83 resultados para 030602 Chemical Thermodynamics and Energetics


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Risks and uncertainties are inevitable in engineering projects and infrastructure investments. Decisions about investment in infrastructure such as for maintenance, rehabilitation and construction works can pose risks, and may generate significant impacts on social, cultural, environmental and other related issues. This report presents the results of a literature review of current practice in identifying, quantifying and managing risks and predicting impacts as part of the planning and assessment process for infrastructure investment proposals. In assessing proposals for investment in infrastructure, it is necessary to consider social, cultural and environmental risks and impacts to the overall community, as well as financial risks to the investor. The report defines and explains the concept of risk and uncertainty, and describes the three main methodology approaches to the analysis of risk and uncertainty in investment planning for infrastructure, viz examining a range of scenarios or options, sensitivity analysis, and a statistical probability approach, listed here in order of increasing merit and complexity. Forecasts of costs, benefits and community impacts of infrastructure are recognised as central aspects of developing and assessing investment proposals. Increasingly complex modelling techniques are being used for investment evaluation. The literature review identified forecasting errors as the major cause of risk. The report contains a summary of the broad nature of decision-making tools used by governments and other organisations in Australia, New Zealand, Europe and North America, and shows their overall approach to risk assessment in assessing public infrastructure proposals. While there are established techniques to quantify financial and economic risks, quantification is far less developed for political, social and environmental risks and impacts. The report contains a summary of the broad nature of decision-making tools used by governments and other organisations in Australia, New Zealand, Europe and North America, and shows their overall approach to risk assessment in assessing public infrastructure proposals. While there are established techniques to quantify financial and economic risks, quantification is far less developed for political, social and environmental risks and impacts. For risks that cannot be readily quantified, assessment techniques commonly include classification or rating systems for likelihood and consequence. The report outlines the system used by the Australian Defence Organisation and in the Australian Standard on risk management. After each risk is identified and quantified or rated, consideration can be given to reducing the risk, and managing any remaining risk as part of the scope of the project. The literature review identified use of risk mapping techniques by a North American chemical company and by the Australian Defence Organisation. This literature review has enabled a risk assessment strategy to be developed, and will underpin an examination of the feasibility of developing a risk assessment capability using a probability approach.

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This paper reports the application of multicriteria decision making techniques, PROMETHEE and GAIA, and receptor models, PCA/APCS and PMF, to data from an air monitoring site located on the campus of Queensland University of Technology in Brisbane, Australia and operated by Queensland Environmental Protection Agency (QEPA). The data consisted of the concentrations of 21 chemical species and meteorological data collected between 1995 and 2003. PROMETHEE/GAIA separated the samples into those collected when leaded and unleaded petrol were used to power vehicles in the region. The number and source profiles of the factors obtained from PCA/APCS and PMF analyses were compared. There are noticeable differences in the outcomes possibly because of the non-negative constraints imposed on the PMF analysis. While PCA/APCS identified 6 sources, PMF reduced the data to 9 factors. Each factor had distinctive compositions that suggested that motor vehicle emissions, controlled burning of forests, secondary sulphate, sea salt and road dust/soil were the most important sources of fine particulate matter at the site. The most plausible locations of the sources were identified by combining the results obtained from the receptor models with meteorological data. The study demonstrated the potential benefits of combining results from multi-criteria decision making analysis with those from receptor models in order to gain insights into information that could enhance the development of air pollution control measures.

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Films of piezoelectric PVDF and P(VDF-TrFE) were exposed to vacuum UV (115-300 nm VUV) and -radiation to investigate how these two forms of radiation affect the chemical, morphological, and piezoelectric properties of the polymers. The extent of crosslinking was almost identical in both polymers after -irradiation, but surprisingly, was significantly higher for the TrFE copolymer after VUV-irradiation. Changes in the melting behavior were also more significant in the TrFE copolymer after VUV-irradiation due to both surface and bulk crosslinking, compared with only surface crosslinking for the PVDF films. The piezoelectric properties (measured using d33 piezoelectric coefficients and D-E hysteresis loops) were unchanged in the PVDF homopolymer, while the TrFE copolymer exhibited more narrow D-E loops after exposure to either - or VUV-radiation. The more severe damage to the TrFE copolymer in comparison with the PVDF homopolymer after VUV-irradiation is explained by different energy deposition characteristics. The short wavelength, highly energetic photons are undoubtedly absorbed in the surface layers of both polymers, and we propose that while the longer wavelength components of the VUV-radiation are absorbed by the bulk of the TrFE copolymer causing crosslinking, they are transmitted harmlessly in the PVDF homopolymer.

