Zircon chronochemistry of high heat-producing granites in Queensland and Europe

High heat-producing granites (HHPGs) are reservoir rocks for enhanced geothermal systems (EGS), yet the origins of their anomalous chemistry remain poorly understood. To gain a better understanding of the characteristic distribution of elemental depletions and enrichments (focussing on U, Th & K) within granite suites of different heritage and tectonic setting, and the processes that lead to these enrichments, we are undertaking a systematic accessory-mineral chronochemical study of two suites of S- and I-type granites in northern Queensland, as well as two archetypal HHPGs in Cornwall, England (S-type) and Soultz-sous- Forêts, France (I-type). Novel zircon LA-ICP-MS chronochemical methods will later be underpinned by a systematic petrographic, scanning electron microscope (SEM), and electron microprobe (EPMA) study of all the REE-Y-Th-U-rich accessory minerals to fully characterise how the composition, textural distributions and associations change with rock chemistry between and among the suites. Preliminary results indicate that zircons with inherited ages do not have anomalously high U (>1000 ppm) & Th (>400 ppm) values (Ahrens, 1965). Instead, enrichment in these HPE is seen in zircons dated to around the time of magmatic emplacement. These results indicate that enrichment arose primarily through fractional crystallisation of the granitic magmas. Our results support the suggestion that a source pre-enriched in the HPEs does not appear to be fundamental for the formation of all HHPGs. Instead fractional crystallisation processes, and the accessory minerals formed in magmas of differing initial compositions, are the key controls on the levels of enrichment observed (e.g. Champion & Chappell, 1992; Chappell & Hine, 2006). One implication is that the most fractionated granites may not be the most enriched in the HPEs and therefore prospective to future EGS development.

Studies on self-assembly hydrothermal fabrication and thermal stability of Chromium oxyhydroxide nanomaterials synthesised from Chromium oxide colloids

Chromium oxyhydroxide nanomaterials with narrow size-distribution were synthesised through a simple hydrothermal method. Experimental conditions, such as reaction duration and pH values of the precipitation process and hydrothermal treatment played important roles in determining the nature of the final product chromium oxyhydroxide nanomaterials. The effect of these synthesis parameters were studied with the assistance of X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and thermogravimetric analyses. This research has developed a controllable synthesis of Chromium oxyhydroxide nanomaterials from Chromium oxide colloids.

High resolution transmission electron microscopy of the Murchison Carbonaceous Chondrite and the Kenna Ureilite

Fine-grained matrices in carbonaceous chondrites and small, micron-sized inclusions in achondrites can be characterized effectively using high resolution transmission electron micro­scopy (HRTEM).

Stress distribution of CFRP strengthened steel hollow sections under tension

Carbon fibre reinforced polymer (CFRP) sheets have many outstanding properties such as high strength, high elastic modulus, light weight and good durability which are made them a suitable alternative for steel in strengthening work. This paper describe the ultimate load carrying capacity of steel hollow sections at effective bond length in terms of its cross sectional area and the stress distribution within bond region for different layers CFRP. It was found that depending on their size and orientation of uni- directional CFRP layers, the ultimate tensile load was different. Along with these tests, non linear finite element analysis was also performed to validate the ultimate load carrying capacity depending on their cross sections. The predicted ultimate loads from FE analysis are found very close to the laboratory test results. The validated model has been used to determine the stress distribution at bond joint for different orientation of CFRP. This research shows the effect of stress distribution and suitable wrapping layer to be used for the strengthening of steel hollow sections in tension.

