas stream suitable for supplementing the algal growth and the partitioning of most contaminant metals to the solid residue where they would be readily amenable for recovery and/or disposal.

Assessing hydrothermal liquefaction for the production of bio-oil and enhanced metal recovery from microalgae cultivated on acid mine drainage

The hydrothermal liquefaction(HTL) of algal biomass is a promising route to viable second generation biofuels. In this investigation HTL was assessed for the valorisation of algae used in the remediation of acid mine drainage (AMD). Initially the HTL process was evaluated using Arthrospira platensis (Spirulina) with additional metal sulphates to simulate metal remediation. Optimised conditions were then used to process a natural algal community (predominantly Chlamydomonas sp.) cultivated under two scenarios: high uptake and low uptake of metals from AMD. High metal concentrations appear to catalyse the conversion to bio-oil, and do not significantly affect the heteroatom content or higher heating value of the bio-oil produced. The associated metals were found to partition almost exclusively into the solid residue, favourable for potential metal recovery. High metal loadings also caused partitioning of phosphates from the aqueous phase to the solid phase, potentially compromising attempts to recycle process water as a growth supplement. HTL was therefore found to be a suitable method of processing algae used in AMD remediation, producing a crude oil suitable for upgrading into hydrocarbon fuels, an aqueous and gas stream suitable for supplementing the algal growth and the partitioning of most contaminant metals to the solid residue where they would be readily amenable for recovery and/or disposal.