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NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.

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Harmful Algal Blooms (HABs) have become an important environmental concern along the western coast of the United States. Toxic and noxious blooms adversely impact the economies of coastal communities in the region, pose risks to human health, and cause mortality events that have resulted in the deaths of thousands of fish, marine mammals and seabirds. One goal of field-based research efforts on this topic is the development of predictive models of HABs that would enable rapid response, mitigation and ultimately prevention of these events. In turn, these objectives are predicated on understanding the environmental conditions that stimulate these transient phenomena. An embedded sensor network (Fig. 1), under development in the San Pedro Shelf region off the Southern California coast, is providing tools for acquiring chemical, physical and biological data at high temporal and spatial resolution to help document the emergence and persistence of HAB events, supporting the design and testing of predictive models, and providing contextual information for experimental studies designed to reveal the environmental conditions promoting HABs. The sensor platforms contained within this network include pier-based sensor arrays, ocean moorings, HF radar stations, along with mobile sensor nodes in the form of surface and subsurface autonomous vehicles. FreewaveTM radio modems facilitate network communication and form a minimally-intrusive, wireless communication infrastructure throughout the Southern California coastal region, allowing rapid and cost-effective data transfer. An emerging focus of this project is the incorporation of a predictive ocean model that assimilates near-real time, in situ data from deployed Autonomous Underwater Vehicles (AUVs). The model then assimilates the data to increase the skill of both nowcasts and forecasts, thus providing insight into bloom initiation as well as the movement of blooms or other oceanic features of interest (e.g., thermoclines, fronts, river discharge, etc.). From these predictions, deployed mobile sensors can be tasked to track a designated feature. This focus has led to the creation of a technology chain in which algorithms are being implemented for the innovative trajectory design for AUVs. Such intelligent mission planning is required to maneuver a vehicle to precise depths and locations that are the sites of active blooms, or physical/chemical features that might be sources of bloom initiation or persistence. The embedded network yields high-resolution, temporal and spatial measurements of pertinent environmental parameters and resulting biology (see Fig. 1). Supplementing this with ocean current information and remotely sensed imagery and meteorological data, we obtain a comprehensive foundation for developing a fundamental understanding of HAB events. This then directs labor- intensive and costly sampling efforts and analyses. Additionally, we provide coastal municipalities, managers and state agencies with detailed information to aid their efforts in providing responsible environmental stewardship of their coastal waters.

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The expanding interest in electrospinning fibers for bioengineering includes a significant use of polyesters, including poly(3-caprolactone) (PCL). This review summarizes literature on PCL and selected blends, and provides extensive descriptions of the broad range of parameters used in manufacturing such electrospun fibers. Furthermore the chemical, physical and biological approaches for characterizing the electrospun material are described and opinions offered on important information to include in future publications with this electrospun material.

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Iron (Fe) biogeochemistry is potentially of environmental significance in plantation-forested, subtropical coastal ecosystems where soil disturbance and seasonal water logging may lead to elevation of Fe mobilization and associated water quality deterioration. Using wet-chemical extraction and laboratory cultivation, we examined the occurrence of Fe forms and associated bacterial populations in diverse soils of a representative subtropical Australian coastal catchment (Poona Creek). Total reactive Fe was abundant throughout 0e30 cm soil cores, consisting primarily of crystalline forms in well-drained sand soils and water-logged loam soils, whereas in water-logged, low clay soils, over half of total reactive Fe was present in poorly-crystalline forms due to organic and inorganic complexation, respectively. Forestry practices such as plantation clear-felling and replanting, seasonal water logging and mineral soil properties significantly impacted soil organic carbon (C), potentially-bioavailable Fe pools and densities of S-, but not Fe-, bacterial populations. Bacterial Fe(III) reduction and abiotic Fe(II) oxidation, as well as chemolithotrophic S oxidation and aerobic, heterotrophic respiration were integral to catchment terrestrial FeeC cycling. This work demonstrates bacterial involvement in terrestrial Fe cycling in a subtropical coastal circumneutral-pH ecosystem.