Distinguishing new science from calibration effects in the electron-volt neutron spectrometer VESUVIO at ISIS

The "standard" procedure for calibrating the Vesuvio eV neutron spectrometer at the ISIS neutron source, forming the basis for data analysis over at least the last decade, was recently documented in considerable detail by the instrument’s scientists. Additionally, we recently derived analytic expressions of the sensitivity of recoil peak positions with respect to fight-path parameters and presented neutron–proton scattering results that together called in to question the validity of the "standard" calibration. These investigations should contribute significantly to the assessment of the experimental results obtained with Vesuvio. Here we present new results of neutron–deuteron scattering from D2 in the backscattering angular range (theata > 90 degrees) which are accompanied by a striking energy increase that violates the Impulse Approximation, thus leading unequivocally the following dilemma: (A) either the "standard" calibration is correct and then the experimental results represent a novel quantum dynamical effect of D which stands in blatant contradiction of conventional theoretical expectations; (B) or the present "standard" calibration procedure is seriously deficient and leads to artificial outcomes. For Case(A), we allude to the topic of attosecond quantumdynamical phenomena and our recent neutron scattering experiments from H2 molecules. For Case(B),some suggestions as to how the "standard" calibration could be considerably improved are made.

A USANS/SANS study of the accessibility of pores in the barnett shale to methane and water

Shale is an increasingly important source of natural gas in the United States. The gas is held in fine pores that need to be accessed by horizontal drilling and hydrofracturing techniques. Understanding the nature of the pores may provide clues to making gas extraction more efficient. We have investigated two Mississippian Barnett Shale samples, combining small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) to determine the pore size distribution of the shale over the size range 10 nm to 10 μm. By adding deuterated methane (CD4) and, separately, deuterated water (D2O) to the shale, we have identified the fraction of pores that are accessible to these compounds over this size range. The total pore size distribution is essentially identical for the two samples. At pore sizes >250 nm, >85% of the pores in both samples are accessible to both CD4 and D2O. However, differences in accessibility to CD4 are observed in the smaller pore sizes (∼25 nm). In one sample, CD4 penetrated the smallest pores as effectively as it did the larger ones. In the other sample, less than 70% of the smallest pores (<25 nm) were accessible to CD4, but they were still largely penetrable by water, suggesting that small-scale heterogeneities in methane accessibility occur in the shale samples even though the total porosity does not differ. An additional study investigating the dependence of scattered intensity with pressure of CD4 allows for an accurate estimation of the pressure at which the scattered intensity is at a minimum. This study provides information about the composition of the material immediately surrounding the pores. Most of the accessible (open) pores in the 25 nm size range can be associated with either mineral matter or high reflectance organic material. However, a complementary scanning electron microscopy investigation shows that most of the pores in these shale samples are contained in the organic components. The neutron scattering results indicate that the pores are not equally proportioned in the different constituents within the shale. There is some indication from the SANS results that the composition of the pore-containing material varies with pore size; the pore size distribution associated with mineral matter is different from that associated with organic phases.

Scanning electron microscopy of condensation related minerals : the Bjurbole meteorite

Filamentary single crystals, blades, sheets, euhedral crystals and powders may form by vapor phase condensation depending on the supersauration conditions in the vapor with respect to the condensing species [1]. Filamentary crystal growth requires the operation of an axial screw dislocation [2]. A Vapor-Liquid-Solid (VLS) mechanism may also produce filamentary single crystals, ribbons and blades. The latter two morphologies are typically twinned. Crystals grown by this mechanism do not require the presence of an axial screw dislocation. Impurities may either promote or inhibit crystal growth [3]. The VLS mechanism allows crystals to grow at small supersaturation of the vapor. Thin enstatite blades, ribbons and sheets have been observed in chondritic porous Interplanetary Dust Partics (IDP's) [4, 5]. The requisite screw dislocation for vapor phase condensation [1] has been observed in these enstatite blades [4]. Bradley et al. [4] suggest that these crystals are primary vapor phase condensates which could have formed either in the solar nebula or in presolar environments. These observations [4,5] are significant in that they may provide a demonstrable link to theoretical predictions: viz. that in the primordial solar nebula filamentary condensates could cluster into 'lint balls' and form the predecessors to comets [6].

