Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O – a mineral found in lithium bearing pegmatites

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O from Boa Vista mine, Galiléia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm−1 are assigned to the symmetric stretching mode of and units. Raman bands at 548, 564, 599 and 634 cm−1 are assigned to the ν4 bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm−1 and infrared bands at 2623, 2838, 3136 and 3185 cm−1 are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed.

Vibrational spectroscopic characterization of the phosphate mineral hureaulite – (Mn, Fe)5(PO4)2(HPO4)2·4(H2O)

This research was done on hureaulite samples from the Cigana claim, a lithium bearing pegmatite with triphylite and spodumene. The mine is located in Conselheiro Pena, east of Minas Gerais. Chemical analysis was carried out by Electron Microprobe analysis and indicated a manganese rich phase with partial substitution of iron. The calculated chemical formula of the studied sample is: (Mn3.23, Fe1.04, Ca0.19, Mg0.13)(PO4)2.7(HPO4)2.6(OH)4.78. The Raman spectrum of hureaulite is dominated by an intense sharp band at 959 cm−1 assigned to PO stretching vibrations of HPO42− units. The Raman band at 989 cm−1 is assigned to the PO43− stretching vibration. Raman bands at 1007, 1024, 1047, and 1083 cm−1 are attributed to both the HOP and PO antisymmetric stretching vibrations of HPO42− and PO43− units. A set of Raman bands at 531, 543, 564 and 582 cm−1 are assigned to the ν4 bending modes of the HPO42− and PO43− units. Raman bands observed at 414, and 455 cm−1 are attributed to the ν2 HPO42− and PO43− units. The intense A series of Raman and infrared bands in the OH stretching region are assigned to water stretching vibrations. Based upon the position of these bands hydrogen bond distances are calculated. Hydrogen bond distances are short indicating very strong hydrogen bonding in the hureaulite structure. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral hureaulite to be understood.

Depth of focus of the human eye

In general optical systems, the range of distances over which the detector cannot detect any change in focus is called the depth-of-field. This may be specified by movement of the object or image planes, with the former being referred to as depth-of-field and the latter as depth-of-focus (DOF). Either term can be used in vision science, where we refer to changes in vergence which have the same value in both object and image space.

‘The health-location connection’: using GIS and social media on smartphones to track engagement with the Local urban environment for work, recreation, and physical activity

A technologically innovative study was undertaken across two suburbs in Brisbane, Australia, to assess socioeconomic differences in women's use of the local environment for work, recreation, and physical activity. Mothers from high and low socioeconomic suburbs were instructed to continue with usual daily routines, and to use mobile phone applications (Facebook Places, Twitter, and Foursquare) on their mobile phones to ‘check-in’ at each location and destination they reached during a one-week period. These smartphone applications are able to track travel logistics via built-in geographical information systems (GIS), which record participants’ points of latitude and longitude at each destination they reach. Location data were downloaded to Google Earth and excel for analysis. Women provided additional qualitative data via text regarding the reasons and social contexts of their travel. We analysed 2183 ‘check-ins’ for 54 women in this pilot study to gain quantitative, qualitative, and spatial data on human-environment interactions. Data was gathered on distances travelled, mode of transport, reason for travel, social context of travel, and categorised in terms of physical activity type – walking, running, sports, gym, cycling, or playing in the park. We found that the women in both suburbs had similar daily routines with the exception of physical activity. We identified 15% of ‘check-ins’ in the lower socioeconomic group as qualifying for the physical activity category, compared with 23% in the higher socioeconomic group. This was explained by more daily walking for transport (1.7kms to 0.2kms) and less car travel each week (28.km to 48.4kms) in the higher socioeconomic suburb. We ascertained insights regarding the socio-cultural influences on these differences via additional qualitative data. We discuss the benefits and limitations of using new technologies and Google Earth with implications for informing future physical and social aspects of urban design, and health promotion in socioeconomically diverse cities.

