Nutrient and phytoplankton status of Lakes Purrumbete and Bullen Merri, western Victoria

The thesis investigates two adjacent volcanic maar lakes, with differences in chemical and biological properties. Lake Bullen Merri a brackish, phosphorous-limited lake that suffers from nuisance algal blooms and Lake Purrumbete a fresh, nitrogen-limited lake with diverse phytoplankton assemblage. Nutrient fluxes for both lakes are dominated by internal cycling.

Characterisation and impedance spectroscopy of substituted Li1.3Al0.3Ti1.7(PO4)3−x(ZO4)x (Z=V, Nb) ceramics*1

Lithium ion conducting ceramics based on the lithium aluminium titanium phosphate (LATP) NASICON structure have been prepared with various substitutions of the phosphorous. The effect of the processing method has been shown to be the key factor in determining the conductivity, both bulk and grain boundary, as well as the conductivity trends observed as a function of substitution.

Solid state NMR characterization of polyrrole : the nature of the dopant in PF6− doped films

³¹P and ¹⁹F solid state NMR have been used to study the nature of the PF₆− anion in polypyrrole films at various levels of oxidation. It appears that the symmetric PF₆− unit remains undistorted and unchanged throughout, suggesting that it is predominantly acting only as a counterion and not as a true ‘dopant’, since any distortion in the phosphorous environments would result at the very least in chemical shift anisotropy of the ³¹P nucleus. A second set of phosphorous and fluorine resonances, which are consistent with a difluoride phosphorous compound, appeared in the films. Upon electrochemical reduction of the polymer, the undistorted PF₆− anion leaves the film whereas the second phosphorous species remains. Re-oxidation of the polymer reverses the processes observed during reduction.

NMR studies of modified nasicon-like, lithium conducting solid electrolytes*1

²⁷Al, ³¹P and ⁷Li NMR measurements have been performed on lithium conducting ceramics based on the LiTi₂(PO₄)₃ structure with Al, V and Nb metal ions substituted for either Ti or P within the framework NASICON structure. The ²⁷Al magic angle spinning NMR measurements have revealed that, although Al is intended to substitute for octahedral Ti sites, additional substitution into tetrahedral environments (presumably phosphorous sites) occurs with increasing amount of Al addition. This tetrahedral substitution appears to occur more readily in the presence of vanadium, in Li_1+xAl_xTi_2−x(PO₄)_2.9(VO₄)_0.1, whereas similar niobium additions (in place of vanadium) appear to stifle tetrahedral substitution. ⁷Li static NMR spectra reveal quadrupolar structure with C_q approximately 42 kHz, largely independent of substitution. Measurement of the ⁷Li central transition linewidth at room temperature reveals a relatively mobile lithium species (300–900 Hz) with linewidth tending to decrease with Al substitution and increase with increasing V or Nb. This new structural information is discussed in the context of ionic conduction in these ceramics.

Solid state NMR analysis of polypyrrole grown in a phosphonium ionic liquid

³¹P, ¹⁹F and ¹³C solid state NMR analysis has been used to investigate the intercalation/de-intercalation of both anions and cations in electrochemically synthesized polypyrrole films. Use of a phosphonium-based ionic liquid, tri(hexyl)(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide, allows the separate detection of the cation and anion by analysis of the phosphorous and fluorine resonances, respectively. Initial results indicate the incorporation of both cations and anions during film growth in the ionic liquid. There is a notable change in the ³¹P chemical shift of the cation on incorporation into the film, consistent with a significant change in environment compared to the pure ionic liquid. Despite its large size, the phosphonium cation can be completely expelled from the film by oxidation.

The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys

An electrochemical approach to the formation of a protective surface film on Mg alloys immersed in the ionic liquid (IL), trihexyl(tetradecyl)phosphonium–bis 2,4,4-trimethylpentylphosphinate, was investigated in this work. Initially, cyclic voltammetry was used with the Mg alloy being cycled from OCP to more anodic potentials. EIS data indicate that, under these circumstances, an optimum level of protection was achieved at intermediate potentials (e.g., 0 or 0.25 V versus Ag/AgCl). In the second part of this paper, a small constant bias was applied to the Mg alloy immersed in the IL for extended periods using a novel cell design. This electrochemical cell allowed us to monitor in situ surface film formation on the metal surface as well as the subsequent corrosion behaviour of the metal in a corrosive medium. This apparatus was used to investigate the evolution of the surface film on an AZ31 magnesium alloy under a potential bias (between ±100 mV versus open circuit) applied for over 24 h, and the film evolution was monitored using electrochemical impedance spectroscopy (EIS). A film resistance was determined from the EIS data and it was shown that this increased substantially during the first few hours (independent of the bias potential used) with a subsequent decrease upon longer exposure of the surface to the IL. Preliminary characterization of the film formed on the Mg alloy surface using ToF-SIMS indicates that a multilayer surface exists with a phosphorous rich outer layer and a native oxide/hydroxide film underlying this. The corrosion performance of a treated AZ31 specimen when exposed to 0.1 M NaCl aqueous solution showed considerable improvement, consistent with electrochemical data.

