Pelagic phosphorus accumulation in the Pacific Ocean

As a limiting nutrient to marine life, phosphorus (P) is an effective tracer of today's marine productivity. The distribution of P in marine sediments likewise tracks the history of marine productivity because of its relative insolubility in seawater. CaCO3, biogenic opal, terrigenous sediment, and total P have been measured in cores from nine Pacific sites (Deep Sea Drilling Project (DSDP) 65, 66, 310, 77, 62, 572, 463, 586, and GPC-3) and one subantarctic (DSDP 266) site. These sites were specifically chosen to provide information on biota burial flux changes with time for sedimentary sinks that represent key oceanographic variables, i.e., rate of upwelling, water depth, and carbonate dissolution gradient. The accumulation rates of these components for the last 10 Ma were then calculated from determined core age versus depth plots, core bulk density, and porosity data. The accumulation of P weakly correlates with that of CaCO3, moderately with that of total sediment, and very strongly with carbonate-free accumulation. Two prominent peaks for all components occur at 2-3 Ma and 5-6 Ma, and record the chemical loading of dissolved CaCO3, SiO2, and P from glacially emergent continental shelves. These results indicate that continental shelf phosphorites form during interglacially high sea levels and correspond to low deep-sea P accumulation rates, whereas glacially lowered sea levels allow for shelf bypassing and greater deep-sea P accumulation rates.

Foliar phosphorus application enhances nutrient balance and growth of phosphorus deficient sugarcane

Although it is well known that nutrient imbalance in shoot tissues may impair plant performance, the interactive effect between foliar phosphorus (P) application and varying P availability in the rooting medium on the nutritional status of sugarcane has not been well studied. To fill this research gap, four sugarcane varieties (IAC91-1099, IACSP94-2101, IACSP94-2094 and IACSP95-5000) were evaluated using a combination of two concentrations of P in nutrient solution (P-deficient, PD = 0.02 mmol L^(−1) and P-sufficient, PS = 0.5 mmol L^(−1)) and foliar P application (none and 0.16 mol L^(−1)). The spray was applied until drip point three times during the experiment with 15 days intervals, after which the plants were harvested to quantify growth and shoot concentration of nitrogen (N), P, magnesium (Mg), sulphur (S) and manganese (Mn). The responses of sugarcane plants to foliar P spray at different levels of P supply in the rooting medium was not genotype-dependent. It was demonstrated for the averaged values across varieties, that foliar P application enhanced sugarcane performance under low P, as revealed by improvements of leaf area and dry matter production of shoot and root of PD plants. Under P limitation we also observed diminished shoot concentration of N, P, Mg, S and increased concentration of Mn. However, foliar P spray increased the concentrations of N, P, S and reduced shoot Mn. Furthermore, shoot P:N, P:Mg, P:S, P:Mn and Mg:Mn concentration ratios exhibited a positive relationship with shoot dry matter production. In conclusion, low P supply in the rooting medium impairs nutrient balance in shoot tissues of sugarcane at early growth; however, this effect was ameliorated by foliar P application which merits further study under field conditions.

Trapping phosphorus (III) into polyoxometalates: synthesis, characterisation and electronic behaviour study

