A study of the oxygen electrochemistry of ruthenium and iridium

This thesis is concerned with an investigation of the anodic behaviour of ruthenium and iridium in aqueous solution and particularly of oxygen evolution on these metals. The latter process is of major interest in the large-scale production of hydrogen gas by the electrolysis of water. The presence of low levels of ruthenium trichloride ca. 10-4 mol dm-3 in acid solution give a considerable increase in the rate of oxygen evolution from platinum and gold, but not graphite, anodes. The mechanism of this catalytic effect was investigated using potential step and a.c. impedance technique. Earlier suggestions that the effect is due to catalysis by metal ions in solution were proved to be incorrect and it was shown that ruthenium species were incorporated into the surface oxide film. Changes in the oxidation state of these ruthenium species is probably responsible for the lowering of the oxygen overvoltage. Both the theoretical and practical aspects of the reaction were complicated by the fact that at constant potential the rates of both the catalysed and the uncatalysed oxygen evolution processes exhibit an appreciable, continuous decrease with either time or degree of oxidation of the substrate. The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface. The behaviour of iridium at higher anodic potentials in acid solution was investigated. Current-time curves at constant potential and Tafel plots suggested that a change in the mechanism of the oxygen evolution reaction occurs at ca. 1.8 V. Above this potential, corrosion of the metal occurred, giving rise to an absorbance in the visible spectrum of the electrolyte (λ max = 455 nm). It is suggested that the species involved was Ir(O2)2+. A similar investigation in the case of alkaline electrolyte gave no evidence for a change in mechanism at 1.8 V and corrosion of the iridium was not observed. Oxygen evolution overpotentials were much lower for iridium than for platinum in both acidic and alkaline solutions.

Ryanodine receptor expression in trophoblasts

Trophoblasts of the placenta are the frontline cells involved in communication and exchange of materials between the mother and fetus. Within trophoblasts, calcium signalling proteins are richly expressed. Intracellular free calcium ions are a key second messenger, regulating various cellular activities. Transcellular Ca2+ transport through trophoblasts is essential in fetal skeleton formation. Ryanodine receptors (RyRs) are high conductance cation channels that mediate Ca2+ release from intracellular stores to the cytoplasm. To date, the roles of RyRs in trophoblasts have not been reported. By use of reverse transcription PCR and western blotting, the current study revealed that RyRs are expressed in model trophoblast cell lines (BeWo and JEG-3) and in human first trimester and term placental villi. Immunohistochemistry of human placental sections indicated that both syncytiotrophoblast and cytotrophoblast cell layers were positively stained by antibodies recognising RyRs; likewise, expression of RyR isoforms was also revealed in BeWo and JEG-3 cells by immunofluorescence microscopy. In addition, changes in [Ca2+]i were observed in both BeWo and JEG-3 cells upon application of various RyR agonists and antagonists, using fura-2 fluorescent videomicroscopy. Furthermore, endogenous placental peptide hormones, namely angiotensin II, arginine vasopressin and endothelin 1, were demonstrated to increase [Ca2+]i in BeWo cells, and such increases were suppressed by RyR antagonists and by blockers of the corresponding peptide hormone receptors. These findings indicate that 1) multiple RyR subtypes are expressed in human trophoblasts; 2) functional RyRs in BeWo and JEG-3 cells response to both RyR agonists and antagonists; 3) RyRs in BeWo cells mediate Ca2+ release from intracellular store in response to the indirect stimulation by endogenous peptides. These observations suggest that RyR contributes to trophoblastic cellular Ca2+ homeostasis; trophoblastic RyRs are also involved in the functional regulation of human placenta by coupling to endogenous placental peptide-induced signalling pathways.

A knowledge management system to optimise comfort throughout the building life-cycle

