Rapid nutrient determination of sugarcane milling by-products using near infrared spectroscopy

This thesis investigates the use of near infrared (NIR) spectroscopic methods for rapid measurement of nutrient elements in mill mud and mill ash. Adoption of NIR-based analyses for carbon, nitrogen, phosphorus, potassium and silicon will allow Australian sugarcane farmers to comply with recent legislative changes, and act within recommended precision farming frameworks. For these analyses, NIR spectroscopic methods surpass several facets of traditional wet chemistry techniques, dramatically reducing costs, required expertise and chemical exposure, while increasing throughput and access to data. Further, this technology can be applied in various modes, including laboratory, at-line and on-line installations, allowing targeted measurement.

Experimental study of Australian sugarcane bagasse pulp permeability

In this experimental study the permeability of Australian bagasse chemical pulps obtained from different bagasse fractions were measured in a simple permeability cell and the results compared to one another as well as to eucalypt, Argentinean bagasse and pine pulps. The pulps were characterised in terms of the permeability parameters, the specific surface area, Sv, and the swelling factor, α. It was found that the bagasse fraction used affects these parameters. Fractionation of whole bagasse prior to pulping produced pulps that have permeability properties that compare favourably with eucalypt pulp. The values of Sv and α for bagasse pulp also depend on whether a constant or a variable Kozeny factor is used.

Phylogenetic placement of the sugarcane orange rust pathogen Puccinia kuehnii in a historical and regional context

Sugarcane orange rust, caused by Puccinia kuehnii, was once considered a minor disease in the Australian sugar industry. However, in 2000 a new race of the pathogen devastated the high-performing sugarcane cultivar Q124, and caused the industry Aus$150–210 million in yield losses. At the time of the epidemic, very little was known about the genetic and pathogenic diversity of the fungus in Australia and neighbouring sugar industries. DNA sequence data from three rDNA regions were used to determine the genetic relationships between isolates within two P. kuehnii collections. The first collection comprised only recent Australian field isolates and limited sequence variation was detected within this population. In the second study, Australian isolates were compared with isolates from Papua New Guinea, Indonesia, China and historical herbarium collections. Greater sequence variation was detected in this collection and phylogenetic analyses grouped the isolates into three clades. All isolates from commercial cane fields clustered together including the recent Australianfield isolates and the Australian historical isolate from 1898.The other two clades included rust isolates from wild and garden canes in Indonesia and PNG. These rusts appeared morphologically similar to P. kuehnii and could potentially pose a quarantine threat to the Australian sugar industry. The results have revealed greater diversity in sugarcane rusts than previously thought.

An ecological assessment of secondary poisoning risk in the Australian sugarcane industry

Rodenticide use in agriculture can lead to the secondary poisoning of avian predators. Currently the Australian sugarcane industry has two rodenticides, Racumin® and Rattoff®, available for in-crop use but, like many agricultural industries, it lacks an ecologically-based method of determining the potential secondary poisoning risk the use of these rodenticides poses to avian predators. The material presented in this thesis addresses this by: a. determining where predator/prey interactions take place in sugar producing districts; b. quantifying the amount of rodenticide available to avian predators and the probability of encounter; and c. developing a stochastic model that allows secondary poisoning risk under various rodenticide application scenarios to be investigated. Results demonstrate that predator/prey interactions are highly constrained by environmental structure. Rodents used crops that provided high levels of canopy cover and therefore predator protection and poorly utilised open canopy areas. In contrast, raptors over-utilised areas with low canopy cover and low rodent densities, but which provided high accessibility to prey. Given this pattern of habitat use, and that industry baiting protocols preclude rodenticide application in open canopy crops, these results indicate that secondary poisoning can only occur if poisoned rodents leave closed canopy crops and become available for predation in open canopy areas. Results further demonstrate that after in-crop rodenticide application, only a small proportion of rodents available in open areas are poisoned and that these rodents carry low levels of toxicant. Coupled with the low level of rodenticide use in the sugar industry, the high toxic threshold raptors have to these toxicants and the low probability of encountering poisoned rodents, results indicate that the risk of secondary poisoning events occurring is minimal. A stochastic model was developed to investigate the effect of manipulating factors that might influence secondary poisoning hazard in a sugarcane agro-ecosystem. These simulations further suggest that in all but extreme scenarios, the risk of secondary poisoning is also minimal. Collectively, these studies demonstrate that secondary poisoning of avian predators associated with the use of the currently available rodenticides in Australian sugar producing districts is minimal. Further, the ecologically-based method of assessing secondary poisoning risk developed in this thesis has broader applications in other agricultural systems where rodenticide use may pose risks to avian predators.

