957 resultados para water-soluble P


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The monoaromatic compounds are toxic substances present in petroleum derivades and used broadly in the chemical and petrochemical industries. Those compounds are continuously released into the environment, contaminating the soil and water sources, leading to the possible unfeasibility of those hydrous resources due to their highly carcinogenic and mutagenic potentiality, since even in low concentrations, the BTEX may cause serious health issues. Therefore, it is extremely important to develop and search for new methodologies that assist and enable the treatment of BTEX-contaminated matrix. The bioremediation consists on the utilization of microbial groups capable of degrading hydrocarbons, promoting mineralization, or in other words, the permanent destruction of residues, eliminating the risks of future contaminations. This work investigated the biodegradation kinetics of water-soluble monoaromatic compounds (benzene, toluene and ethylbenzene), based on the evaluation of its consummation by the Pseudomonas aeruginosa bacteria, for concentrations varying from 40 to 200 mg/L. To do so, the performances of Monod kinetic model for microbial growth were evaluated and the material balance equations for a batch operation were discretized and numerically solved by the fourth order Runge-Kutta method. The kinetic parameters obtained using the method of least squares as statistical criteria were coherent when compared to those obtained from the literature. They also showed that, the microorganism has greater affinity for ethylbenzene. That way, it was possible to observe that Monod model can predict the experimental data for the individual biodegradation of the BTEX substrates and it can be applied to the optimization of the biodegradation processes of toxic compounds for different types of bioreactors and for different operational conditions.

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This thesis presents the synthesis, characterization and study of the associative behaviour in aqueous media of new responsive graft copolymers, based on carboxymethylcellulose as the water-soluble backbone and Jeffamine® M-2070 e Jeffamine® M-600 (commercial polyetheramines) as the thermoresponsive grafts with high cloud point temperatures in water. The synthesis was performed on aqueous medium, by using 1-ethyl-3- (3-(dimethylamino)-propyl)carbodiimide hydrochloride and N-hydroxysuccinimide as activators of the reaction between carboxylategroupsfrom carboxymethylcellulose and amino groups from polyetheramines. The grafting reaction was confirmed by infrared spectroscopy and the grafting percentage by 1H NMR. The molar mass of the polyetheramines was determined by 1H NMR, whereas the molar mass of CMC and graft copolymers was determined by static light scattering. The salt effect on the association behaviour of the copolymers was evaluated in different aqueous media (Milli-Q water, 0.5M NaCl, 0.5M K2CO3 and synthetic sea water), at different temperatures, through UV-vis, rheology and dynamic light scattering. None of the copolymers solutions, at 5 g/L, turned turbid in Milli-Q water when heated from 25 to 95 °C, probably because of the increase in hydrophibicity promoted by CMC backbone. However, they became turbid in the presence of salts, due to the salting out effect, where the lowest cloud point was observed in 0.5M K2CO3, which was attributed to the highest ionic strength in water, combined to the ability of CO3 2- to decrease polymer-solvents interactions. The hydrodynamic radius and apparent viscosity of the copolymers in aqueous medium changed as a function of salts dissolved in the medium, temperature and copolymer composition. Thermothickening behaviour was observed in 0.5M K2CO3 when the temperature was raised from 25 to 60°C. This performance can be attributed to intermolecular associations as a physical network, since the temperature is above the cloud point of the copolymers in this solvent.

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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.

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The effects of eutrophication on short term changes in the microbial community were investigated using high resolution lipid biomarker and trace metal data for sediments from the eutrophic Lake Rotsee (Switzerland). The lake has been strongly influenced by sewage input since the 1850s and is an ideal site for studying an anthropogenically altered ecosystem. Historical remediation measures have had direct implications for productivity and microbial biota, leading to community composition changes and abundance shifts. The higher sewage and nutrient input resulted in a productivity increase, which led predominantly to a radiation in diatoms, primary producers and methanogens between about 1918 and 1921, but also affected all microorganism groups and macrophytes between about 1958 and 1972. Bacterial biomass increased in 1933, which may have been related to the construction of a mechanical sewage treatment plant. Biomarkers also allowed tracing of fossil organic matter/biodegraded oil contamination in the lake. Stephanodiscus parvus, Cyclotella radiosa and Asterionella formosa were the dominant sources of specific diatom biomarkers. Since the 1850s, the cell density of methanogenic Archaea (Methanosaeta spp.) ranged within ca. 0.5-1.8 x 10**9 cells/g dry sediment and the average lipid content of Rotsee Archaea was ca. 2.2 fg iGDGTs/cell. An altered BIT index (BITCH), indicating changes in terrestrial organic matter supply to the lake, is proposed.