The introduction of electronically-active heteroanions into polyoxometalates (POMs) is one of the emerging topics in this field. The novel clusters have shown unprecedented intramolecular electron-transfer features that can be directly mediated by the incorporated heteroanions. In this thesis, we will focus on the study of phosphite (HPO32-) as new non-traditional heteroanions, discover HPO32- templated nanostructures, investigate their electronic behaviours as well as understand the self-assembly process of HPO32--templated species. The thesis starts with incorporating HPO32- into POM cages. The feasibility of this work was illustrated by the successful trapping of HPO32- into a “Trojan Horse” type {W18O56} nanocage. The reactivity of embedded {HPO3} was fully studied, showing the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerise to form a weakly interacting (O3PH···HPO3) moiety. In the crystalline state a temperature-dependent intramolecular redox reaction and structural rearrangement occurs. This rearrangement appears to proceed via an intermediate containing two different templates, a pyramidal {HPO3} and a tetrahedral {PO4} moiety. {HPO3} templated POM cages were then vigorously expanded and led to the isolation of five either fully oxidised or mixed-valence clusters trapped with mono-, di-, or tri- {HPO3}. Interestingly, an intriguing 3D honeycomb-like host-guest structure was also synthesised. The porous framework was self-aggregated by a tri-phopshite anion templated {W21} cluster with a {VO4} templated Wells-Dawson type {W18} acting as a guest species within the hexagonal channels. Based on this work, we further extended the templating anions to two different redox-active heteroanions, and discovered a unique mixed-heteroatom templated system built by pairing redox-active {HPIIIO3} with {TeO3}, {SeO3} or {AsO3}. Two molecular systems were developed, ie. “Trojan Horse” type [W18O56(HPO3)0.8(SeO3)1.2(H2O)2]8- and cross-shaped [H4P4X4W64O224]32-/36-, where X=TeIV, SeIV, AsIII. In the case of {W18(HPO3)0.8(SeO3)1.2}, the compound is found to be a mixture of heteroleptic {W18(HPO3)(SeO3)} and homoleptic {W18(SeO3)2} and {W18(HPO3)2}, identified by single crystal x-ray diffraction, NMR as well as high resolution mass spectrometry. The cluster exhibited similar temperature-dependent electronic features to “Trojan Horse” type {W18(HPO3)2O56}. However, due to the intrinsic reactivity difference between {HPO3} and {SeO3}, the thermal treatment leads to the formation of an unusual species [W18O55(PO4)(SeO3)]5-, in which {HPO3} was fully oxidised to {PO4} within the cage, whereas and lone-pair-containing {SeO3} heteroanions were kept intact inside the shell. This finding is extremely interesting, as it demonstrated that multiple and independent intramolecular electronic performance can be achieved by the coexistence of distinct heteroatoms within a single molecule. On the other hand, the cross-shaped [H4P4X4W64O224]32-/36- were constructed by four {W15(HPO3)(XO3)} building units linked by four {WO6} octahedra. Each building unit traps two different heteroatoms. It is interesting to note that the mixed heteroatom species show self-sorting, with a highly selective positional preference. Smaller ionic sized {HPO3} are self-organised into the uncapped side of {W15} cavity, whereas closed side are occupied by larger heteroatoms, which is surprisingly opposed to steric hindrance. Density functional theory (DFT) calculations are currently underway to have a full understanding of the preference of heteroatom substitutions. This series of clusters is of great interest in terms of achieving single molecule-based heteroatom-dependent multiple levels of electron transfer. It has opened a new way to design and synthesise POMs with higher diversity of electrical states, which may lead to a new type of Q-bits for quantum computing. The third chapter is focused on developing polyoxotungstate building blocks templated by {HPO3}. A series of building blocks, {W15O48(HPO3)2}, {W9O30(HPO3)} {W12O40(HPO3)2} and hexagonal {W6O18(HPO3)} have been obtained. The first four building blocks have been reported with {SeO3} and/or {TeO3} heteroanions. This result demonstrates {HPO3} has a similar reactivity as {SeO3} and {TeO3}, therefore studying the self-assembly of {HPO3}-based building blocks would be helpful to have a general understanding of pyramidal heteroatom-based molecular systems. The hexagonal {W6O18(HPO3)} is observed for the first time in polyoxotungstates, showing some of reactivity difference between {HPO3} and {SeO3} and {TeO3}. Furthermore, inorganic salts and pH values have some directing influence on the formation and transformation of various building blocks, resulting in the discovery of a family of {HPO3}-based clusters with nuclearity ranging from {W29} to {W106}. High resolution mass spectrometry was also carried out to investigate the cluster solution behaviour and also gain information of building block speciation. It is found that some clusters experienced decomposition, which gives rise to potential building blocks accountable for the self-assembly.

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.

Phosphorus quantification in fertilizers using laser induced breakdown spectroscopy (LIBS): a methodology of analysis to correct physical matrix effcts.

2016

Gradual correction of phosphorus availability in the no-tillage system.

2016

Growth, mineral composition, fruit yield, and mycorrhizal colonization of feijoa in response to lime and phosphorus application.

2016

Phytate-phosphorus and phytase contents on the relative weight of organs, intestinal morphometry and performance of broilers.