Scores on the dietary guideline index for children and adolescents are associated with nutrient intake and socio-economic position but not adiposity 1-3

Diet quality indices reflect overall dietary patterns better than single nutrients or food groups. The study aims were to develop a measure of adherence with dietary guidelines applicable to child and adolescent populations in Australia and determine the association between index scores and food and nutrient intake, socio-demographic characteristics, and measures of adiposity. Data were analyzed from 4- to 16-y-old participants of the 2007 Australian Children’s Nutrition and Physical Activity Survey (n = 3416). The Dietary Guideline Index for Children and Adolescents (DGI-CA) comprises 11 components: 5 core food groups, wholegrain bread, reduced-fat dairy foods, extra foods (nutrient poor and high in fat, salt, and added sugar), healthy fats/oils, water, and diet variety (possible score of 100). The index criteria were age specific. The mean DGI-CA score was low (53.6 ± 0.4), similar between boys and girls, and differed by age; the youngest children scored higher than the oldest children (P < 0.0001). Higher DGI-CA scores were associated with lower energy intake, energy density, total and saturated fat, and sugar intake; higher protein, carbohydrate, fiber, calcium, iron, vitamin C, vitamin A, folate, phosphorous, magnesium, zinc, and iodine intakes; and a higher polyunsaturated:saturated fat ratio (P < 0.0001). DGI-CA scores were associated with socio-economic characteristics and measures of family circumstance. Weak positive associations were observed between DGI-CA score and BMI or waist circumference Z-scores in the 4- to 10-y and 12- to 16-y age groups only. This index is the first validated index in Australia and one of the few international indices to describe the diet quality of children and adolescents.

Profiling of secondary metabolites in blue lupin inoculated with Phytophthora cinnamomi following phosphite treatment

In order to discover phytochemicals that are potentially bioactive against Phytophthora cinnamomi, (a soil-borne plant pathogen) a metabolite profiling protocol for investigation of metabolic changes in Lupinus angustifolius L. plant roots in response to pathogen challenge has been established. Analysis of the metabolic profiles from healthy and P. cinnamomi-inoculated root tissue with high resolution mass spectrometry and nuclear magnetic resonance spectroscopy confirmed that although susceptible, L. angustifolius upregulated a defence associated genistein and 2′-hydroxygenistein-based isoflavonoid and a soyasapogenol saponin at 12h post inoculation which increased in concentration at 72h post inoculation. In contrast to the typical susceptible interaction, the application of a phosphorous-based treatment to L. angustifolius foliage 48h before P. cinnamomi challenge negated the ability of the pathogen to colonise the root tissue and cause disease. Importantly, although the root profiles of water-treated and phosphite-treated plants post pathogen inoculation contained the same secondary metabolites, concentration variations were observed. Accumulation of secondary metabolites within the P. cinnamomi-inoculated plants confirms that pathogen ingress of the root interstitially occurs in phosphite-treated plants, confirming a direct mode of action against the pathogen upon breaching the root cells.

A biocompatible ionic liquid as an antiwear additive for biodegradable lubricants

A biocompatible ionic liquid, tributyl(methyl)phosphonium diphenylphosphate, P1444DPP (IL1) was investigated as an antiwear additive and compared against Amine Phosphate (AP), one of the commonly used conventional antiwear additives in biodegradable lubricants. IL1 showed excellent antiwear performance, using a pin-on-disc tribometer, when blended in biodegradable base stocks. The steel balls after the test were analyzed using SEM-EDS techniques which confirmed the presence of phosphorous. The tribological properties under reciprocating conditions were also carried out using Optimol SRV oscillating friction and wear tester and the steel discs were observed under Atomic Force Microscopy (AFM), to show the buildup of tribofilm formed by IL1. The thickness of the lubricant film was confirmed by Elastohydrodynamic (EHD) Ultra Thin Film Measurement System. It was observed that IL1 has a better film forming ability than AP. © 2014 Elsevier Ltd.