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Assessing the soil nutrient availability to plants under lab conditions is one of the main challenges to Soil Fertility and Chemistry, due to the complex behavior and the interaction of the soil properties. Many extractant solutions associated with mechanical forms of agitation have been proposed, showing different correlations with plant growth and nutrients absorption. Using ultrasonic energy is a agitation procedure of the soil:extractant solution suspension (based on the cavitation phenomenon). It allows the establishment of relations between the amount of extracted nutrient and the ultrasonic energy level. Thus, this work aims: to evaluate the effect of cavitation intensity on the extraction of P, Zn, Cu, Mn and Fe in soil samples from five Latosols under different uses around Uberlândia and Uberaba, Minas Gerais State; to obtain extracting curves as function of ultrasonic energy levels; and to obtain an index from extracting curves to expresses the nutrient retention by the soil solid phase. A soil-solution suspension (ratio 1:10) was sonicated using a probe ultrasound equipment under different combinations of power and time: i) 30 W for 35, 70, 140 and 280 s; ii) 50 W for 21, 42, 84 and 168 s; and iii) 70 W for 15, 30, 60 and 120 s. The extractant solutions used were Mehlich-1 (for all elements), Olsen and distilled water for P. After each sonication, P concentration was quantified by molybdenum blue colorimetric method and Zn, Cu, Mn and Fe by flame atomic absorption spectrophotometry. The cavitation intensity did not affect the P extraction, only the total energy applied. The P extraction was influenced by extractant solution, decreasing as follows: Mehlich-1>Olsen>water. In cultivated Latosols, the P extraction increased linearly with ultrasonic energy, and the slope of the 1:1 linear regression reflects the P retention in the soil. The Zn and Fe extractions were influenced only by total energy applied. Mn and Cu extractions were influenced by both cavitation intensity and total ultrasonic energy. Soils containing similar amounts of P, Cu, Zn, Mn, and Fe may have a different extraction rate. Likewise, soils containing different amounts of those elements may have the same extraction rate.

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This paper explored a new approach to prepare phase change microcapsules using carbon-based particles via Pickering emulsions for energy storage applications. Rice-husk-char, a by-product in biofuel production, containing 53.58 wt% of carbon was used as a model carbon-based material to encapsulate hexadecane. As a model phase change material, hexadecane was emulsified in aqueous suspensions of rice-husk-char nanoparticles. Water soluble polymers poly(diallyldimethyl-ammonium chloride) and poly(sodium styrene sulfonate) were used to fix the rice-husk-char nanoparticles on the emulsion droplets through layer-by-layer assembly to enhance the structural stability of the microcapsules. The microcapsules formed are composed of a thin shell encompassing a large core consisting of hexadecane. Thermal gravimetrical and differential scanning calorimeter analyses showed the phase change enthalpy of 80.9 kJ kg−1 or 120.0 MJ m−3. Design criteria of phase change microcapsules and preparation considerations were discussed in terms of desired applications. This work demonstrated possible utilisations of biomass-originated carbon-based material for thermal energy recovery and storage applications, which can be a new route of carbon capture and utilisation.

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Central nervous system (CNS) drug delivery is often hampered due to the insidious nature of the blood-brain barrier (BBB). Nose-to-brain delivery via olfactory pathways have become a target of attention for drug delivery due to bypassing of the BBB. The antioxidant properties of phytochemicals make them promising as CNS active agents but possess poor water solubility and limited BBB penetration. The primary aim of this study was the development of mesoporous silica nanoparticles (MSNs) loaded with the poorly water-soluble phytochemicals curcumin and chrysin which could be utilised for nose-to-brain delivery. We formulated spherical MSNP using a templating approach resulting in ∼220nm particles with a high surface porosity. Curcumin and chrysin were successfully loaded into MSNP and confirmed through Fourier transformation infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and HPLC approaches with a loading of 11-14% for curcumin and chrysin. Release was pH dependant with curcumin demonstrating increased chemical stability at a lower pH (5.5) with a release of 53.2%±2.2% over 24h and 9.4±0.6% for chrysin. MSNP were demonstrated to be non-toxic to olfactory neuroblastoma cells OBGF400, with chrysin (100μM) demonstrating a decrease in cell viability to 58.2±8.5% and curcumin an IC50 of 33±0.18μM. Furthermore confocal microscopy demonstrated nanoparticles of <500nm were able to accumulate within cells with FITC-loaded MSNP showing membrane localised and cytoplasmic accumulation following a 2h incubation. MSNP are useful carriers for poorly soluble phytochemicals and provide a novel vehicle to target and deliver drugs into the CNS and bypass the BBB through olfactory drug delivery.

