1000 resultados para Hydrochemical processes


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An estuary is formed at the mouth of a river where the tides meet a freshwater flow and it may be classified as a function of the salinity distribution and density stratification. An overview of the broad characteristics of the estuaries of South-East Queensland(Australia) is presented herein, where the small peri-urban estuaries may provide an useful indicator of potential changes which might occur in larger systems with growing urbanisation. Small peri-urban estuaries exhibits many key hydrological features and associated with ecosystem types of larger estuaries, albeit at smaller scales, often with a greater extent of urban development as a proportion of catchment area. We explore the potential for some smaller peri-urban estuaries to be used as natural laboratories to gain some much needed information on the estuarine processes, although any dynamics similarity is presently limited by critical absence of in-depth physical investigation in larger estuarine systems. The absence of the detailed turbulence and sedimentary data hampers the understanding and modelling of the estuarine zones. The interactions between the various stake holders are likely to define the vision for the future of South-East Queensland's peri-urban estuaries. This will require a solid understanding of the bio-physical function and capacity of the peri-urban estuaries. Based upon the knowledge gap, it is recommended that an adaptive trial and error approach be adopted for the future of investigation and management strategies.

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Groundwater flow models are usually characterized as being either transient flow models or steady state flow models. Given that steady state groundwater flow conditions arise as a long time asymptotic limit of a particular transient response, it is natural for us to seek a finite estimate of the amount of time required for a particular transient flow problem to effectively reach steady state. Here, we introduce the concept of mean action time (MAT) to address a fundamental question: How long does it take for a groundwater recharge process or discharge processes to effectively reach steady state? This concept relies on identifying a cumulative distribution function, $F(t;x)$, which varies from $F(0;x)=0$ to $F(t;x) \to \infty$ as $t\to \infty$, thereby providing us with a measurement of the progress of the system towards steady state. The MAT corresponds to the mean of the associated probability density function $f(t;x) = \dfrac{dF}{dt}$, and we demonstrate that this framework provides useful analytical insight by explicitly showing how the MAT depends on the parameters in the model and the geometry of the problem. Additional theoretical results relating to the variance of $f(t;x)$, known as the variance of action time (VAT), are also presented. To test our theoretical predictions we include measurements from a laboratory–scale experiment describing flow through a homogeneous porous medium. The laboratory data confirms that the theoretical MAT predictions are in good agreement with measurements from the physical model.

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Jakarta, Indonesia’s chronic housing shortage poses multiple challenges for contemporary policy-makers. While it may be in the city’s interest to increase the availability of housing, there is limited land to do so. Market pressures, in tandem with government’s desire for housing availability, demand consideration of even marginal lands, such as those within floodplains, for development. Increasingly, planning for a flood resilient Jakarta is complicated by a number of factors, including: the city is highly urbanized and land use data is limited; flood management is technically complex, creating potential barriers to engagement for both decision-makers and the public; inherent uncertainty exists throughout modelling efforts, central to management; and risk and liability for infrastructure investments is unclear. These obstacles require localized watershed-level participatory planning to address risks of flooding where possible and reduce the likelihood that informal settlements occur in areas of extreme risk. This paper presents a preliminary scoping study for determination of an effective participatory planning method to encourage more resilient development. First, the scoping study provides background relevant to the challenges faced in planning for contemporary Jakarta. Second, the study examines the current use of decision-support tools, such as Geographic Information Systems (GIS), in planning for Jakarta. Existing capacity in the use of GIS allows for consideration of the use of an emerging method of community consultation - Multi-Criteria Decision-Making (MCDM) support systems infused with geospatial information - to aid in engagement with the public and improve decision-making outcomes. While these methods have been used in Australia to promote stakeholder engagement in urban intensification, the planned research will be an early introduction of the method to Indonesia. As a consequence of this intervention, it is expected that planning activities will result in a more resilient city, capable of engaging with disaster risk management in a more effective manner.

