Optimisation of process parameters for the removal of hydroxycinnamic acids in sugar solutions

Colour is one of the most important parameters in sugar quality and its presence in raw sugar plays a key role in the marketing strategy of sugar industries worldwide. This study investigated the degradation of a mixture of colour precursors using the Fenton oxidation process. These colour precursors are caffeic acid, p–coumaric acid and ferulic acid, which are present in cane juice. Results showed that with a Fe(II) to H2O2 molar ratio of 1:15 in an aqueous system at 25 °C, 77% of the total phenolic acid content was removed at pH 4.72. However, in a synthetic juice solution which contained 13 mass % sucrose (35 °C, pH 5.4), only 60% of the total phenolic acid content was removed.

Environmental factors controlling temporal and spatial variability in the soil-atmosphere exchange of CO2, CH4 and N2O from an Australian subtropical rainforest

The temporal variations in CO2, CH4 and N2O fluxes were measured over two consecutive years from February 2007 to March 2009 from a subtropical rainforest in south-eastern Queensland, Australia, using an automated sampling system. A concurrent study using an additional 30 manual chambers examined the spatial variability of emissions distributed across three nearby remnant rainforest sites with similar vegetation and climatic conditions. Interannual variation in fluxes of all gases over the 2 years was minimal, despite large discrepancies in rainfall, whereas a pronounced seasonal variation could only be observed for CO2 fluxes. High infiltration, drainage and subsequent high soil aeration under the rainforest limited N2O loss while promoting substantial CH4 uptake. The average annual N2O loss of 0.5 ± 0.1 kg N2O-N ha−1 over the 2-year measurement period was at the lower end of reported fluxes from rainforest soils. The rainforest soil functioned as a sink for atmospheric CH4 throughout the entire 2-year period, despite periods of substantial rainfall. A clear linear correlation between soil moisture and CH4 uptake was found. Rates of uptake ranged from greater than 15 g CH4-C ha−1 day−1 during extended dry periods to less than 2–5 g CH4-C ha−1 day−1 when soil water content was high. The calculated annual CH4 uptake at the site was 3.65 kg CH4-C ha−1 yr−1. This is amongst the highest reported for rainforest systems, reiterating the ability of aerated subtropical rainforests to act as substantial sinks of CH4. The spatial study showed N2O fluxes almost eight times higher, and CH4 uptake reduced by over one-third, as clay content of the rainforest soil increased from 12% to more than 23%. This demonstrates that for some rainforest ecosystems, soil texture and related water infiltration and drainage capacity constraints may play a more important role in controlling fluxes than either vegetation or seasonal variability

Removal of toxic metals in a multi metal system using sorbents for potential application to urban stormwater treatment