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As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June, 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the N. E. Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm(-3), while background marine air aerosol concentrations were between 400-600 cm(-3). The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm(-3), was observed and attributed to open ocean particle formation. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40-50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water soluble organic carbon, which, in turn, was dominated by methanesulphonic acid (MSA). Sulphate concentrations were highest in marine tropical air - even higher than in continental air. MSA was present at twice the concentrations of previously-reported concentrations at the same location and the same season. Both continental and marine air exhibited aerosol GFs significantly less than ammonium sulphate aerosol pointing to a significant organic contribution to all air mass aerosol properties.

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<p>Species invasions are more prevalent than ever before. While the addition of a species can dramatically change critical ecosystem processes, factors that mediate the direction and magnitude of those impacts have received less attention. A better understanding of the factors that mediate invasion impacts on ecosystem functioning is needed in order to target which exotic species will be most harmful and which systems are most vulnerable. The role of invasion on nitrogen (N) cycling is particularly important since N cycling controls ecosystem services that provision human health, e.g. nutrient retention and water quality.p><p>We conducted a meta-analysis and in-depth studies focused on the invasive grass species, Microstegium vimineum, to better understand how (i) plant characteristics, (ii) invader abundance and neighbor identity, and (iii) environmental conditions mediate the impacts of invasion on N pools and fluxes. The results of our global meta-analysis support the concept that invasive species and reference community traits such as leaf %N and leaf C:N are useful for understanding invasion impacts on soil N cycling, but that trait dissimilarities between invaded and reference communities are most informative. Regarding the in-depth studies of Microstegium, we did not find evidence to suggest that invasion increases net nitrification as other studies have shown. Instead, we found that an interaction between its abundance and the neighboring plant identify were important for determining soil nitrate concentrations and net nitrification rates in the greenhouse. In field, we found that variability in environmental conditions mediated the impact of Microstegium invasion on soil N pools and fluxes, primarily net ammonification, between sites through direct, indirect, and interactive pathways. Notably, we detected a scenario in which forest openness has a negative direct effect and indirect positive effect on ammonification in sites with high soil moisture and organic matter. Collectively, our findings suggest that dissimilarity in plant community traits, neighbor identity, and environmental conditions can be important drivers of invasion impacts on ecosystem N cycling and should be considered when evaluating the ecosystem impacts of invasive species across heterogeneous landscapes.p>

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<p>Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.p><p>The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment. p><p>In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.p><p>I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters. p><p>Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.p>