Comfort is, in essence, satisfaction with the environment, and with respect to the indoor environment it is primarily satisfaction with the thermal conditions and air quality. Improving comfort has social, health and economic benefits, and is more financially significant than any other building cost. Despite this, comfort is not strictly managed throughout the building lifecycle. This is mainly due to the lack of an appropriate system to adequately manage comfort knowledge through the construction process into operation. Previous proposals to improve knowledge management have not been successfully adopted by the construction industry. To address this, the BabySteps approach was devised. BabySteps is an approach, proposed by this research, which states that for an innovation to be adopted into the industry it must be implementable through a number of small changes. This research proposes that improving the management of comfort knowledge will improve comfort. ComMet is a new methodology proposed by this research that manages comfort knowledge. It enables comfort knowledge to be captured, stored and accessed throughout the building life-cycle and so allowing it to be re-used in future stages of the building project and in future projects. It does this using the following: Comfort Performances – These are simplified numerical representations of the comfort of the indoor environment. Comfort Performances quantify the comfort at each stage of the building life-cycle using standard comfort metrics. Comfort Ratings - These are a means of classifying the comfort conditions of the indoor environment according to an appropriate standard. Comfort Ratings are generated by comparing different Comfort Performances. Comfort Ratings provide additional information relating to the comfort conditions of the indoor environment, which is not readily determined from the individual Comfort Performances. Comfort History – This is a continuous descriptive record of the comfort throughout the project, with a focus on documenting the items and activities, proposed and implemented, which could potentially affect comfort. Each aspect of the Comfort History is linked to the relevant comfort entity it references. These three components create a comprehensive record of the comfort throughout the building lifecycle. They are then stored and made available in a common format in a central location which allows them to be re-used ad infinitum. The LCMS System was developed to implement the ComMet methodology. It uses current and emerging technologies to capture, store and allow easy access to comfort knowledge as specified by ComMet. LCMS is an IT system that is a combination of the following six components: Building Standards; Modelling & Simulation; Physical Measurement through the specially developed Egg-Whisk (Wireless Sensor) Network; Data Manipulation; Information Recording; Knowledge Storage and Access.Results from a test case application of the LCMS system - an existing office room at a research facility - highlighted that while some aspects of comfort were being maintained, the building’s environment was not in compliance with the acceptable levels as stipulated by the relevant building standards. The implementation of ComMet, through LCMS, demonstrates how comfort, typically only considered during early design, can be measured and managed appropriately through systematic application of the methodology as means of ensuring a healthy internal environment in the building.

Characterisation and spectroscopy of laser-cooled atoms with an optical nanofibre

In this thesis, a magneto-optical trap setup is used to laser cool and confine a cloud of 85Rb. The cloud typically contains 108 atoms in a 1 mm3 volume at a temperature in the region of the Doppler Limit (146 _K for 85Rb). To study the cold cloud, a subwavelength optical fibre - a nanofibre, or ONF - is positioned inside the cloud. The ONF can be used in two ways. Firstly, it is an efficient fluorescence collection tool for the cold atoms. Loading times, lifetimes and temperatures can be measured by coupling the atomic fluorescence to the evanescent region of the ONF. Secondly, the ONF is used as a probe beam delivery tool using the evanescent field properties of the device, allowing one to perform spectroscopy on few numbers of near-surface atoms. With improvements in optical density of the cloud, this system is an ideal candidate in which to generate electromagnetically induced transparency and slow light. A theoretical study of the van der Waals and Casimir-Polder interactions between an atom and a dielectric surface is also presented in this work in order to understand their effects in the spectroscopy of near-surface atoms.

A distributed architecture for the monitoring and analysis of time series data

It is estimated that the quantity of digital data being transferred, processed or stored at any one time currently stands at 4.4 zettabytes (4.4 × 2 70 bytes) and this figure is expected to have grown by a factor of 10 to 44 zettabytes by 2020. Exploiting this data is, and will remain, a significant challenge. At present there is the capacity to store 33% of digital data in existence at any one time; by 2020 this capacity is expected to fall to 15%. These statistics suggest that, in the era of Big Data, the identification of important, exploitable data will need to be done in a timely manner. Systems for the monitoring and analysis of data, e.g. stock markets, smart grids and sensor networks, can be made up of massive numbers of individual components. These components can be geographically distributed yet may interact with one another via continuous data streams, which in turn may affect the state of the sender or receiver. This introduces a dynamic causality, which further complicates the overall system by introducing a temporal constraint that is difficult to accommodate. Practical approaches to realising the system described above have led to a multiplicity of analysis techniques, each of which concentrates on specific characteristics of the system being analysed and treats these characteristics as the dominant component affecting the results being sought. The multiplicity of analysis techniques introduces another layer of heterogeneity, that is heterogeneity of approach, partitioning the field to the extent that results from one domain are difficult to exploit in another. The question is asked can a generic solution for the monitoring and analysis of data that: accommodates temporal constraints; bridges the gap between expert knowledge and raw data; and enables data to be effectively interpreted and exploited in a transparent manner, be identified? The approach proposed in this dissertation acquires, analyses and processes data in a manner that is free of the constraints of any particular analysis technique, while at the same time facilitating these techniques where appropriate. Constraints are applied by defining a workflow based on the production, interpretation and consumption of data. This supports the application of different analysis techniques on the same raw data without the danger of incorporating hidden bias that may exist. To illustrate and to realise this approach a software platform has been created that allows for the transparent analysis of data, combining analysis techniques with a maintainable record of provenance so that independent third party analysis can be applied to verify any derived conclusions. In order to demonstrate these concepts, a complex real world example involving the near real-time capturing and analysis of neurophysiological data from a neonatal intensive care unit (NICU) was chosen. A system was engineered to gather raw data, analyse that data using different analysis techniques, uncover information, incorporate that information into the system and curate the evolution of the discovered knowledge. The application domain was chosen for three reasons: firstly because it is complex and no comprehensive solution exists; secondly, it requires tight interaction with domain experts, thus requiring the handling of subjective knowledge and inference; and thirdly, given the dearth of neurophysiologists, there is a real world need to provide a solution for this domain