ABSTRACT: In order to evaluate the efficiency of phytase in diets with low and high phytate phosphorus (PP) content, as a consequence of wheat bran inclusion, on the relative weight of organs, intestinal morphometry and performance, three hundred and eighty-four male Cobb500 broilers were housed in metabolic cages. Animals were assigned into four treatments in a 2x2 factorial scheme in a randomized block design with eight replicates of 12 birds each. From 11 days of age birds received experimental diets, which consisted of: Diet low in PP; Diet low in PP with phytase (500FTU kg-1); Diet with a high PP and Diet with a high PP with phytase (500FTU kg-1). At 22 and 32 days of age two birds were slaughtered in order to collect gizzard, heart, liver, cecum, cloacal bursa, and at 32 days, a portion of the duodenum, jejunum and ileum was collected for morphometric evaluation. From 22 to 32 days of age average feed intake, average weight gain, average body weight and feed conversion ratio were also evaluated. Data were subjected to analysis of variance, fixed effects of diet and phytase and interaction between factors as well as the random block effects were tested. There was no significant interaction for the variables studied, concluding that phytase in diets with low or high phytate phosphorus content did not change the relative weight of organs, intestinal morphometrics and performance; only isolated effects were observed. RESUMO: Para avaliar a eficiência da fitase em dietas com baixo e alto teor de fósforo fítico (PP), em função da inclusão ou não do farelo de trigo, sobre o peso relativo de órgãos, morfometria intestinal e desempenho, foram alojados 384 frangos de corte, machos da linhagem Cobb500, em gaiolas metabólicas. Os animais foram distribuídos em quatro tratamentos em um arranjo fatorial 2x2 em delineamento de blocos casualizados com oito repetições e 12 aves por unidade experimental (UE). A partir de 11 dias de idade as aves receberam as dietas experimentais, que consistiram em: Dieta com baixo teor de PP; Dieta com baixo teor de PP com fitase (500FTU kg-1); Dieta com alto teor de PP e Dieta com alto teor de PP com fitase (500FTU kg-1). Aos 22 e 32 dias de idade foram abatidas duas aves por UE para coletar a moela, coração, fígado, ceco, bolsa cloacal, e aos 32 dias foi coletada uma porção do duodeno, jejuno e íleo para avaliação da morfometria. No período de 22 a 32 dias de idade foram avaliados o consumo médio de ração, ganho de peso médio, peso médio corporal e a conversão alimentar. Os dados foram submetidos à análise de variância, onde foram testados os efeitos fixos de dieta e fitase e a interação entre os fatores, bem como o efeito aleatório de bloco. Não foi observada interação significativa para nenhuma das variáveis estudadas, concluindo-se que a fitase em dietas com baixo ou alto de PP não altera o peso relativo dos órgãos, a morfometria intestinal e o desempenho, apenas efeitos isolados foram observados.

Overexpression and characterization of rice Phosphorus-Starvation Tolerance 1 gene and its sorghum and maize homologs in transgenic tobacco.

2016

GWAS of a maize Phosphorus-Starvation Tolerance 1 homolog expression in a tropical diverse panel.

2016

Comprehensive analysis of regulatory elements of maize Phosphorus-Starvation Tolerance 1.

2016

Investigating the links between muscle strength, sun exposure, dietary vitamin D intake and the vitamin D status of ambulatory older adults in South East Queensland