Efeitos de manipulações ascendentes e descendentes sobre a comunidade fitoplanctônica em um reservatório eutrófico no semi-árido brasileiro

Top-down (grazing) and bottom-up (nutrient, light) controls are important in freshwater ecosystems regulation. Relative importance of these factors could change in space and time, but in tropical lakes bottom-up regulation has to been appointed as more influent. Present study aimed to test the hypothesis that phytoplankton growths rate in Armando Ribeiro reservoir, a huge eutrophic reservoir in semi-arid region of Rio Grande do Norte state, is more limited by nutrient available then zooplankton grazing pressure. Bioassay was conduced monthly from September (2008) to August (2009) manipulating two levels of nutrients (with/without addition) and two level of grazers (with/without removal). Experimental design was factorial 2X2 with four treatments (X5), (i) control with water and zooplankton from natural spot ( C ), (ii) with nutrient addition ( +NP ), (iii) with zooplankton remove ( -Z ) and (iv) with zooplankton remove and nutrient addition ( -Z+NP ). For bioassay confection transparent plastic bottles (500ml) was incubate for 4 or 5 days in two different depths, Secchi`s depth (high luminosity) and 3 times Secchi`s depth (low luminosity). Water samples were collected from each bottle in begins and after incubates period for chlorophyll a concentration analysis and zoopalnktonic organisms density. Phytoplankton growths rates were calculated. Bifactorial ANOVA was performance to test if had a significant effect (p<0,005) of nutrient addition and grazers remove as well a significant interaction between factors on phytoplankton growths rates. Effect magnitude was calculated the relative importance of each process. Results show that phytoplankton growth was in generally stimulated by nutrient addition, as while zooplankton remove rarely stimulated phytoplankton growth. Some significant interactions happening between nutrient additions and grazers remove on phytoplankton growth. In conclusion this study suggests that in studied reservoir phytoplankton growth is more controlled by ascendent factors than descendent

Osteopenia diabética e pós-menopausa: efeito metabólico do zinco na recuperação do volume ósseo trabecular

Diabetes mellitus has been associated with bone metabolism alterations, such as osteopenia and osteporosis. So, the search of new anabolic agents promote bone mass gain can be important to prevent osteoporosis. The aim of this study was evaluate zinc anabolic effect over bone in diabetic and post-menopausal osteopenic models. Diabetes was induced by STZ (45mg/Kg of body weight) administration and post-menopausal by bilateral ovariectomy. Adults female Wistar rats (n=65) were divided in 5 groups: control group (n=15), ovariectomized without (n=15) and with zinc supplementation (n=10) groups, diabetic and ovarioctomized without (n=15) and with zinc supplementation (n=10) groups. Studied periods had been untill 90 days. Diabetic condition was confirmed hiperglicemic state and alterations of state with polyuria, polyphagia, polydipsia and glucosuria. Histomorphometric analysis showed that zinc supplementation increased trabecular thickness and reduced trabecular distance significantly in diabetic groups with similar values to those showed in control group. Correlation analysis of histomorphometric parameters with serum glucose concentration showed that more time in hyperglycemia more bone damage, as well as, zinc supplementation contributed to prevent this damage. Elevated serum glucose caused hyperzincuria, phosphaturia and calciuria. Zinc supplementation promoted increased levels of calcium and phosphorous ions in 90th days diabetic group. No alteration was observed by ovariectomy in mineral (Ca, P and Zn) serum and urine concentrations. Total serum Alkaline Phosphatase activity increased in diabetic groups, supplemented or not, compared with control group. However, Tartarate-Resistant Acid Phosphatase, magnesium and serum zinc did not altered in studied groups. Serum albumin was reduced only in diabetic groups. Serum creatinine was unaltered. These results support the hypotesis that zinc can be used to prevent and treat diabetic and post-menopausal osteopenia

Efeitos da tilápia do Nilo, Oreochromis niloticus, sobre a biomassa planctônica e a transparência da água ao longo de um gradiente de enriquecimento por nutrientes

The omnivorous filter-feeding fish, Nile tilapia (Oreochromis niloticus), can have negative effects on water quality enhancing the eutrophication process. These effects depend on the nutrient enrichment level in the water. We carried out a mesocosm experiment for five weeks in a tropical man-made lake in Brazil to test ifthe effects of tilapias depend on of the level of nutrient enrichment. The experiment lasted for 5 weeks and a factorial 2x5 experimental design was used where the presence and absence of tilapias were manipulated in combination to 5 different levels of nutrient load in a total of 10 treatments. A two way repeated measure ANOVA was performed to evaluate the effects of time (t), tilapia (F), nutrients (NP) and the interactions among these factors on: chlorophyll a, water transparency, total phosphorous, total nitrogen, N:P ratio, zooplankton biomass and phytoplankton biovolume. The tilapia effect was evident, but nutrient enrichment didn t have any effect on the variables analyzed. Tilapia decreased the water transparency, total zooplankton biomass, calanoid copepod biomass, nauplii copepod biomass and cladocerans biomass. On the other hand, tilapia had no effect on phytoplankton biovolume. This lack of effect on phytoplankton is probably due to tilapia grazing that may counteract the positive effect of tilapia on phytoplankton via trophic cascades and nutrient recycling. Hence, a reduction in tilapia stock would not be an effective way to reduce phytoplankton biomass and improve water quality