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Blooms of the toxic cyanobacterium majuscula Lyngbya in the coastal waters of southeast Queensland have caused adverse impacts on both environmental health and human health, and on local economies such as fishing and tourism. A number of studies have confirmed that the main limiting nutrients (“nutrients of concern”) that contribute to these blooms area Fe, DOC, N, P and also pH. This study is conducted to establish the distribution of these parameters in a typical southeast Queensland coastal setting. The study maps the geochemistry of shallow groundwater in the mainland Pumicestone catchment with an emphasis on the nutrients of concern to understand how these nutrients relate to aquifer materials, landuse and anthropogenic activities. The results of the study form a GIS information layer which will be incorporated into a larger GIS model being produced by Queensland Department of Environment and Resource Management (DERM) to support landuse management to avoid/minimize blooms of Lyngbya in Moreton Bay, southeast Queensland, and other similar settings. A total of 38 boreholes were established in the mainland Pumicestone region and four sampling rounds of groundwater carried out in both dry and wet conditions. These groundwater samples were measured in the field for physico-chemical parameters, and in the laboratory analyses for the nutrients of concern, and other major and minor ions. Aquifer materials were confirmed using the Geological Survey of Queensland digital geology map, and geomaterials were assigned to seven categories which are A (sands), B (silts, sandy silts), C (estuarine mud, silts), D (humid soils), E (alluvium), F (sandstone) and G (other bedrock). The results of the water chemistry were examined by use of the software package AquaChem/AqQA, and divided into six groundwater groups, based on groundwater chemical types and location of boreholes. The type of aquifer material and location, and proximity to waterways was found to be important because they affected physico-chemical properties and concentrations of nutrients of concern and dissolved ions. The analytical results showed that iron concentrations of shallow groundwaters were high due to acid sulfate soils, and also mud and silt, but were lower in sand materials. DOC concentrations of these shallow groundwaters in the sand material were high probably due to rapid infiltration. In addition, DOC concentrations in some boreholes were high because they were installed in organic rich wetlands. The pH values of boreholes were from acidic to near neutral; some boreholes with pH values were low (< 4), showing acid sulfate soils in these boreholes. Concentrations of total nitrogen and total phosphorus of groundwaters were generally low, and the main causes of elevated concentrations of total nitrogen and total phosphorus are largely due to animal and human wastes and tend to be found in localized source areas. Comparison of the relative percentage of nitrogen species (NH3/NH4< Org-N, NO3-N and NO2-N) demonstrated that they could be related to sources such as animal waste, residential and agricultural fertilizers, forest and vegetation, mixed residents and farms, and variable setting and vegetation covers. Total concentrations of dissolved ions in sampling round 3 (dry period) were higher than those in sampling round 2 (wet period) due to both evaporation of groundwater in the dry period and the dilution of rainfall in the wet period. This showed that the highest concentrations of nutrients of concern were due to acid sulfate soils, aquifer materials, landuse and anthropogenic activities and were typically in aquifer materials of E (alluvium) and C (estuarine muds) and locations of Burpengary, Caboolture, and Glass Mountain catchments.

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Sexual maturation and mating in insects are generally accompanied by major physiological and behavioural changes. Many of these changes are related to the need to locate a mate and subsequently, in the case of females, to switch from mate searching to oviposition behaviour. The prodigious reproductive capacity of the Mediterranean fruit fly, Ceratitis capitata, is one of the factors that has led to its success as an invasive pest species. To identify the molecular changes related to maturation and mating status in male and female medfly, a microarray-based gene expression approach was used to compare the head transcriptomes of sexually immature, mature virgin, and mated individuals. Attention was focused on the changes in abundance of transcripts related to reproduction, behaviour, sensory perception of chemical stimulus, and immune system processes. Broad transcriptional changes were recorded during female maturation, while post-mating transcriptional changes in females were, by contrast, modest. In male medfly, transcriptional changes were consistent both during maturation and as a consequence of mating. Of particular note was the lack of the mating-induced immune responses that have been recorded for Drosophila melanogaster, that may be due to the different reproductive strategies of these species. This study, in addition to increasing our understanding of the molecular machinery behind maturation and mating in the medfly, has identified important gene targets that might be useful in the future management of this pest.