Electron microscopy of stratospheric particles

A recent NASA program to collect stratospheric dust particles using high-flying WB57 aircraft has made available many more potential candidates for the study of extraterrestrial materials. This preliminary report provides an interpretation of the types of particles returned from one flag (W7017) collected in August, 1981 using a subset of 81 allocated particles. This particular collection period is after the Mt. St. Helen's eruptions. Therefore, the flag may contain significant quantities of volcanic debris in addition to the expected terrestrial contaminants [1]. All particles were mounted on nucleopore filters and have been examined using a modified JEOL100CX analytical electron microscope. For most of the particles, X-ray energy dispersive spectra and images were obtained at 40kV on samples which have not received any conductive coating. However, in order to improve resolution (to ~30A) some images are recorded at 100kV. In addition, 16 samples have been coated with a thin layer (<50A) of Au/Pd.

Electron microscopy of micron-sized lunar soil

We have performed electron-microscopic analysis on 0.5-1.0µm grains in order to study radiation damage by the solar-wind. We are reporting some interesting results we have found in monomineralic grains from core sample 15010,1130. This is a submature soil which has been studied for rare gas abundance and ferromagnetic resonance by (1) and modal petrology by (2).

Measurement of anisotropies of the kinetic energy and anharmonicity in pyrolytic graphite by neutron Compton scattering

Neutron Compton scattering (NCS) measurements of the anisotropy of the momentum distribution and the mean Laplacian of the interatomic potential ∇2V have been performed using electron volt neutrons, with wave vector transfers between 24 Å−1 and 98 Å−1. The measured momentum distribution of the atoms displays significantly more anisotropy than a calculation using a model density of states. We have observed anisotropies in ∇2V for the first time. The results suggest that the atomic potential is harmonic within the graphite planes, but anharmonic for vibrations perpendicular to the planes.

Cell death control : the interplay of apoptosis and autophagy in the pathogenicity of sclerotinia sclerotiorum

Programmed cell death is characterized by a cascade of tightly controlled events that culminate in the orchestrated death of the cell. In multicellular organisms autophagy and apoptosis are recognized as two principal means by which these genetically determined cell deaths occur. During plant-microbe interactions cell death programs can mediate both resistant and susceptible events. Via oxalic acid (OA), the necrotrophic phytopathogen Sclerotinia sclerotiorum hijacks host pathways and induces cell death in host plant tissue resulting in hallmark apoptotic features in a time and dose dependent manner. OA-deficient mutants are non-pathogenic and trigger a restricted cell death phenotype in the host that unexpectedly exhibits markers associated with the plant hypersensitive response including callose deposition and a pronounced oxidative burst, suggesting the plant can recognize and in this case respond, defensively. The details of this plant directed restrictive cell death associated with OA deficient mutants is the focus of this work. Using a combination of electron and fluorescence microscopy, chemical effectors and reverse genetics, we show that this restricted cell death is autophagic. Inhibition of autophagy rescued the non-pathogenic mutant phenotype. These findings indicate that autophagy is a defense response in this necrotrophic fungus/plant interaction and suggest a novel function associated with OA; namely, the suppression of autophagy. These data suggest that not all cell deaths are equivalent, and though programmed cell death occurs in both situations, the outcome is predicated on who is in control of the cell death machinery. Based on our data, we suggest that it is not cell death per se that dictates the outcome of certain plant-microbe interactions, but the manner by which cell death occurs that is crucial.