Distribuição de fósforo no bulbo molhado, aplicado via fertirrigação por gotejamento com ácido fosfórico

Foram investigados a distribuição do fósforo, o pH e a umidade do solo no bulbo molhado em um Latossolo sem vegetação, após fertirrigação com ácido fosfórico, durante 21 dias. O experimento foi instalado na UNESP/Jaboticabal - SP, em blocos casualizados, com cinco repetições. Os tratamentos foram 0; 30; 60; 90 e 120 kg ha-1 de P2O5, dividindo-se as doses em quatro aplicações semanais, via fertirrigação. Após a última aplicação, foram abertas trincheiras nos bulbos molhados e coletadas amostras de solo em quadrículas de 100 cm². O ácido fosfórico provocou aumento da acidez e elevados teores de fósforo no bulbo, principalmente até 30 cm de distância lateral e até 40 cm de profundidade, em relação ao ponto de gotejamento. O aumento da dose de ácido fosfórico (90 e 120 kg ha-1 de P2O5) provocou maiores teores de fósforo e maior acidificação do solo até 30 cm de distância lateral e até 40 cm de profundidade. A distribuição do fósforo e seu efeito no pH no volume de solo molhado não seguiram a distribuição de umidade no mesmo.

Caracterização da água da microbacia do córrego rico avaliada pelo índice de qualidade de água e de estado trófico

A avaliação do índice de qualidade da água (IQA) e do índice de estado trófico médio (IETm) pode subsidiar a formulação de planos de manejo e gestão de sistemas aquáticos. Neste trabalho, foi avaliada a qualidade da água da microbacia do Córrego Rico, que abastece a cidade de Jaboticabal (SP), utilizando o IQA e IETm. As amostragens de água foram realizadas entre setembro-2007 e agosto-2008, em três pontos: a) em uma das nascentes; b) após a Estação de Tratamento de Esgoto de Monte Alto, e c) na captação de água para abastecimento público de Jaboticabal. As amostras foram analisadas quanto aos parâmetros físicos, químicos e microbiológicos: temperatura, oxigênio dissolvido, pH, DBO5, nitrogênio total, fósforo total, turbidez, resíduo total, ortofosfato, clorofila-a e Escherichia coli. de acordo com os resultados obtidos, concluiu-se que: a) as atividades antrópicas às margens do Córrego Rico reduzem a qualidade de sua água, durante os diferentes períodos do ano; b) os valores médios de IQA nos três pontos analisados apresentaram relação direta com os valores médios de IETm, porém ocorreu maior discriminação da qualidade da água pelo IETm, identificando diferentes graus de trofia para os pontos e períodos de amostragens; c) o IQA apresentou melhor diferenciação da qualidade da água entre pontos no período seco e o IETm diferenciou melhor no período chuvoso; d) o processo de autodepuração e/ou a confluência do Córrego Tijuco com o Córrego Rico contribuem para melhor qualidade da água, tornando-a adequada ao abastecimento urbano após tratamento convencional.

The status of soil phosphate fractions and the ability of fungi to dissolve hardly soluble phosphates

Brazilian soils predominantly consist of iron and aluminum oxides and have a low phosphorus content. The present study was carried out in order to assess the status of phosphate fractions in pasture, forest and agricultural soils and the ability of soil fungi to solubilize iron and aluminum phosphates. The abundance of P fractions in the soils studied occurred in the following order: Fe-P > reductant-soluble Fe-P > occluded Fe-P > occluded Al-P > Al-P > Ca-P. of the 481 fungi isolated, 33 showed the ability to solubilize the inorganic phosphates in culture. of these, 14 were considered to be high or very high solubilizers based on a solubilization capacity > 1000 mu g PO43- ml(-1). Isolate F-111 was the only one that dissolved all the insoluble phosphates used. Nine isolates solubilized both Al-P and Ca-P, and four other isolates only solubilized Ca-P. The highest number of isolates with high solubilization capacity were detected in pasture soil, followed by tropical rain forest and forest patch soils. Pasture soil presented both the largest contents of insoluble phosphates and the largest number of fungal isolates with phosphate-solubilizing ability. The range and size of P fractions influenced the number of fungi and their ability to solubilize hardly soluble phosphates. (c) 2004 Elsevier B.V. All rights reserved.