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The importance of applying unsaturated soil mechanics to geotechnical engineering design has been well understood. However, the consumption of time and the necessity for a specific laboratory testing apparatus when measuring unsaturated soil properties have limited the application of unsaturated soil mechanics theories in practice. Although methods for predicting unsaturated soil properties have been developed, the verification of these methods for a wide range of soil types is required in order to increase the confidence of practicing engineers in using these methods. In this study, a new permeameter was developed to measure the hydraulic conductivity of unsaturated soils using the steady-state method and directly measured suction (negative pore-water pressure) values. The apparatus is instrumented with two tensiometers for the direct measurement of suction during the tests. The apparatus can be used to obtain the hydraulic conductivity function of sandy soil over a low suction range (0-10 kPa). Firstly, the repeatability of the unsaturated hydraulic conductivity measurement, using the new permeameter, was verified by conducting tests on two identical sandy soil specimens and obtaining similar results. The hydraulic conductivity functions of the two sandy soils were then measured during the drying and wetting processes of the soils. A significant hysteresis was observed when the hydraulic conductivity was plotted against the suction. However, the hysteresis effects were not apparent when the conductivity was plotted against the volumetric water content. Furthermore, the measured unsaturated hydraulic conductivity functions were compared with predictions using three different predictive methods that are widely incorporated into numerical software. The results suggest that these predictive methods are capable of capturing the measured behavior with reasonable agreement.

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Energy prices are highly volatile and often feature unexpected spikes. It is the aim of this paper to examine whether the occurrence of these extreme price events displays any regularities that can be captured using an econometric model. Here we treat these price events as point processes and apply Hawkes and Poisson autoregressive models to model the dynamics in the intensity of this process.We use load and meteorological information to model the time variation in the intensity of the process. The models are applied to data from the Australian wholesale electricity market, and a forecasting exercise illustrates both the usefulness of these models and their limitations when attempting to forecast the occurrence of extreme price events.

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Packaged software is pre-built with the intention of licensing it to users in domestic settings and work organisations. This thesis focuses upon the work organisation where packaged software has been characterised as one of the latest ‘solutions’ to the problems of information systems. The study investigates the packaged software selection process that has, to date, been largely viewed as objective and rational. In contrast, this interpretive study is based on a 21⁄2 year long field study of organisational experiences with packaged software selection at T.Co, a consultancy organisation based in the United Kingdom. Emerging from the iterative process of case study and action research is an alternative theory of packaged software selection. The research argues that packaged software selection is far from the rationalistic and linear process that previous studies suggest. Instead, the study finds that aspects of the traditional process of selection incorporating the activities of gathering requirements, evaluation and selection based on ‘best fit’ may or may not take place. Furthermore, even where these aspects occur they may not have equal weight or impact upon implementation and usage as may be expected. This is due to the influence of those multiple realities which originate from the organisational and market environments within which packages are created, selected and used, the lack of homogeneity in organisational contexts and the variously interpreted characteristics of the package in question.

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This paper aims to contribute to an understanding of what actually takes place during consulting engagements. It draws on data collected from a qualitative case study of eight engagements by a niche consultancy in Australia to describe how consultants actively engage boundary crossing processes to address knowledge boundaries encountered during formal interactions with clients. While consultants actively managed knowledge boundary processes during interactions, by applying techniques such as evoking an ‘ideal state’ for clients, the engagements also yielded many missed opportunities for knowledge transformation.

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Mathematical descriptions of birth–death–movement processes are often calibrated to measurements from cell biology experiments to quantify tissue growth rates. Here we describe and analyze a discrete model of a birth–death-movement process applied to a typical two–dimensional cell biology experiment. We present three different descriptions of the system: (i) a standard mean–field description which neglects correlation effects and clustering; (ii) a moment dynamics description which approximately incorporates correlation and clustering effects, and; (iii) averaged data from repeated discrete simulations which directly incorporates correlation and clustering effects. Comparing these three descriptions indicates that the mean–field and moment dynamics approaches are valid only for certain parameter regimes, and that both these descriptions fail to make accurate predictions of the system for sufficiently fast birth and death rates where the effects of spatial correlations and clustering are sufficiently strong. Without any method to distinguish between the parameter regimes where these three descriptions are valid, it is possible that either the mean–field or moment dynamics model could be calibrated to experimental data under inappropriate conditions, leading to errors in parameter estimation. In this work we demonstrate that a simple measurement of agent clustering and correlation, based on coordination number data, provides an indirect measure of agent correlation and clustering effects, and can therefore be used to make a distinction between the validity of the different descriptions of the birth–death–movement process.