Thermoanalytical studies of natural potassium, sodium and ammonium alunites

Dynamic and controlled rate thermal analysis (CRTA) has been used to characterise alunites of formula [M(Al)3(SO4)2(OH)6 ] where M+ is the cations K+, Na+ or NH4+. Thermal decomposition occurs in a series of steps. (a) dehydration, (b) well defined dehydroxylation and (c) desulphation. CRTA offers a better resolution and a more detailed interpretation of water formation processes via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of water formation reveal the subtle nature of dehydration and dehydroxylation.

Delamination of kaolinite - potassium acetate intercalates by ball-milling

Structural changes in intercalated kaolinite after wet ball-milling were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), specific surface area (SSA) and Fourier Transform Infrared spectroscopy (FTIR). The X-ray diffraction pattern at room temperature indicated that the intercalation of potassium acetate into kaolinite causes an increase of the basal spacing from 0.718 to 1.42 nm, and with the particle size reduction, the surface area increased sharply with the intercalation and delamination by ball-milling. The wet ball-milling kaolinite after intercalation did not change the structural order, and the particulates have high aspect ratio according SEM images.

Some aspects of calcium phosphate chemistry in sugarcane clarification

This paper reviews some aspects of calcium phosphate chemistry since phosphate in juice is an important parameter in all sugar juice clarification systems. It uses basic concepts to try and explain the observed differences in clarification performance obtained with various liming techniques. The paper also examines the current colorimetric method used for the determination of phosphate in sugar juice. In this method, a phosphomolybdate blue complex formed due to the addition of a dye is measured at 660 nm. Unfortunately, at this wavelength there is interference of the colour arising from within the juice and results in the underestimation of the amount of soluble inorganic phosphate content of juice. It is suggested that phosphate analysis be conducted at the higher wavelength of 875 nm where the interference of the juice colour is minimised.

Thermal analysis and infrared emission spectroscopic study of halloysite-potassium acetate intercalation compound

The thermal decomposition of halloysite-potassium acetate intercalation compound was investigated by thermogravimetric analysis and infrared emission spectroscopy. The X-ray diffraction patterns indicated that intercalation of potassium acetate into halloysite caused an increase of the basal spacing from 1.00 to 1.41 nm. The thermogravimetry results show that the mass losses of intercalation the compound occur in main three main steps, which correspond to (a) the loss of adsorbed water (b) the loss of coordination water and (c) the loss of potassium acetate and dehydroxylation. The temperature of dehydroxylation and dehydration of halloysite is decreased about 100 °C. The infrared emission spectra clearly show the decomposition and dehydroxylation of the halloysite intercalation compound when the temperature is raised. The dehydration of the intercalation compound is followed by the loss of intensity of the stretching vibration bands at region 3600-3200 cm-1. Dehydroxylation is followed by the decrease in intensity in the bands between 3695 and 3620 cm-1. Dehydration was completed by 300 °C and partial dehydroxylation by 350 °C. The inner hydroxyl group remained until around 500 °C.

Influencing factors on kaolinite-potassium acetate intercalation complexes

This paper presents an immersion method for preparing the kaolinite-potassium acetate intercalation complexes. The effectiveness of intercalation and influencing factors were analysed and evaluated. The results show that the intercalation of kaolinite by potassium acetate is strongly related to crystallinity of kaolinite, concentration of intercalating agent solution, aging time and pH. The well-crystallized kaolinite is conducive to intercalation by potassium acetate. A higher concentration of intercalating agent (≥30%) can complete the intercalation in a short time (<12h), but at lower concentrations intercalation took significantly longer (≥144h). The weak alkaline condition of pH=10 proved to be the most suitable environment for the formation of intercalation complex. A good intercalated complex can be obtained at room temperature.