Geochemistry, mineralogy, and chemical modeling of the acid crater lake of Kawah Ijen volcano, Indonesia

The Kawah Ijen volcano-with a record of phreatic eruptions-has its 1000 m wide crater filled with a lake that has existed for at least one century. At present, the lake waters are hot (T ≈ 37°C), strongly mineralized (TDS = 105 g/L) and extremely acidic (pH ≈ 0.4). By its volume, the Javanese lake is probably the largest accumulation in the world of such acidic waters. Mineralogy of the suspended solids within the lake waters suggests that concentrations of Si, Ca, Ti, and Ba are controlled by precipitation of silica, gypsum, anatase, and barite. Lake sediment is composed of chemical precipitates with composition similar to the suspended solids. Thermodynamic calculations predict that the lake waters have reached equilibrium with respect to α-cristobalite, barite, gypsum, anglesite, celestite, and amorphous silica, in agreement with the analytical observations. Significant concentrations of ferric iron suggest that the current lake waters are fairly oxidized. Sulfides are absent in the water column but are always present in the native S spherules that form porous aggregates which float on the lake. The presence of native S provides direct evidence of more reduced conditions at the lake floor where H2S is probably being injected into the lake. With progressive addition of H2S to the acid waters, native S, pyrite, and enargite are theoretically predicted to be saturated. Reactions between upward streaming H2S-bearing gases discharged by subaqueous fumaroles, and metals dissolved in the acidic waters could initiate precipitation of these sulfides. A model of direct absorption of hot magmatic gases into cool water accounts for the extreme acidity of the crater lake. Results show that strongly acidic, sulfate-rich solutions are formed under oxidizing conditions at high gas/water ratios. Reactions between the acidic fluids and the Ijen andesite were modeled to account for elevated cation concentrations in lake water. Current concentrations of conservative rockforming elements are produced by dissolution of approximately 60 g of andesite per kg of acid solution. Complete neutralization of the acid lake waters by reaction with the wallrock produces a theoretical alteration assemblage equivalent to that observed in volcano-hosted, acid-sulfate epithermal ore deposits. © 1994.

Bunching-induced optical nonlinearity and instability in cold atoms [Invited].

We report a new nonlinear optical process that occurs in a cloud of cold atoms at low-light-levels when the incident optical fields simultaneously polarize, cool, and spatially-organize the atoms. We observe an extremely large effective fifth-order nonlinear susceptibility of χ(⁵) = 7.6 × 10⁻¹⁵ (m/V)⁴, which results in efficient Bragg scattering via six-wave mixing, slow group velocities (∼ c/10⁵), and enhanced atomic coherence times (> 100 μs). In addition, this process is particularly sensitive to the atomic temperatures, and provides a new tool for in-situ monitoring of the atomic momentum distribution in an optical lattice. For sufficiently large light-matter couplings, we observe an optical instability for intensities as low as ∼ 1 mW/cm² in which new, intense beams of light are generated and result in the formation of controllable transverse optical patterns.

The impact of geologic variability on capacity and cost estimates for storing CO 2 in deep-saline aquifers

While numerous studies find that deep-saline sandstone aquifers in the United States could store many decades worth of the nation's current annual CO 2 emissions, the likely cost of this storage (i.e. the cost of storage only and not capture and transport costs) has been harder to constrain. We use publicly available data of key reservoir properties to produce geo-referenced rasters of estimated storage capacity and cost for regions within 15 deep-saline sandstone aquifers in the United States. The rasters reveal the reservoir quality of these aquifers to be so variable that the cost estimates for storage span three orders of magnitude and average>$100/tonne CO 2. However, when the cost and corresponding capacity estimates in the rasters are assembled into a marginal abatement cost curve (MACC), we find that ~75% of the estimated storage capacity could be available for<$2/tonne. Furthermore, ~80% of the total estimated storage capacity in the rasters is concentrated within just two of the aquifers-the Frio Formation along the Texas Gulf Coast, and the Mt. Simon Formation in the Michigan Basin, which together make up only ~20% of the areas analyzed. While our assessment is not comprehensive, the results suggest there should be an abundance of low-cost storage for CO 2 in deep-saline aquifers, but a majority of this storage is likely to be concentrated within specific regions of a smaller number of these aquifers. © 2011 Elsevier B.V.