In the context of increasing demand for potable water and the depletion of water resources, stormwater is a logical alternative. However, stormwater contains pollutants, among which metals are of particular interest due to their toxicity and persistence in the environment. Hence, it is imperative to remove toxic metals in stormwater to the levels prescribed by drinking water guidelines for potable use. Consequently, various techniques have been proposed, among which sorption using low cost sorbents is economically viable and environmentally benign in comparison to other techniques. However, sorbents show affinity towards certain toxic metals, which results in poor removal of other toxic metals. It was hypothesised in this study that a mixture of sorbents that have different metal affinity patterns can be used for the efficient removal of a range of toxic metals commonly found in stormwater. The performance of six sorbents in the sorption of Al, Cr, Cu, Pb, Ni, Zn and Cd, which are the toxic metals commonly found in urban stormwater, was investigated to select suitable sorbents for creating the mixtures. For this purpose, a multi criteria analytical protocol was developed using the decision making methods: PROMETHEE (Preference Ranking Organisation METHod for Enrichment Evaluations) and GAIA (Graphical Analysis for Interactive Assistance). Zeolite and seaweed were selected for the creation of trial mixtures based on their metal affinity pattern and the performance on predetermined selection criteria. The metal sorption mechanisms employed by seaweed and zeolite were defined using kinetics, isotherm and thermodynamics parameters, which were determined using the batch sorption experiments. Additionally, the kinetics rate-limiting steps were identified using an innovative approach using GAIA and Spearman correlation techniques developed as part of the study, to overcome the limitation in conventional graphical methods in predicting the degree of contribution of each kinetics step in limiting the overall metal removal rate. The sorption kinetics of zeolite was found to be primarily limited by intraparticle diffusion followed by the sorption reaction steps, which were governed mainly by the hydrated ionic diameter of metals. The isotherm study indicated that the metal sorption mechanism of zeolite was primarily of a physical nature. The thermodynamics study confirmed that the energetically favourable nature of sorption increased in the order of Zn < Cu < Cd < Ni < Pb < Cr < Al, which is in agreement with metal sorption affinity of zeolite. Hence, sorption thermodynamics has an influence on the metal sorption affinity of zeolite. On the other hand, the primary kinetics rate-limiting step of seaweed was the sorption reaction process followed by intraparticle diffusion. The boundary layer diffusion was also found to limit the metal sorption kinetics at low concentration. According to the sorption isotherm study, Cd, Pb, Cr and Al were sorbed by seaweed via ion exchange, whilst sorption of Ni occurred via physisorption. Furthermore, ionic bonding is responsible for the sorption of Zn. The thermodynamics study confirmed that sorption by seaweed was energetically favourable in the order of Zn < Cu < Cd < Cr . Al < Pb < Ni. However, this did not agree with the affinity series derived for seaweed suggesting a limited influence of sorption thermodynamics on metal affinity for seaweed. The investigation of zeolite-seaweed mixtures indicated that mixing sorbents have an effect on the kinetics rates and the sorption affinity. Additionally, the theoretical relationships were derived to predict the boundary layer diffusion rate, intraparticle diffusion rate, the sorption reaction rate and the enthalpy of mixtures based on that of individual sorbents. In general, low coefficient of determination (R2) for the relationships between theoretical and experimental data indicated that the relationships were not statistically significant. This was attributed to the heterogeneity of the properties of sorbents. Nevertheless, in relative terms, the intraparticle diffusion rate, sorption reaction rate and enthalpy of sorption had higher R2 values than the boundary layer diffusion rate suggesting that there was some relationship between the former set of parameters of mixtures and that of sorbents. The mixture, which contained 80% of zeolite and 20% of seaweed, showed similar affinity for the sorption of Cu, Ni, Cd, Cr and Al, which was attributed to approximately similar sorption enthalpy of the metal ions. Therefore, it was concluded that the seaweed-zeolite mixture can be used to obtain the same affinity for various metals present in a multi metal system provided the metal ions have similar enthalpy during sorption by the mixture.

CO2 emissions from the combustion of native Australian trees

Carbon dioxide (CO2), as a primary product of combustion, is a known factor affecting climate change and global warming. In Australia, CO2 emissions from biomass burning are a significant contributor to total carbon in the atmosphere and therefore, it is important to quantify the CO2 emission factors from biomass burning in order to estimate their magnitude and impact on the Australian atmosphere. This paper presents the quantification of CO2 emission factors for five common tree species found in South East Queensland forests, as well as several grasses taken from savannah lands in the Northern Territory of Australia, under controlled ‘fast burning’ and ‘slow burning’ laboratory conditions. The results showed that CO2 emission factors varied according to the type of vegetation and burning conditions, with emission factors for fast burning being 2574 ± 254 g/kg for wood, 394 ± 40 g/kg for branches and leaves, and 2181 ± 120 g/kg for grass. Under slow burning conditions, the CO2 emission factors were 218 ± 20 g/kg for wood, 392± 80 g/kg for branches and leaves, and 2027 ± 809 g/kg for grass.

Vestibular rehabilitation following the removal of an acoustic neuroma : a systematic review of randomized trials

An acoustic neuroma (also known as a vestibular schwannoma) is an intracranial tumour of the vestibular nerve that is commonly treated by surgical resection. Following resection of an acoustic neuroma, patients may experience a range of symptoms that include deficits in gaze stability, mobility and balance. Vestibular rehabilitation may be useful in reducing the severity and minimizing the impact of these symptoms.

Nutrient removal from wastewaters using high performance materials

Return side streams from anaerobic digesters and dewatering facilities at wastewater treatment plants (WWTPs) contribute a significant proportion of the total nitrogen load on a mainstream process. Similarly, significant phosphate loads are also recirculated in biological nutrient removal (BNR) wastewater treatment plants. Ion exchange using a new material, known by the name MesoLite, shows strong potential for the removal of ammonia from these side streams and an opportunity to concurrently reduce phosphate levels. A pilot plant was designed and operated for several months on an ammonia rich centrate from a dewatering centrifuge at the Oxley Creek WWTP, Brisbane, Australia. The system operated with a detention time in the order of one hour and was operated for between 12 and 24 hours prior to regeneration with a sodium rich solution. The same pilot plant was used to demonstrate removal of phosphate from an abattoir wastewater stream at similar flow rates. Using MesoLite materials, >90% reduction of ammonia was achieved in the centrate side stream. A full-scale process would reduce the total nitrogen load at the Oxley Creek WWTP by at least 18%. This reduction in nitrogen load consequently improves the TKN/COD ratio of the influent and enhances the nitrogen removal performance of the biological nutrient removal process.