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Carbon nanotubes (CNTs), experimentally observed for the first time twenty years ago, have triggered an unprecedented research effort, on the account of their astonishing structural, mechanical and electronic properties. Unfortunately, the current inability in predicting the CNTs’ properties and the difficulty in controlling their position on a substrate are often limiting factors for the application of this material in actual devices. This research aims at the creation of specific methodologies for controlled synthesis of CNTs, leading to effectively employ them in various fields of electronics, e.g. photovoltaics. Focused Ion Beam (FIB) patterning of Si surfaces is here proposed as a means for ordering the assembly of vertical-aligned CNTs. With this technique, substrates with specific nano-structured morphologies have been prepared, enabling a high degree of control over CNTs’ position and size. On these nano-structured substrates, the growth of CNTs has been realized by chemical vapor deposition (CVD), i.e. thermal decomposition of hydrocarbon gases over a heated catalyst. The most common materials used as catalysts in CVD are transition metals like Fe and Ni; however, their presence in the CNT products often results in shortcomings for electronic applications, especially for those based on silicon, being the metallic impurities incompatible with very-large-scale integration (VLSI) technology. In the present work the role of Ge dots as an alternative catalysts for CNTs synthesis on Si substrates has been thoroughly assessed, finding a close connection between the catalytic activity of such material and the CVD conditions, which can affect both size and morphology of the dots. Successful CNT growths from Ge dots have been obtained by CVD at temperatures ranging from 750 to 1000°C, with mixtures of acetylene and hydrogen in an argon carrier gas. The morphology of the Si surface is observed to play a crucial role for the outcome of the CNT synthesis: natural (i.e. chemical etching) and artificial (i.e. FIB patterning, nanoindentation) means of altering this morphology in a controlled way have been then explored to optimize the CNTs yield. All the knowledge acquired in this study has been finally applied to synthesize CNTs on transparent conductive electrodes (indium-tin oxide, ITO, coated glasses), for the creation of a new class of anodes for organic photovoltaics. An accurate procedure has been established which guarantees a controlled inclusion of CNTs on ITO films, preserving their optical and electrical properties. By using this set of conditions, a CNTenhanced electrode has been built, contributing to improve the power conversion efficiency of polymeric solar cells.

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Bacterially mediated iron redox cycling exerts a strong influence on groundwater geochemistry, but few studies have investigated iron biogeochemical processes in coastal alluvial aquifers from a microbiological viewpoint. The shallow alluvial aquifer located adjacent to Poona estuary on the subtropical Southeast Queensland coast represents a redox-stratified system where iron biogeochemical cycling potentially affects water quality. Using a 300 m transect of monitoring wells perpendicular to the estuary, we examined groundwater physico-chemical conditions and the occurrence of cultivable bacterial populations involved in iron (and manganese, sulfur) redox reactions in this aquifer. Results showed slightly acidic and near-neutral pH, suboxic conditions and an abundance of dissolved iron consisting primarily of iron(II) in the majority of wells. The highest level of dissolved iron(III) was found in a well proximal to the estuary most likely a result of iron curtain effects due to tidal intrusion. A number of cultivable, (an)aerobic bacterial populations capable of diverse carbon, iron, or sulfur metabolism coexisted in groundwater redox transition zones. Our findings indicated aerobic, heterotrophic respiration and bacterially mediated iron/sulfur redox reactions were integral to carbon cycling in the aquifer. High abundances of dissolved iron and cultivable iron and sulfur bacterial populations in estuary-adjacent aquifers have implications for iron transport to marine waters. This study demonstrated bacterially mediated iron redox cycling and associated biogeochemical processes in subtropical coastal groundwaters using culture-based methods.

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The objective of this research was to investigate the effect of suspension parameters on dynamic load-sharing of longitudinal-connected air suspensions of a tri-axle semi-trailer. A novel nonlinear model of a multi-axle semi-trailer with longitudinal-connected air suspension was formulated based on fluid mechanics and thermodynamics and was validated through test results. The effects of suspension parameters on dynamic load-sharing and road-friendliness of the semi-trailer were analyzed. Simulation results indicate that the road-friendliness metric DLC (Dynamic Load Coefficient), is generally in accordance with the load-sharing metric - DLSC (Dynamic Load Sharing Coefficient). When the static height or static pressure increases, the DLSC optimization ratio declines monotonically. The effect of employing larger air lines and connectors on the DLSC optimization ratio gives varying results as road roughness increases and as driving speed increases. The results also indicate that if the air line diameter is always assumed to be larger than the connector diameter, the influence of air line diameter on load-sharing is more significant than that of the connector.

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In 1991, McNabb introduced the concept of mean action time (MAT) as a finite measure of the time required for a diffusive process to effectively reach steady state. Although this concept was initially adopted by others within the Australian and New Zealand applied mathematics community, it appears to have had little use outside this region until very recently, when in 2010 Berezhkovskii and coworkers rediscovered the concept of MAT in their study of morphogen gradient formation. All previous work in this area has been limited to studying single–species differential equations, such as the linear advection–diffusion–reaction equation. Here we generalise the concept of MAT by showing how the theory can be applied to coupled linear processes. We begin by studying coupled ordinary differential equations and extend our approach to coupled partial differential equations. Our new results have broad applications including the analysis of models describing coupled chemical decay and cell differentiation processes, amongst others.