Distribution of organic-rich sediments through the Phanerozoic

It is commonly assumed that rates of accumulation of organic-rich strata have varied through geologic time with some periods that were particularly favorable for accumulation of petroleum source rocks or coals. A rigorous analysis of the validity of such an assumption requires consideration of the basic fact that although sedimentary rocks have been lost through geologic time to erosion and metamorphism. Consequently, their present-day global abundance decreases with their geologic age. Measurements of the global abundance of coal-bearing strata suggest that conditions for coal accumulation were exceptionally favorable during the late Carboniferous. Strata of this age constitute 21% of the world's coal-bearing strata. Global rates of coal accumulation appear to have been relatively constant since the end of the Carboniferous, with the exception of the Triassic which contains only 1.75% of the world's coal-bearing strata. Estimation of the global amount of discovered oil by age of the source rock show that 58% of the world's oil has been sourced from Cretaceous or younger strata and 99% from Silurian or younger strata. Although most geologic periods were favourable for oil source-rock accumulation the mid-Permian to mid-Jurassic appears to have been particularly unfavourable accounting for less than 2% of the world's oil. Estimation of the global amount of discovered natural gas by age of the source rock show that 48% of the world's oil has been sourced from Cretaceous or younger strata and 99% from Silurian or younger strata. The Silurian and Late Carboniferous were particularly favourable for gas source-rock accumulation respectively accounting for 12.9% and 6.9% of the world's gas. By contrast, Permian and Triassic source rocks account for only 1.7% of the world's natural gas. Rather than invoking global climatic or oceanic events to explain the relative abundance of organic rich sediments through time, examination of the data suggests the more critical control is tectonic. The majority of coals are associated with foreland basins and the majority of oil-prone source rocks are associated with rifting. The relative abundance of these types of basin through time determines the abundance and location of coals and petroleum source rocks.

The distribution of construction project bids

This paper describes an analysis of construction project bids to determine (a) the global distribution and (b) factors influencing the distribution of bids. The global distribution of bids was found, by using a battery of ll test statistics, to be approximated by a three-parameter log normal distribution. No global spread parameter was found. A multivariate analysis revealed the year of tender to be the major influencing factor. Consideration of the construction order, tender price and output indices lead to the conclusion that distributional spread reflected the degree of difference in pricing policies between bidders and the skewness of the distributions reflected the degree of competition. The paper concludes with a tentative model of the causal relationships between the factors and distributional characteristics involved.

A description of the Mei2-like protein family; structure, phylogenetic distribution and biological context

The Schizosaccharomyces pombe Mei2 gene encodes an RNA recognition motif (RRM) protein that stimulates meiosis upon binding a specific non-coding RNA and subsequent accumulation in a “mei2-dot” in the nucleus. We present here the first systematic characterization of the family of proteins with characteristic Mei2-like amino acid sequences. Mei2-like proteins are an ancient eukaryotic protein family with three identifiable RRMs. The C-terminal RRM (RRM3) is unique to Mei2-like proteins and is the most highly conserved of the three RRMs. RRM3 also contains conserved sequence elements at its C-terminus not found in other RRM domains. Single copy Mei2-like genes are present in some fungi, in alveolates such as Paramecium and in the early branching eukaryote Entamoeba histolytica, while plants contain small families of Mei2-like genes. While the C-terminal RRM is highly conserved between plants and fungi, indicating conservation of molecular mechanisms, plant Mei2-like genes have changed biological context to regulate various aspects of developmental pattern formation.

A catchment modelling approach integrating surface and groundwater processes, land use and distribution of nutrients : Elimbah Creek, southeast Queensland