Vitamin D deficiency and insufficiency are now seen as a contemporary health problem in Australia with possible widespread health effects not limited to bone health1. Despite this, the Vitamin D status (measured as serum 25-hydroxyvitamin D (25(OH)D)) of ambulatory adults has been overlooked in this country. Serum 25(OH)D status is especially important among this group as studies have shown a link between Vitamin D and fall risk in older adults2. Limited data also exists on the contributions of sun exposure via ultraviolet radiation and dietary intake to serum 25(OH)D status in this population. The aims of this project were to assess the serum 25(OH)D status of a group of older ambulatory adults in South East Queensland, to assess the association between their serum 25(OH)D status and functional measures as possible indicators of fall risk, obtain data on the sources of Vitamin D in this population and assess whether this intake was related to serum 25(OH)D status and describe sun protection and exposure behaviors in this group and investigate whether a relationship existed between these and serum 25(OH)D status. The collection of this data assists in addressing key gaps identified in the literature with regard to this population group and their Vitamin D status in Australia. A representative convenience sample of participants (N=47) over 55 years of age was recruited for this cross-sectional, exploratory study which was undertaken in December 2007 in south-east Queensland (Brisbane and Sunshine coast). Participants were required to complete a sun exposure questionnaire in addition to a Calcium and Vitamin D food frequency questionnaire. Timed up and go and handgrip dynamometry tests were used to examine functional capacity. Serum 25(OH)D status and blood measures of Calcium, Phosphorus and Albumin were determined through blood tests. The Mean and Median serum 25-Hydroxyvitamin D (25(OH)D) for all participants in this study was 85.8nmol/L (Standard Deviation 29.7nmol/L) and 81.0nmol/L (Range 22-158nmol/L), respectively. Analysis at the bivariate level revealed a statistically significant relationship between serum 25(OH)D status and location, with participants living on the Sunshine Coast having a mean serum 25(OH)D status 21.3nmol/L higher than participants living in Brisbane (p=0.014). While at the descriptive level there was an apparent trend towards higher outdoor exposure and increasing levels of serum 25(OH)D, no statistically significant associations between the sun measures of outdoor exposure, sun protection behaviors and phenotypic characteristics and serum 25(OH)D status were observed. Intake of both Calcium and Vitamin D was low in this sample with sixty-eight (68%) of participants not meeting the Estimated Average Requirements (EAR) for Calcium (Median=771.0mg; Range=218.0-2616.0mg), while eighty-seven (87%) did not meet the Adequate Intake for Vitamin D (Median=4.46ug; Range=0.13-30.0ug). This raises the question of how realistic meeting the new Adequate Intakes for Vitamin D is, when there is such a low level of Vitamin D fortification in this country. However, participants meeting the Adequate Intake (AI) for Vitamin D were observed to have a significantly higher serum 25(OH)D status compared to those not meeting the AI for Vitamin D (p=0.036), showing that meeting the AI for Vitamin D may play a significant role in determining Vitamin D status in this population. By stratifying our data by categories of outdoor exposure time, a trend was observed between increased importance of Vitamin D dietary intake as a possible determinant of serum 25(OH)D status in participants with lower outdoor exposures. While a trend towards higher Timed Up and Go scores in participants with higher 25(OH) D status was seen, this was only significant for females (p=0.014). Handgrip strength showed statistically significant association with serum 25(OH)D status. The high serum 25(OH)D status in our sample almost certainly explains the limited relationship between functional measures and serum 25(OH)D. However, the observation of an association between slower Time Up and Go speeds, and lower serum 25(OH)D levels, even with a small sample size, is significant as slower Timed Up and Go speeds have been associated with increased fall risk in older adults3. Multivariable regression analysis revealed Location as the only significant determinant of serum 25(OH)D status at p=0.014, with trends (p=>0.1) for higher serum 25(OH)D being shown for participants that met the AI for Vitamin D and rated themselves as having a higher health status. The results of this exploratory study show that 93.6% of participants had adequate 25(OH)D status-possibly due to measurement being taken in the summer season and the convenience nature of the sample. However, many participants do not meet their dietary Calcium and Vitamin D requirements, which may indicate inadequate intake of these nutrients in older Australians and a higher risk of osteoporosis. The relationship between serum 25(OH)D and functional measures in this population also requires further study, especially in older adults displaying Vitamin D insufficiency or deficiency.

Determining a set of surrogate parameters to evaluate urban stormwater quality

This thesis details methodology to estimate urban stormwater quality based on a set of easy to measure physico-chemical parameters. These parameters can be used as surrogate parameters to estimate other key water quality parameters. The key pollutants considered in this study are nitrogen compounds, phosphorus compounds and solids. The use of surrogate parameter relationships to evaluate urban stormwater quality will reduce the cost of monitoring and so that scientists will have added capability to generate a large amount of data for more rigorous analysis of key urban stormwater quality processes, namely, pollutant build-up and wash-off. This in turn will assist in the development of more stringent stormwater quality mitigation strategies. The research methodology was based on a series of field investigations, laboratory testing and data analysis. Field investigations were conducted to collect pollutant build-up and wash-off samples from residential roads and roof surfaces. Past research has identified that these impervious surfaces are the primary pollutant sources to urban stormwater runoff. A specially designed vacuum system and rainfall simulator were used in the collection of pollutant build-up and wash-off samples. The collected samples were tested for a range of physico-chemical parameters. Data analysis was conducted using both univariate and multivariate data analysis techniques. Analysis of build-up samples showed that pollutant loads accumulated on road surfaces are higher compared to the pollutant loads on roof surfaces. Furthermore, it was found that the fraction of solids smaller than 150 ìm is the most polluted particle size fraction in solids build-up on both roads and roof surfaces. The analysis of wash-off data confirmed that the simulated wash-off process adopted for this research agrees well with the general understanding of the wash-off process on urban impervious surfaces. The observed pollutant concentrations in wash-off from road surfaces were different to pollutant concentrations in wash-off from roof surfaces. Therefore, firstly, the identification of surrogate parameters was undertaken separately for roads and roof surfaces. Secondly, a common set of surrogate parameter relationships were identified for both surfaces together to evaluate urban stormwater quality. Surrogate parameters were identified for nitrogen, phosphorus and solids separately. Electrical conductivity (EC), total organic carbon (TOC), dissolved organic carbon (DOC), total suspended solids (TSS), total dissolved solids (TDS), total solids (TS) and turbidity (TTU) were selected as the relatively easy to measure parameters. Consequently, surrogate parameters for nitrogen and phosphorus were identified from the set of easy to measure parameters for both road surfaces and roof surfaces. Additionally, surrogate parameters for TSS, TDS and TS which are key indicators of solids were obtained from EC and TTU which can be direct field measurements. The regression relationships which were developed for surrogate parameters and key parameter of interest were of a similar format for road and roof surfaces, namely it was in the form of simple linear regression equations. The identified relationships for road surfaces were DTN-TDS:DOC, TP-TS:TOC, TSS-TTU, TDS-EC and TSTTU: EC. The identified relationships for roof surfaces were DTN-TDS and TSTTU: EC. Some of the relationships developed had a higher confidence interval whilst others had a relatively low confidence interval. The relationships obtained for DTN-TDS, DTN-DOC, TP-TS and TS-EC for road surfaces demonstrated good near site portability potential. Currently, best management practices are focussed on providing treatment measures for stormwater runoff at catchment outlets where separation of road and roof runoff is not found. In this context, it is important to find a common set of surrogate parameter relationships for road surfaces and roof surfaces to evaluate urban stormwater quality. Consequently DTN-TDS, TS-EC and TS-TTU relationships were identified as the common relationships which are capable of providing measurements of DTN and TS irrespective of the surface type.