Enhancing agrobacterium-mediated transformation efficiency of sugarcane : progress towards an efficient, genotype-independent method

Several key issues need to be resolved before an efficient and reproducible Agrobacterium-mediated sugarcane transformation method can be developed for a wider range of sugarcane cultivars. These include loss of morphogenetic potential in sugarcane cells after Agrobacterium-mediated transformation, effect of exposure to abiotic stresses during in vitro selection, and most importantly the hypersensitive cell death response of sugarcane (and other nonhost plants) to Agrobacterium tumefaciens. Eight sugarcane cultivars (Q117, Q151, Q177, Q200, Q208, KQ228, QS94-2329, and QS94-2174) were evaluated for loss of morphogenetic potential in response to the age of the culture, exposure to Agrobacterium strains, and exposure to abiotic stresses during selection. Corresponding changes in the polyamine profiles of these cultures were also assessed. Strategies were then designed to minimize the negative effects of these factors on the cell survival and callus proliferation following Agrobacterium-mediated transformation. Some of these strategies, including the use of cell death protector genes and regulation of intracellular polyamine levels, will be discussed.

Thermal analysis and infrared emission spectroscopic study of kaolinite-potassium acetate intercalate complex

The thermal behavior and decomposition of kaolinite-potassium acetate intercalation complex was investigated through a combination of thermogravimetric analysis and infrared emission spectroscopy. Three main changes were observed at 48, 280, 323 and 460 °C which were attributed to (a) the loss of adsorbed water (b) loss of the water coordinated to acetate ion in the layer of kaolinite (c) loss of potassium acetate in the complex and (d) water through dehydroxylation. It is proposed that the KAc intercalation complex is stability except heating at above 300 °C. The infrared emission spectra clearly show the decomposition and dehydroxylation of the kaolinite intercalation complex when the temperature is raised. The dehydration of the intercalation complex is followed by the loss of intensity of the stretching vibration bands at region 3600-3200 cm-1. Dehydroxylation is followed by the decrease in intensity in the bands between 3695 and 3620 cm-1. Dehydration is completed by 400 °C and partial dehydroxylation by 650 °C. The inner hydroxyl group remained until around 700 °C.

Infrared spectroscopic study of halloysite-potassium acetate intercalation complex

Mid-infrared (MIR) and near-infrared (NIR) spectroscopy have been used to study the molecular structure of halloysite and potassium acetate intercalated halloysite and to determine the structural changes of halloysite through intercalation. The MIR spectra show all fundamental vibrations including the hydroxyl units, basic aluminosilicate framework and water molecules in the structure of halloysite and its intercalation complex. Comparison between halloysite and halloysite-potassium acetate intercalation complex shows almost all bands observed for halloysite are also observed for halloysite-potassium acetate intercalation complex apart from bands observed in the 1700-1300 cm-1 region, but with differences in band intensity. However, NIR, based on MIR spectra, provide sufficient evidence to analyze the structural changes of halloysite through intercalation. There are obvious differences between halloysite and halloysite-potassium acetate intercalation complex in the all spectral ranges. Therefore, the reproducibility of measurement and richness of qualitative information should be simultaneously considered for proper selection of a spectroscopic method for molecular structural analysis.

Thermal behavior and decomposition of kaolinite-potassium acetate intercalation composite

A series of kaolinite-potassium acetate intercalation composite was prepared. The thermal behavior and decomposition of these composites were investigated by simultaneous differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), X-ray diffraction (XRD) and Fourier-transformation infrared (FT-IR). The XRD pattern at room temperature indicated that intercalation of potassium acetate into kaolinite causes an increase of the basal spacing from 0.718 to 1.428nm. The peak intensity of the expanded phase of the composite decreased with heating above 300°C, and the basal spacing reduced to 1.19nm at 350°C and 0.718nm at 400°C. These were supported by DSC-TGA and FT-IR measurements, where the endothermic reactions are observed between 300 and 600°C. These reactions can be divided into two stages: 1) Removal of the intercalated molecules between 300-400°C. 2) Dehydroxylation of kaolinite between 400-600°C. Significant changes were observed in the infrared bands assigned to outer surface hydroxyl, inner surface hydroxyl, inner hydroxyl and hydrogen bands.