Heteroscedastic probabilistic linear discriminant analysis for manifold learning in video-based face recognition

To recognize faces in video, face appearances have been widely modeled as piece-wise local linear models which linearly approximate the smooth yet non-linear low dimensional face appearance manifolds. The choice of representations of the local models is crucial. Most of the existing methods learn each local model individually meaning that they only anticipate variations within each class. In this work, we propose to represent local models as Gaussian distributions which are learned simultaneously using the heteroscedastic probabilistic linear discriminant analysis (PLDA). Each gallery video is therefore represented as a collection of such distributions. With the PLDA, not only the within-class variations are estimated during the training, the separability between classes is also maximized leading to an improved discrimination. The heteroscedastic PLDA itself is adapted from the standard PLDA to approximate face appearance manifolds more accurately. Instead of assuming a single global within-class covariance, the heteroscedastic PLDA learns different within-class covariances specific to each local model. In the recognition phase, a probe video is matched against gallery samples through the fusion of point-to-model distances. Experiments on the Honda and MoBo datasets have shown the merit of the proposed method which achieves better performance than the state-of-the-art technique.

The molecular structure of the phosphate mineral chalcosiderite – a vibrational spectroscopic study

The mineral chalcosiderite with formula CuFe6(PO4)4(OH)8⋅4H2O has been studied by Raman spectroscopy and by infrared spectroscopy. A comparison of the chalcosiderite spectra is made with the spectra of turquoise. The spectra of the mineral samples are very similar in the 1200–900 cm−1 region but strong differences are observed in the 900–100 cm−1 region. The effect of substitution of Fe for Al in chalcosiderite shifts the bands to lower wave numbers. Factor group analysis (FGA) implies four OH stretching vibrations for both the water and hydroxyl units. Two bands ascribed to water are observed at 3276 and 3072 cm−1. Three hydroxyl stretching vibrations are observed. Calculations using a Libowitzky type formula show that the hydrogen bond distances of the water molecules are 2.745 and 2.812 Å which are considerably shorter than the values for the hydroxyl units 2.896, 2.917 and 2.978 Å. Two phosphate stretching vibrations at 1042 and 1062 cm−1 in line with the two independent phosphate units in the structure of chalcosiderite. Three bands are observed at 1102, 1159 and 1194 cm−1 assigned to the phosphate antisymmetric stretching vibrations. FGA predicts six bands but only three are observed due to accidental degeneracy. Both the ν2 and ν4 bending regions are complex. Four Raman bands observed at 536, 580, 598 and 636 cm−1 are assigned to the ν4 bending modes. Raman bands at 415, 420, 475 and 484 cm−1are assigned to the phosphate ν2 bending modes. Vibrational spectroscopy enables aspects of the molecular structure of chalcosiderite to be assessed.

The feral horse foot. Part A : observational study of the effect of environment on the morphometrics of the feet of 100 Australian feral horses

Aim To better understand the morphology of, and the effect of different travel patterns and varying substrate environments on, the feral horse foot to better manage the feet of domestic horses. Methods The left forefeet of 20 adult feral horses from each of five geographically separated populations in Australia (n = 100) were investigated. Populations were selected on the basis of substrate hardness under foot and the amount of travel typical for the population. Feet were radiographed and photographed and 40 morphometric measurements of each foot were obtained. Results Of the 40 parameters, 37 differed significantly (P < 0.05) among the populations, which suggested that substrate hardness and travel distance have an effect on foot morphology. Harder substrates and longer travel distances were associated with short hoof walls and minimal hoof wall flaring. Softer substrates and moderate travel distances were associated with long flared walls, similar to that of typical untrimmed feet of domestic horses. Conclusions The morphology of the feral horse foot appeared to be affected by the distance travelled and by the abrasive qualities and mechanical properties of the substrate under foot. There were marked differences in some conformation parameters between the feral horses in the current study and domestic horses in previous studies. Although the conformation of the feral horse foot may have some prescriptive value, concerns regarding abnormal foot anatomy warrant further investigation.