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Construction contracts often provide that the decision of an independent certifier is final and binding. The effect of a contractual term like this has been debated in the courts over time. This paper considers the binding nature of certificates in the context of traditional construction contract arrangements and also considers the implications for more complex contracts like those entered into to facilitate public private partnerships. This article considers the response of the courts and the drafting implications and argues that a different focus would be advantageous.

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The ability of metals to store or trap considerable amounts of energy, and thus exist in a non-equilibrium or metastable state, is very well known in metallurgy; however, such behaviour, which is intimately connected with the defect character of metals, has been largely ignored in noble metal surface electrochemistry. Techniques for generating unusually high energy surface states for gold, and the unusual voltammetric responses of such states, are outlined. The surprisingly high (and complex) electrocatalytic activity of gold in aqueous media is attributed to the presence of a range of such non-equilibrium states as the vital entities at active sites on conventional gold surfaces. The possible relevance of these ideas to account for the remarkable catalytic activity of oxide-supported gold microparticles is briefly outlined.

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Semi-conducting phase I CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which is of considerable interest as a switching device for memory storage materials, can be electrocrystallized from CH3CN via two distinctly different pathways when TCNQ is reduced to TCNQ˙− in the presence of [Cu(MeCN)4]+. The first pathway, identified in earlier studies, occurs at potentials where TCNQ is reduced to TCNQ˙− and involves a nucleation–growth mechanism at preferred sites on the electrode to produce arrays of well separated large branched needle-shaped phase I CuTCNQ crystals. The second pathway, now identified at more negative potentials, generates much smaller needle-shaped phase I CuTCNQ crystals. These electrocrystallize on parts of the surface not occupied in the initial process and give rise to film-like characteristics. This process is attributed to the reduction of Cu+[(TCNQ˙−)(TCNQ)] or a stabilised film of TCNQ via a solid–solid conversion process, which also involves ingress of Cu+via a nucleation–growth mechanism. The CuTCNQ surface area coverage is extensive since it occurs at all areas of the electrode and not just at defect sites that dominate the crystal formation sites for the first pathway. Infrared spectra, X-ray diffraction, surface plasmon resonance, quartz crystal microbalance, scanning electron microscopy and optical image data all confirm that two distinctly different pathways are available to produce the kinetically-favoured and more highly conducting phase I CuTCNQ solid, rather than the phase II material.

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Electrochemical processes in mesoporous TiO2-Nafion thin films deposited on indium tin oxide (ITO) electrodes are inherently complex and affected by capacitance, Ohmic iR-drop, RC-time constant phenomena, and by potential and pH-dependent conductivity. In this study, large-amplitude sinusoidally modulated voltammetry (LASMV) is employed to provide access to almost purely Faradaic-based current data from second harmonic components, as well as capacitance and potential domain information from the fundamental harmonic for mesoporous TiO2-Nafion film electrodes. The LASMV response has been investigated with and without an immobilized one-electron redox system, ferrocenylmethyltrimethylammonium+. Results clearly demonstrate that the electron transfer associated with the immobilized ferrocene derivative follows two independent pathways i) electron hopping within the Nafion network and ii) conduction through the TiO2 backbone. The pH effect on the voltammetric response for the TiO2 reduction pathway (ii) can be clearly identified in the 2nd harmonic LASMV response with the diffusion controlled ferrocene response (i) acting as a pH independent reference. Application of second harmonic data derived from LASMV measurement, because of the minimal contribution from capacitance currents, may lead to reference-free pH sensing with systems like that found for ferrocene derivatives.