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Germanium was of great interest in the 1950’s when it was used for the first transistor device. However, due to the water soluble and unstable oxide it was surpassed by silicon. Today, as device dimensions are shrinking the silicon oxide is no longer suitable due to gate leakage and other low-κ dielectrics such as Al2O3 and HfO2 are being used. Germanium (Ge) is a promising material to replace or integrate with silicon (Si) to continue the trend of Moore’s law. Germanium has better intrinsic mobilities than silicon and is also silicon fab compatible so it would be an ideal material choice to integrate into silicon-based technologies. The progression towards nanoelectronics requires a lot of in depth studies. Dynamic TEM studies allow observations of reactions to allow a better understanding of mechanisms and how an external stimulus may affect a material/structure. This thesis details in situ TEM experiments to investigate some essential processes for germanium nanowire (NW) integration into nanoelectronic devices; i.e. doping and Ohmic contact formation. Chapter 1 reviews recent advances in dynamic TEM studies on semiconductor (namely silicon and germanium) nanostructures. The areas included are nanowire/crystal growth, germanide/silicide formation, irradiation, electrical biasing, batteries and strain. Chapter 2 details the study of ion irradiation and the damage incurred in germanium nanowires. An experimental set-up is described to allow for concurrent observation in the TEM of a nanowire following sequential ion implantation steps. Grown nanowires were deposited on a FIB labelled SiN membrane grid which facilitated HRTEM imaging and facile navigation to a specific nanowire. Cross sections of irradiated nanowires were also performed to evaluate the damage across the nanowire diameter. Experiments were conducted at 30 kV and 5 kV ion energies to study the effect of beam energy on nanowires of varied diameters. The results on nanowires were also compared to the damage profile in bulk germanium with both 30 kV and 5 kV ion beam energies. Chapter 3 extends the work from chapter 2 whereby nanowires are annealed post ion irradiation. In situ thermal annealing experiments were conducted to observe the recrystallization of the nanowires. A method to promote solid phase epitaxial growth is investigated by irradiating only small areas of a nanowire to maintain a seed from which the epitaxial growth can initiate. It was also found that strain in the nanowire greatly effects defect formation and random nucleation and growth. To obtain full recovery of the crystal structure of a nanowire, a stable support which reduces strain in the nanowire is essential as well as containing a seed from which solid phase epitaxial growth can initiate. Chapter 4 details the study of nickel germanide formation in germanium nanostructures. Rows of EBL (electron beam lithography) defined Ni-capped germanium nanopillars were extracted in FIB cross sections and annealed in situ to observe the germanide formation. Chapter 5 summarizes the key conclusions of each chapter and discusses an outlook on the future of germanium nanowire studies to facilitate their future incorporation into nanodevices.

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This paper explored a new approach to prepare phase change microcapsules using carbon-based particles via Pickering emulsions for energy storage applications. Rice-husk-char, a by-product in biofuel production, containing 53.58 wt% of carbon was used as a model carbon-based material to encapsulate hexadecane. As a model phase change material, hexadecane was emulsified in aqueous suspensions of rice-husk-char nanoparticles. Water soluble polymers poly(diallyldimethyl-ammonium chloride) and poly(sodium styrene sulfonate) were used to fix the rice-husk-char nanoparticles on the emulsion droplets through layer-by-layer assembly to enhance the structural stability of the microcapsules. The microcapsules formed are composed of a thin shell encompassing a large core consisting of hexadecane. Thermal gravimetrical and differential scanning calorimeter analyses showed the phase change enthalpy of 80.9 kJ kg−1 or 120.0 MJ m−3. Design criteria of phase change microcapsules and preparation considerations were discussed in terms of desired applications. This work demonstrated possible utilisations of biomass-originated carbon-based material for thermal energy recovery and storage applications, which can be a new route of carbon capture and utilisation.

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El objetivo es proponer un procedimiento y un dispositivo que permitan la extracción de un fertilizante contenido en una envoltura hidrosoluble sin generar residuos provenientes del envase vacío, evitando el contacto con el producto, garantizando la extracción del fertilizante mediante la disolución previa del envoltorio y a una circulación de agua a su través, incorporando un sistema de filtrado final, y facilitando el llenado y limpieza del dispositivo mediante un sistema de apertura y cierre roscado.

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The phenolic ellagic acid (EA) is receiving increasing attention for its nutritional and pharmacological potential as an antioxidant and antimicrobial agent. The Australian native Kakadu plum (Terminalia ferdinandiana) fruit is an abundant source of this phytochemical. The fruit also contains large amounts of vitamin C (mainly as ascorbic acid, AA) and possibly the undesirable oxalic acid (OA). Regular consumption of high oxalate foods poses a variety of health risks in humans including interference with calcium absorption and kidney stone formation. Oxalate is also the end-product of AA metabolism so that consumption of fruit with heightened AA content has the potential to elevate urinary oxalate levels. The aims of this study were to investigate the distribution of EA and the presence of other bioactives in other Kakadu plum tissues. Chemical analysis of Kakadu plum fruit and leaves for EA (free and total), OA (water-soluble and total), calcium (Ca) and AA indicated that EA and AA concentrations were high in the fruit while the leaves had significantly higher EA levels but little or no detectable AA. OA content in fruit and leaves was substantial with the fruit being placed in the high-Oxalate category. These findings suggest that there is potential to elevate oxalate levels in the urine of susceptible people and intake of fruit-derived products should be closely monitored. By measuring tissues collected from specific trees, high EA-producing or low OA-containing individuals were identified.