Object files can be purely episodic.

Our ability to track an object as the same persisting entity over time and motion may primarily rely on spatiotemporal representations which encode some, but not all, of an object's features. Previous researchers using the 'object reviewing' paradigm have demonstrated that such representations can store featural information of well-learned stimuli such as letters and words at a highly abstract level. However, it is unknown whether these representations can also store purely episodic information (i.e. information obtained from a single, novel encounter) that does not correspond to pre-existing type-representations in long-term memory. Here, in an object-reviewing experiment with novel face images as stimuli, observers still produced reliable object-specific preview benefits in dynamic displays: a preview of a novel face on a specific object speeded the recognition of that particular face at a later point when it appeared again on the same object compared to when it reappeared on a different object (beyond display-wide priming), even when all objects moved to new positions in the intervening delay. This case study demonstrates that the mid-level visual representations which keep track of persisting identity over time--e.g. 'object files', in one popular framework can store not only abstract types from long-term memory, but also specific tokens from online visual experience.

The Effect of Wood Burial and Submersion on Decomposition: Implications for Reducing Carbon Emissions

Gemstone Team Carbon Sinks

Archaeological Excavations at 18AP14: The Victualling Warehouse Site, 77 Main Street, Annapolis, Maryland, 1982 - 1984

The Victualling Warehouse Site, located at 77 Main Street in Annapolis, Maryland, was excavated by Archaeology in Annapolis during the summers of 1982 and 1983 and the fall of 1984. Funding was provided by Historic Annapolis, Incorporated (now Historic Annapolis Foundation), the University of Maryland, the Maryland Committee for the Humanities, and the Maryland Commission on the Capital City. This site has been used for commercial and residential purposes since the 1740's. During the Revolution the warehouses were used as a victualling office to supply American troops. A fire in 1970 destroyed these buildings and the present structure, also used as a store, was built about twenty years later. Over the three years of excavation, a total of 36 5 foot by 5 foot units were excavated revealing several features, including the foundations of one of the eighteenth century warehouses.

Implementation of customer relationship management and inventory control software: a multiple case study of small retailers

Gemstone Team Small Business Solutions

Facial and expression recognition for the blind using computer vision

Gemstone Team FACE

A basic-systems approach to autobiographical memory

Memory for complex everyday events involving vision, hearing, smell, emotion, narrative, and language cannot be understood without considering the properties of the separate systems that process and store each of these forms of information. Using this premise as a starting point, my colleagues and I found that visual memory plays a central role in autobiographical memory: The strength of recollection of an event is predicted best by the vividness of its visual imagery, and a loss of visual memory causes a general amnesia. Examination of autobiographical memories in individuals with posttraumatic stress disorder (PTSD) suggests that the lack of coherence often noted in memories of traumatic events is not due to a lack of coherence either of the memory itself or of the narrative that integrates the memory into the life story. Rather, making the traumatic memory central to the life story correlates positively with increased PTSD symptoms. The basic-systems approach has yielded insights into autobiographical memory's phenomenology, neuropsychology, clinical disorders, and neural basis. Copyright © 2005 American Psychological Society.

Visual memory-deficit amnesia: a distinct amnesic presentation and etiology.

We describe a form of amnesia, which we have called visual memory-deficit amnesia, that is caused by damage to areas of the visual system that store visual information. Because it is caused by a deficit in access to stored visual material and not by an impaired ability to encode or retrieve new material, it has the otherwise infrequent properties of a more severe retrograde than anterograde amnesia with no temporal gradient in the retrograde amnesia. Of the 11 cases of long-term visual memory loss found in the literature, all had amnesia extending beyond a loss of visual memory, often including a near total loss of pretraumatic episodic memory. Of the 6 cases in which both the severity of retrograde and anterograde amnesia and the temporal gradient of the retrograde amnesia were noted, 4 had a more severe retrograde amnesia with no temporal gradient and 2 had a less severe retrograde amnesia with a temporal gradient.