As the world’s population is growing, so is the demand for agricultural products. However, natural nitrogen (N) fixation and phosphorus (P) availability cannot sustain the rising agricultural production, thus, the application of N and P fertilisers as additional nutrient sources is common. It is those anthropogenic activities that can contribute high amounts of organic and inorganic nutrients to both surface and groundwaters resulting in degradation of water quality and a possible reduction of aquatic life. In addition, runoff and sewage from urban and residential areas can contain high amounts of inorganic and organic nutrients which may also affect water quality. For example, blooms of the cyanobacterium Lyngbya majuscula along the coastline of southeast Queensland are an indicator of at least short term decreases of water quality. Although Australian catchments, including those with intensive forms of land use, show in general a low export of nutrients compared to North American and European catchments, certain land use practices may still have a detrimental effect on the coastal environment. Numerous studies are reported on nutrient cycling and associated processes on a catchment scale in the Northern Hemisphere. Comparable studies in Australia, in particular in subtropical regions are, however, limited and there is a paucity in the data, in particular for inorganic and organic forms of nitrogen and phosphorus; these nutrients are important limiting factors in surface waters to promote algal blooms. Therefore, the monitoring of N and P and understanding the sources and pathways of these nutrients within a catchment is important in coastal zone management. Although Australia is the driest continent, in subtropical regions such as southeast Queensland, rainfall patterns have a significant effect on runoff and thus the nutrient cycle at a catchment scale. Increasingly, these rainfall patterns are becoming variable. The monitoring of these climatic conditions and the hydrological response of agricultural catchments is therefore also important to reduce the anthropogenic effects on surface and groundwater quality. This study consists of an integrated hydrological–hydrochemical approach that assesses N and P in an environment with multiple land uses. The main aim is to determine the nutrient cycle within a representative coastal catchment in southeast Queensland, the Elimbah Creek catchment. In particular, the investigation confirms the influence associated with forestry and agriculture on N and P forms, sources, distribution and fate in the surface and groundwaters of this subtropical setting. In addition, the study determines whether N and P are subject to transport into the adjacent estuary and thus into the marine environment; also considered is the effect of local topography, soils and geology on N and P sources and distribution. The thesis is structured on four components individually reported. The first paper determines the controls of catchment settings and processes on stream water, riverbank sediment, and shallow groundwater N and P concentrations, in particular during the extended dry conditions that were encountered during the study. Temporal and spatial factors such as seasonal changes, soil character, land use and catchment morphology are considered as well as their effect on controls over distributions of N and P in surface waters and associated groundwater. A total number of 30 surface and 13 shallow groundwater sampling sites were established throughout the catchment to represent dominant soil types and the land use upstream of each sampling location. Sampling comprises five rounds and was conducted over one year between October 2008 and November 2009. Surface water and groundwater samples were analysed for all major dissolved inorganic forms of N and for total N. Phosphorus was determined in the form of dissolved reactive P (predominantly orthophosphate) and total P. In addition, extracts of stream bank sediments and soil grab samples were analysed for these N and P species. Findings show that major storm events, in particular after long periods of drought conditions, are the driving force of N cycling. This is expressed by higher inorganic N concentrations in the agricultural subcatchment compared to the forested subcatchment. Nitrate N is the dominant inorganic form of N in both the surface and groundwaters and values are significantly higher in the groundwaters. Concentrations in the surface water range from 0.03 to 0.34 mg N L..1; organic N concentrations are considerably higher (average range: 0.33 to 0.85 mg N L..1), in particular in the forested subcatchment. Average NO3-N in the groundwater has a range of 0.39 to 2.08 mg N L..1, and organic N averages between 0.07 and 0.3 mg N L..1. The stream bank sediments are dominated by organic N (range: 0.53 to 0.65 mg N L..1), and the dominant inorganic form of N is NH4-N with values ranging between 0.38 and 0.41 mg N L..1. Topography and soils, however, were not to have a significant effect on N and P concentrations in waters. Detectable phosphorus in the surface and groundwaters of the catchment is limited to several locations typically in the proximity of areas with intensive animal use; in soil and sediments, P is negligible. In the second paper, the stable isotopes of N (14N/15N) and H2O (16O/18O and 2H/H) in surface and groundwaters are used to identify sources of dissolved inorganic and organic N in these waters, and to determine their pathways within the catchment; specific emphasis is placed on the relation of forestry