Removal of epoxy-attached thin-sections from glass slides by plasma-etching

Thin-sectioned samples mounted on glass slides with common petrographic epoxies cannot be easily removed (for subsequent ion-milling) by standard methods such as heating or dissolution in solvents. A method for the removal of such samples using a radio frequency (RF) generated oxygen plasma has been investigated for a number of typical petrographic and ceramic thin sections. Sample integrity and thickness were critical factors that determined the etching rate of adhesive and the survivability of the sample. Several tests were performed on a variety of materials in order to estimate possible heating or oxidation damage from the plasma. Temperatures in the plasma chamber remained below 138°C and weight changes in mineral powders etched for 76 hr were less than ±4%. A crystal of optical grade calcite showed no apparent surface damage after 48 hr of etching. Any damage from the oxygen plasma is apparently confined to the surface of the sample, and is removed during the ion-milling stage of transmission electron microscopy (TEM) sample preparation.

Soil N2O and CO2 emissions from cotton in Australia under varying irrigation management

Irrigation is known to stimulate soil microbial carbon and nitrogen turnover and potentially the emissions of nitrous oxide (N2O) and carbon dioxide (CO2). We conducted a study to evaluate the effect of three different irrigation intensities on soil N2O and CO2 fluxes and to determine if irrigation management can be used to mitigate N2O emissions from irrigated cotton on black vertisols in South-Eastern Queensland, Australia. Fluxes were measured over the entire 2009/2010 cotton growing season with a fully automated chamber system that measured emissions on a sub-daily basis. Irrigation intensity had a significant effect on CO2 emission. More frequent irrigation stimulated soil respiration and seasonal CO2 fluxes ranged from 2.7 to 4.1 Mg-C ha−1 for the treatments with the lowest and highest irrigation frequency, respectively. N2O emission happened episodic with highest emissions when heavy rainfall or irrigation coincided with elevated soil mineral N levels and seasonal emissions ranged from 0.80 to 1.07 kg N2O-N ha−1 for the different treatments. Emission factors (EF = proportion of N fertilizer emitted as N2O) over the cotton cropping season, uncorrected for background emissions, ranged from 0.40 to 0.53 % of total N applied for the different treatments. There was no significant effect of the different irrigation treatments on soil N2O fluxes because highest emission happened in all treatments following heavy rainfall caused by a series of summer thunderstorms which overrode the effect of the irrigation treatment. However, higher irrigation intensity increased the cotton yield and therefore reduced the N2O intensity (N2O emission per lint yield) of this cropping system. Our data suggest that there is only limited scope to reduce absolute N2O emissions by different irrigation intensities in irrigated cotton systems with summer dominated rainfall. However, the significant impact of the irrigation treatments on the N2O intensity clearly shows that irrigation can easily be used to optimize the N2O intensity of such a system.

In situ SANS study of the surface and pore filling adsorption of subcritical and supercritical CO2 in porous silica as a function of pore size

We applied small-angle neutron scattering (SANS) and ultra small-angle neutron scattering (USANS) to monitor evolution of the CO2 adsorption in porous silica as a function of CO2 pressure and temperature in pores of different sizes. The range of pressures (0 < P < 345 bar) and temperatures (T=18 OC, 35 OC and 60 OC) corresponded to subcritical, near critical and supercritical conditions of bulk fluid. We observed that the adsorption behavior of CO2 is fundamentally different in large and small pores with the sizes D > 100 Å and D < 30 Å, respectively. Scattering data from large pores indicate formation of a dense adsorbed film of CO2 on pore walls with the liquid-like density (ρCO2)ads≈0.8 g/cm3. The adsorbed film coexists with unadsorbed fluid in the inner pore volume. The density of unadsorbed fluid in large pores is temperature and pressure dependent: it is initially lower than (ρCO2)ads and gradually approaches it with pressure. In small pores compressed CO2 gas completely fills the pore volume. At the lowest pressures of the order of 10 bar and T=18 OC, the fluid density in smallest pores available in the matrix with D ~ 10 Å exceeds bulk fluid density by a factor of ~ 8. As pressure increases, progressively larger pores become filled with the condensed CO2. Fluid densification is only observed in pores with sizes less than ~ 25 – 30 Å. As the density of the invading fluid reaches (ρCO2)bulk~ 0.8 g/cm3, pores of all sizes become uniformly filled with CO2 and the confinement effects disappear. At higher densities the fluid in small pores appears to follow the equation of state of bulk CO2 although there is an indication that the fluid density in the inner volume of large pores may exceed the density of the adsorbed layer. The equivalent internal pressure (Pint) in the smallest pores exceeds the external pressure (Pext) by a factor of ~ 5 for both sub- and supercritical CO2. Pint gradually approaches Pext as D → 25 – 30 Å and is independent of temperature in the studied range of 18 OC ≤ T ≤ 60 OC. The obtained results demonstrate certain similarity as well as differences between adsorption of subcritical and supercritical CO2 in disordered porous silica. High pressure small angle scattering experiments open new opportunities for in situ studies of the fluid adsorption in porous media of interest to CO2 sequestration, energy storage, and heterogeneous catalysis.