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Unlike the case with other divalent transition metal M\[TCNQ](2)(H(2)O)(2) (M = Fe, Co, Ni) analogues, the electrochemically induced solid-solid phase interconversion of TCNQ microcrystals (TCNQ = 7,7,8,8-tetracyanoquinodimethane) to Mn\[TCNQ](2)(H(2)O)(2) occurs via two voltammetrically distinct, time dependent processes that generate the coordination polymer in nanofiber or rod-like morphologies. Careful manipulation of the voltammetric scan rate, electrolysis time, Mn(2+)((aq)) concentration, and the method of electrode modification with solid TCNQ allows selective generation of either morphology. Detailed ex situ spectroscopic (IR, Raman), scanning electron microscopy (SEM), and X-ray powder diffraction (XRD) characterization clearly establish that differences in the electrochemically synthesized Mn-TCNQ material are confined to morphology. Generation of the nanofiber form is proposed to take place rapidly via formation and reduction of a Mn-stabilized anionic dimer intermediate, \[(Mn(2+))(TCNQ-TCNQ)(2)(*-)], formed as a result of radical-substrate coupling between TCNQ(*-) and neutral TCNQ, accompanied by ingress of Mn(2+) ions from the aqueous solution at the triple phase TCNQ/electrode/electrolyte boundary. In contrast, formation of the nanorod form is much slower and is postulated to arise from disproportionation of the \[(Mn(2+))(TCNQ-TCNQ)(*-)(2)] intermediate. Thus, identification of the time dependent pathways via the solid-solid state electrochemical approach allows the crystal size of the Mn\[TCNQ](2)(H(2)O)(2) material to be tuned and provides new mechanistic insights into the formation of different morphologies.

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The creation of electrocatalysts based on noble metals has received a significant amount of research interest due to their extensive use as fuel cell catalysts and electrochemical sensors. There have been many attempts to improve the activity of these metals through creating nanostructures, as well as post-synthesis treatments based on chemical, electrochemical, sonochemical and thermal approaches. In many instances these methods result in a material with active surface states, which can be considered to be adatoms or clusters of atoms on the surface that have a low lattice co-ordination number making them more prone to electrochemical oxidation at a wide range of potentials that are significantly less positive than those of their bulk metal counterparts. This phenomenon has been termed pre-monolayer oxidation and has been reported to occur on a range of metallic surfaces. In this work we present findings on the presence of active sites on Pd that has been: evaporated as a thin film; electrodeposited as nanostructures; as well as commercially available Pd nanoparticles supported on carbon. Significantly, advantage is taken of the low oxidation potential of these active sites whereby bimetallic surfaces are created by the spontaneous deposition of Ag from AgNO3 to generate Pd/Ag surfaces. Interestingly this approach does not increase the surface area of the original metal but has significant implications for its further use as an electrode material. It results in the inhibition or promotion of electrocatalytic activity which is highly dependent on the reaction of interest. As a general approach the decoration of active catalytic materials with less active metals for a particular reaction also opens up the possibility of investigating the role of the initially present active sites on the surface and identifying the degree to which they are responsible for electrocatalytic activity.

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This research explores the relationship between international entrepreneurship characteristics and the use of Internet capabilities for the international business processes of the firm. It has been suggested, that the accumulation of a firms Internet capability can assist international operations, especially when operating in fast changing dynamic Internet environments. However, international entrepreneurship characteristics which are seen as a precursor to leveraging Internet capabilities are still vague. Given this finding, eight case studies of small and medium sized travel and tourism firms were selected to investigate the influence of international entrepreneurship characteristics, and Internet capabilities for international business processes. Based on the eight in-depth case studies, the results signify that successful international entrepreneurial firms which encompass high levels of international innovativeness and proactiveness behaviour integrate Internet capabilities to a greater degree. Our findings also indicate that the prior international business experience, international risk-taking propensity and international networking characteristics are not necessarily precursors to successful integration of Internet capabilities for international business processes. On the contrary, international business experience and international networks actually lead to a reliance on traditional mechanisms of internationalisation and can dilute the development of Internet capabilities for international business processes.