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.

Porous carbon nanotube/polyvinylidene fluoride composite material: Superhydrophobicity/superoleophilicity and tunability of electrical conductivity

Porous carbon nanotube/polyvinylidene fluoride (CNT/PVDF) composite material can be fabricated via formation and freeze-drying of a gel. The field emission scanning electron microscopy, nitrogen adsorption-desorption and pore size distribution analysis reveal that the introduction of a small amount of carbon nanotubes (CNTs) can effectively increase the surface roughness and porosity of polyvinylidene fluoride (PVDF). Contact angle measurements of water and oil indicate that the as-obtained composite material is superhydrophobic and superoleophilic. Further experiments demonstrate that these composite material can be efficiently used to separate/absorb the insoluble oil from oil polluted water as membrane/absorbent. Most importantly, the electrical conductivity of such porous CNT/PVDF composite material can be tuned by adjusting the mass ratio of CNT to PVDF without obviously changing the superhydrophobicity or superoleophilicity. The unique properties of the porous CNT/PVDF composite material make it a promising candidate for oil-polluted water treatment as well as water-repellent catalyst-supporting electrode material.

Performance of constructed evaporation ponds for disposal of smelter waster water: a case study at Portland Aluminum, Victoria, Australia

The construction of evaporative ponds and wetlands for the disposal of waste water high in ionic concentrations is a waste disposal strategy currently considered by many industries. However, the design, construction and management of these ponds and wetlands are not straightforward as complex chemical interactions result in both spatial and temporal changes in water quality. The effects of evaporation and drainage on the water quality in two constructed ponds, an adjacent man-made wetland and local groundwater at Portland Aluminium were investigated. The minimum volume of water entering the ponds during the study period was 0.96±0.16 ML per month. The predicted theoretical evaporative capacity of the two ponds was calculated to be 0.30±0.07 ML per month. More water enters the ponds than it is theoretically possible to evaporate under the ambient weather conditions at Portland, yet the ponds do not overflow, suggesting percolation through the pond lining. No spatial differences in solute concentrations (fluoride, sulphate, bicarbonate, carbonate, sodium, potassium, calcium, and magnesium ions) were found within the waters of either pond, although temporal differences were apparent. The results support the conclusion that the ponds are not impermeable, and that much of the waste water entering the ponds is being lost through seepage. The impacts on local groundwater chemistry of this seepage are addressed. Significant correlations exist between solute presence within and between the ponds, wetland and groundwater. Fluoride and sulphate concentrations were significantly higher in pond waters throughout the duration of the experiment. Pond sediments revealed a high degree of spatial and temporal heterogeneity in the concentration of all monitored ions resulting from the chemical heterogeneity of the material making up the pond linings. Adsorption isotherms for fluoride indicate that the adsorption capacity of the pond linings remains high for this ion. Implications for the management of waste water by this strategy are discussed.

Solar adsorption refrigeration : an alternative/auxiliary way for thermal storage for air conditioning

This paper presents an idea of using solar powered adsorption ice making system as an alternative or an auxiliary way for the traditional ice storage air conditioning systems. A simple solar adsorption refrigeration system runs in intermittent cycle. It makes cooling effect at night, and the cooling effect can be stored for the day use. It fits in well with the cycle of the existing off-peak ice storage air conditioning system. On the top of green effect of the solar powered ice making system, the idea is specifically beneficial for places where the price of the off-peak electricity is not significantly lower than peak price. Based on our many years experience on the solar ice making systems, the paper discusses the technical feature of the solar ice making technology and the solutions we are working on to attack the problems which may have potential damage to application of the solar ice making system for air conditioning purposes.

Sodium adsorption using activated alumina for application in the dairy industry

Basic activated alumina with negatively charged surface is considered as a potential adsorbent for a targeted molecule with positive polarity. Adsorption of sodium by basic activated alumina was investigated as a method for desalting dairy waste streams, in which sodium ion concentration averaged 600 mg/L. Sodium equilibrium and kinetic adsorption were investigated using basic activated alumina with synthetic brines. The results of equilibrium adsorption show that uptake of sodium by activated alumina is significantly higher when the pH is greater than 8 and increases as the pH of the brines increases until pH reaches around 10. The results of kinetic adsorption show that 90 hours were needed to reach equilibrium for sodium adsorption. Binding and diffusion processes are suggested to have taken place within the activated alumina.

Using titania photocatalysts to degrade toluene in a combined adsorption and photocatalysis process

Three types of titania supported materials including titanium dioxide and silicon dioxide composite, titania-coated activated carbon and titania-coated glass beads were prepared and used as photocatalysts to remove toluene from an air stream. Their surface areas were analysed. TEM image reveals titania-silica composites were nanostructured aggregates. XRD was used to determine their crystalline phase which was 100% anatase for the titania component. A fixed bed reactor was designed and built in the laboratory, the toluene with initial concentration of 300 ppm (1149 mg/m³) was fed into the reactor, the destruction efficiencies of toluene were determined by the gas analyser. It was also found that TiO₂-SiO₂ aggregates with high surface area (421.1 m²/g) achieved high destruction efficiencies. The combined effects of adsorption and photocatalysis were further studied by comparing the performance of pure activated carbon (surface area of 932.4 m²/g) and TiO₂ coated activated carbon with BET surface area of 848.4 m²/g. It was found that the TiO₂ coated activated carbon demonstrated comparable results to pure activated carbon, and most importantly, the TiO₂-coated activated carbon can be effectively regenerated by UV irradiation, and was reused as adsorbent. The experimental result of titania-coated glass beads demonstrated a steady degradation efficiency of 15% after a period of 17 hours. It helped to understand that photocatalysis degradation ability of the TiO₂ was constant regardless of the adsorption capacity of the catalysts. This photocatalytic property can be used to degrade the adsorbed toluene and regenerate the catalyst. This study revealed that if the experiments were designed to use adsorption to remove toluene and followed by regeneration of adsorbent using photocatalysis, it could achieve a very high removal efficiency of toluene and reduce the regeneration cost of saturated adsorbent.