Magnetic zeolite NaA : Synthesis, characterization based on metakaolin and its application for the removal of Cu2+, Pb2+

The optimum parameters for synthesis of zeolite NaA based on metakaolin were investigated according to results of cation exchange capacity and static water adsorption of all synthesis products and selected X-ray diffraction (XRD). Magnetic zeolite NaA was synthesized by adding Fe3O4 in the precursor of zeolite. Zeolite NaA and magnetic zeolite NaA were characterized with scanning electron microscopy (SEM) and XRD. Magnetic zeolite NaA with different Fe3O4 loadings was prepared and used for removal of heavy metals (Cu2+, Pb2+). The results show the optimum parameters for synthesis zeolite NaA are SiO2/Al2O3 = 2.3, Na2O/SiO2 = 1.4, H2O/Na2O = 50, crystallization time 8 h, crystallization temperature 95 �C. The addition of Fe3O4 makes the NaA zeolite with good magnetic susceptibility and good magnetic stability regardless of the Fe3O4 loading, confirming the considerable separation efficiency. Additionally, Fe3O4 loading had a little effect on removal of heavy metal by magnetic zeolite, however, the adsorption capacity still reaches 2.3 mmol g�1 for Cu2+, Pb2+ with a removal efficiency of over 95% in spite of 4.7% Fe3O4 loading. This indicates magnetic zeolite can be used to remove metal heavy at least Cu2+, Pb2+ from water with metallic contaminants and can be separated easily after a magnetic process.

Effect of Fe3O4 addition on removal of ammonium by zeolite NaA

Magnetic zeolite NaA with different Fe3O4 loadings was prepared by hydrothermal synthesis based on metakaolin and Fe3O4. The effect of added Fe3O4 on the removal of ammonium by zeolite NaA was investigated by varying the Fe3O4 loading, pH, adsorption temperature, initial concentration, adsorption time. Langmuir, Freundlich, and pseudo-second-order modeling were used to describe the nature and mechanism of ammonium ion exchange using both zeolite and magnetic zeolite. Thermodynamic parameters such as change in Gibbs free energy, enthalpy and entropy were calculated. The results show that all the selected factors affect the ammonium ion exchange by zeolite and magnetic zeolite, however, the added Fe3O4 apparently does not affect the ion exchange performance of zeolite to the ammonium ion. Freundlich model provides a better description of the adsorption process than Langmuir model. Moreover, kinetic analysis indicates the exchange of ammonium on the two materials follows a pseudosecond-order model. Thermodynamic analysis makes it clear that the adsorption process of ammonium is spontaneous and exothermic. Regardless of kinetic or thermodynamic analysis, all the results suggest that no considerable effect on the adsorption of the ammonium ion by zeolite is found after the addition of Fe3O4. According to the results, magnetic zeolite NaA can be used for the removal of ammonium due to the good adsorption performance and easy separation method from aqueous solution.

Structural characterisation and environmental application of organoclays for the removal of phenolic compounds

Modified montmorillonite was prepared at different surfactant (HDTMA) loadings through ion exchange. The conformational arrangement of the loaded surfactants within the interlayer space of MMT was obtained by computational modelling. The conformational change of surfactant molecules enhance the visual understanding of the results obtained from characterization methods such as XRD and surface analysis of the organoclays. Batch experiments were carried out for the adsorption of p-chlorophenol (PCP) and different conditions (pH and temperature) were used in order to determine the optimum sorption. For comparison purpose, the experiments were repeated under the same conditions for p-nitrophenol (PNP). Langmuir and Freundlich equations were applied to the adsorption isotherm of PCP and PNP. The Freundlich isotherm model was found to be the best fit for both of the phenolic compounds. This involved multilayer adsorptions in the adsorption process. In particular, the binding affinity value of PNP was higher than that of PCP and this is attributable to their hydrophobicities. The adsorption of the phenolic compounds by organoclays intercalated with highly loaded surfactants was markedly improved possibly due to the fact that the intercalated surfactant molecules within the interlayer space contribute to the partition phases, which result in greater adsorption of the organic pollutants.