and agriculture. Forestry is predominantly concentrated in the northern subcatchment (Beerburrum Creek) while agriculture is mainly found in the southern subcatchment (Six Mile Creek). Results show that agriculture (horticulture, crops, grazing) is the main source of inorganic N in the surface waters of the agricultural subcatchment, and their isotopic signature shows a close link to evaporation processes that may occur during water storage in farm dams that are used for irrigation. Groundwaters are subject to denitrification processes that may result in reduced dissolved inorganic N concentrations. Soil organic matter delivers most of the inorganic N to the surface water in the forested subcatchment. Here, precipitation and subsequently runoff is the main source of the surface waters. Groundwater in this area is affected by agricultural processes. The findings also show that the catchment can attenuate the effects of anthropogenic land use on surface water quality. Riparian strips of natural remnant vegetation, commonly 50 to 100 m in width, act as buffer zones along the drainage lines in the catchment and remove inorganic N from the soil water before it enters the creek. These riparian buffer zones are common in most agricultural catchments of southeast Queensland and are indicated to reduce the impact of agriculture on stream water quality and subsequently on the estuary and marine environments. This reduction is expressed by a significant decrease in DIN concentrations from 1.6 mg N L..1 to 0.09 mg N L..1, and a decrease in the �15N signatures from upstream surface water locations downstream to the outlet of the agricultural subcatchment. Further testing is, however, necessary to confirm these processes. Most importantly, the amount of N that is transported to the adjacent estuary is shown to be negligible. The third and fourth components of the thesis use a hydrological catchment model approach to determine the water balance of the Elimbah Creek catchment. The model is then used to simulate the effects of land use on the water balance and nutrient loads of the study area. The tool that is used is the internationally widely applied Soil and Water Assessment Tool (SWAT). Knowledge about the water cycle of a catchment is imperative in nutrient studies as processes such as rainfall, surface runoff, soil infiltration and routing of water through the drainage system are the driving forces of the catchment nutrient cycle. Long-term information about discharge volumes of the creeks and rivers do, however, not exist for a number of agricultural catchments in southeast Queensland, and such information is necessary to calibrate and validate numerical models. Therefore, a two-step modelling approach was used to calibrate and validate parameters values from a near-by gauged reference catchment as starting values for the ungauged Elimbah Creek catchment. Transposing monthly calibrated and validated parameter values from the reference catchment to the ungauged catchment significantly improved model performance showing that the hydrological model of the catchment of interest is a strong predictor of the water water balance. The model efficiency coefficient EF shows that 94% of the simulated discharge matches the observed flow whereas only 54% of the observed streamflow was simulated by the SWAT model prior to using the validated values from the reference catchment. In addition, the hydrological model confirmed that total surface runoff contributes the majority of flow to the surface water in the catchment (65%). Only a small proportion of the water in the creek is contributed by total base-flow (35%). This finding supports the results of the stable isotopes 16O/18O and 2H/H, which show the main source of water in the creeks is either from local precipitation or irrigation waters delivered by surface runoff; a contribution from the groundwater (baseflow) to the creeks could not be identified using 16O/18O and 2H/H. In addition, the SWAT model calculated that around 68% of the rainfall occurring in the catchment is lost through evapotranspiration reflecting the prevailing long-term drought conditions that were observed prior and during the study. Stream discharge from the forested subcatchment was an order of magnitude lower than discharge from the agricultural Six Mile Creek subcatchment. A change in land use from forestry to agriculture did not significantly change the catchment water balance, however, nutrient loads increased considerably. Conversely, a simulated change from agriculture to forestry resulted in a significant decrease of nitrogen loads. The findings of the thesis and the approach used are shown to be of value to catchment water quality monitoring on a wider scale, in particular the implications of mixed land use on nutrient forms, distributions and concentrations. The study confirms that in the tropics and subtropics the water balance is affected by extended dry periods and seasonal rainfall with intensive storm events. In particular, the comprehensive data set of inorganic and organic N and P forms in the surface and groundwaters of this subtropical setting acquired during the one year sampling program may be used in similar catchment hydrological studies where these detailed information is missing. Also, the study concludes that riparian buffer zones along the catchment drainage system attenuate the transport of nitrogen from agricultural sources in the surface water. Concentrations of N decreased from upstream to downstream locations and were negligible at the outlet of the catchment.