Nutrients build-up and wash-off processes in urban land uses

This thesis describes outcomes of a research study conducted to investigate the nutrient build-up and wash-off processes on urban impervious surfaces. The data needed for the study was generated through a series of field investigations and laboratory test procedures. The study sites were selected in urbanised catchments to represent typical characteristics of residential, industrial and commercial land uses. The build-up and wash-off samples were collected from road surfaces in the selected study sites. A specially designed vacuum collection system and a rainfall simulator were used for sample collection. According to the data analysis, the solids build-up on road surfaces was significantly finer with more than 80% of the particles below 150 ìm for all the land uses. Nutrients were mostly associated with the particle size range below 150 ìm in both build-up and wash-off samples irrespective of type of land use. Therefore, the finer fraction of solids was the most important for the nutrient build-up and particulate nutrient wash-off processes. Consequently, the design of stormwater quality mitigation measures should target particles less than 150 ìm for the removal of nutrients irrespective of type of land use. Total kjeldahl nitrogen (TKN) was the most dominant form of nitrogen species in build-up on road surfaces. Phosphorus build-up on road surfaces was mainly in inorganic form and phosphate (PO4 3-) was the most dominant form. The nutrient wash-off process was found to be dependent on rainfall intensity and duration. Concentration of both total nitrogen and phosphorus was higher at the beginning of the rain event and decreased with the increase in rainfall duration. Consequently, in the design of stormwater quality mitigation strategies for nutrients removal, it is important to target the initial period of rain events. The variability of wash-off of nitrogen with rainfall intensity was significantly different to phosphorus wash-off. The concentration of nitrogen was higher in the wash-off for low intensity rain events compared to the wash-off for high intensity rain events. On the other hand, the concentration of phosphorus in the wash-off was high for high intensity rain events compared to low intensity rain events. Consequently, the nitrogen washoff can be defined as a source limiting process and phosphorus wash-off as a transport limiting process. This highlights the importance of taking into consideration the wash-off of low intensity rain events in the design of stormwater quality mitigation strategies targeting the nitrogen removal. All the nitrogen species in wash-off are primarily in dissolved form whereas phosphorus is in particulate form. The differences in the nitrogen and phosphorus wash-off processes is principally due to the degree of solubility, attachment to particulates, composition of total nitrogen and total phosphorus and the degree of adherence of the solids particles to the surface to which nutrients are attached. The particulate nitrogen available for wash-off is removed readily as these are mobilised as free solids particles on the surface. Phosphorus is washed-off mostly with the solids particles which are strongly adhered to the surface or as the fixed solids load. Investigation of the nitrogen wash-off process using bulk wash-off samples was in close agreement with the investigation of dissolved fraction of wash-off solids. This was primarily due to the predominant nature of dissolved nitrogen. However, the investigation of the processes which underpin phosphorus wash-off using bulk washoff samples could lead to loss of information. This is due to the composition of total phosphorus in wash-off solids and the inherent variability of the wash-off process for the different particle size ranges. This variability should preferably be taken into consideration as phosphorus wash-off is predominantly in particulate form. Therefore, care needs to be taken in the investigation of the phosphorus wash-off process using bulk wash-off samples to ensure that there is no loss of information and hence result in misleading outcomes. The investigation of different particle size ranges of wash-off solids is preferable in the interest of designing effective stormwater quality management strategies targeting phosphorus removal.