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.

The first dimeric trioganotin fluoride : stabilization by unsymmetrically oriented menthyl substituents

In the solid state, (-)-tris([1R,2S,5R]-menthyl)tin fluoride, Men₃SnF (6), exhibits a dimeric structure in which one tin atom is four-coordinate and the other five-coordinate. This novel dimeric association mode is attributed to the orientation of the unsymmetrical menthyl groups, which are arranged to allow a minimum Sn···Sn separation of 4.84 Å within the dimer. The exocyclic isopropyl groups of the menthyl groups point in opposite directions on each tin atom of the dimer, thus preventing further association (Sn···Sn separation outside the dimer 10.49 Å). ¹¹⁹Sn and ¹⁹F MAS NMR spectroscopy were utilized to probe the diverse coordination numbers found by X-ray crystallography for the geometries of the two tin and fluorine sites. In solution, 6 is a monomer at both room temperature and -100 °C. However, upon addition of Bu₄NF, 6 is in equilibrium with [(Men₃SnF)₂F]- (6a), [Men₃SnF₂]^- (6b), and noncoordinating fluoride anions.

Removal of VOCs by photocatalysis process using adsorption enhanced TiO2–SiO2 catalyst

Volatile organic compounds (VOCs) exist widely in both the indoor and outdoor environment. The main contributing sources of VOCs are motor vehicle exhaust and solvent utilization. Some VOCs are toxic and carcinogenic to human health, such as benzene. In this study, TiO₂–SiO₂ based photocatalysts were synthesized using the sol–gel method, with high surface areas of 274.1–421.1 m²/g obtained. Two types of pellets were used as catalysts in a fixed-bed reactor installed with a UV black light lamp. Experiments were conducted to compare their efficiencies in degrading the VOCs. Toluene was used as the VOC indicator. When the toluene laden gas stream passed through the photocatalytic reactor, the removal efficiencies were determined using a FTIR multi-gas analyser, which was connected to the outlet of the reactor to analyse the toluene concentrations. As the TiO₂–SiO₂ pellets used have a high adsorption capacity, they had dual functions as a photocatalyst and adsorbent in the hybrid photocatalysis and adsorption system. The experiments demonstrated that the porous photocatalyst with very high adsorptive capacity enhanced the subsequent photocatalysis reactions and lead to a positive synergistic effect. The catalyst can be self-regenerated by photocatalytic oxidation of the adsorbed VOCs. When the UV irradiation and feeding gas is continuous, a destruction efficiency of about 25% was achieved over a period of 20 h. Once the system was designed and operated into adsorption/regeneration mode, a higher removal efficiency of about 55% was maintained. It was found that the catalyst pellets with a higher surface area (421 m²/g) achieved higher conversion efficiency (100%) for a longer period than those with a lower surface area. A full spectrum scan was carried out using a Bio-rad Infrared spectrometer, finding that the main components of the treated gas stream leaving the reactor, along with untreated toluene, were CO₂ and water. The suspected intermediates of aliphatic hydrocarbons and CO were found in minimal amounts or were non detectable. The kinetic rate constants were calculated from the experimental results, it appeared that the stronger adsorption capacity, i.e. larger specific surface area, the higher conversion efficiency would be achieved.

Simulation of the solar adsorption refrigeration operating at near atmospheric pressure

To solve the leaking problem faced by current vacuum adsorption refrigeration systems, the authors have carried out a series of studies on the concept of raising the system's pressure to around atmospheric pressure with an inert gas (eg. Helium) as the pressure-adjusting agent. This paper presents the simulation of the performance oj the activated carbon-methanol adsorption refrigeration operating at near atmospheric pressure powered by solar energy. This simulation can be refereed in the prototype design.

Fluoride-assisted synthesis of mullite (Al5.65 Si0.35 O9.175) nanowires

Novel silicon-deficient mullite (Al_5.65Si_0.35O_9.175) single crystal nanowires were synthesized in large quantities on mica substrates assisted by the intermediate fluoride species. The nanowires have diameters in the range 50–100 nm and typical lengths of several µm. Aligned nanowires were observed at the substrate edge. The nanowires have strong photoluminescence (PL) emission bands at 310, 397, 452 and 468 nm.

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.

Adsorption and voltammetry of butyltin compounds

The adsorption of tributyltin onto materials commonly used for the construction of sampling and analytical equipment from aqueous solutions of varying ionic composition has been examined. The adsorption appears to be controlled by non-polar interactions between tributyltin and the surface involved. Since the speciation and hence polarity of tributyltin is affected by the ionic composition of the medium, the extent of adsorption is affected by the salinity and pH of a sample. The adsorption is rapid and, unless strategies are adopted to eliminate its effects, may render analytical results invalid. The electrochemistry of tributyltin, dibutyltin and monobutyltin, individually and in mixtures, has been investigated in aqueous media at mercury electrodes. The basic electrochemistry of each compound is summarised by the reaction BunSn (4-n)+ + (4-n)e- right left harpoons BunSn where n is the number of butyl groups attached to the tin atom. However, the electrochemistry of each compound is largely confined to the surface of the mercury electrode, and the simplicity of the above reaction is disrupted by polymerisation reactions and by butyl exchange processes occurring with the mercury electrode. When mixtures of butyltin compounds are present, the various processes that occur for each individual compound interfere with each other. A direct voltaminetric method for the determination of butyltin compounds in natural waters is therefore probably not possible.