Thermogravimetric analysis of the copper silicate mineral dioptase Cu6[Si6O18]·6H2O

There have been a few studies on the thermal decomposition of dioptase Cu6[Si6O18]·6H2O. The results of these analyses are somewhat conflicting and the conclusions vary among these thermo-analytical studies. The objective of this research is to report the thermal analysis of dioptase from different origins and to show the mechanism of decomposition. Thermal decomposition occurs over a very wide temperature range from around 400 to 730 °C with the loss of water. Two additional mass loss steps are observed at around 793 and 835 °C with loss of oxygen. The infrared spectra of dioptase in the hydroxyl stretching region enables the hydrogen bond distances of water molecules in the dioptase structure to be calculated. The large variation in the hydrogen bond distances offers an explanation as to why the decomposition of dioptase with loss of water occurs over such a wide temperature range.

Dermal fibroblast infiltration of poly(ε-caprolactone) scaffolds fabricated by melt electrospinning in a direct writing mode

Melt electrospinning in a direct writing mode is a recent additive manufacturing approach to fabricate porous scaffolds for tissue engineering applications. In this study, we describe porous and cell-invasive poly (ε-caprolactone) scaffolds fabricated by combining melt electrospinning and a programmable x–y stage. Fibers were 7.5 ± 1.6 µm in diameter and separated by interfiber distances ranging from 8 to 133 µm, with an average of 46 ± 22 µm. Micro-computed tomography revealed that the resulting scaffolds had a highly porous (87%), three-dimensional structure. Due to the high porosity and interconnectivity of the scaffolds, a top-seeding method was adequate to achieve fibroblast penetration, with cells present throughout and underneath the scaffold. This was confirmed histologically, whereby a 3D fibroblast-scaffold construct with full cellular penetration was produced after 14 days in vitro. Immunohistochemistry was used to confirm the presence and even distribution of the key dermal extracellular matrix proteins, collagen type I and fibronectin. These results show that melt electrospinning in a direct writing mode can produce cell invasive scaffolds, using simple top-seeding approaches.

Simplified method for including spatial correlations in mean-field approximations

Biological systems involving proliferation, migration and death are observed across all scales. For example, they govern cellular processes such as wound-healing, as well as the population dynamics of groups of organisms. In this paper, we provide a simplified method for correcting mean-field approximations of volume-excluding birth-death-movement processes on a regular lattice. An initially uniform distribution of agents on the lattice may give rise to spatial heterogeneity, depending on the relative rates of proliferation, migration and death. Many frameworks chosen to model these systems neglect spatial correlations, which can lead to inaccurate predictions of their behaviour. For example, the logistic model is frequently chosen, which is the mean-field approximation in this case. This mean-field description can be corrected by including a system of ordinary differential equations for pair-wise correlations between lattice site occupancies at various lattice distances. In this work we discuss difficulties with this method and provide a simplication, in the form of a partial differential equation description for the evolution of pair-wise spatial correlations over time. We test our simplified model against the more complex corrected mean-field model, finding excellent agreement. We show how our model successfully predicts system behaviour in regions where the mean-field approximation shows large discrepancies. Additionally, we investigate regions of parameter space where migration is reduced relative to proliferation, which has not been examined in detail before, and our method is successful at correcting the deviations observed in the mean-field model in these parameter regimes.

Multicomponent charge transport in electrolyte solutions

The work presented in this thesis investigates the mathematical modelling of charge transport in electrolyte solutions, within the nanoporous structures of electrochemical devices. We compare two approaches found in the literature, by developing onedimensional transport models based on the Nernst-Planck and Maxwell-Stefan equations. The development of the Nernst-Planck equations relies on the assumption that the solution is infinitely dilute. However, this is typically not the case for the electrolyte solutions found within electrochemical devices. Furthermore, ionic concentrations much higher than those of the bulk concentrations can be obtained near the electrode/electrolyte interfaces due to the development of an electric double layer. Hence, multicomponent interactions which are neglected by the Nernst-Planck equations may become important. The Maxwell-Stefan equations account for these multicomponent interactions, and thus they should provide a more accurate representation of transport in electrolyte solutions. To allow for the effects of the electric double layer in both the Nernst-Planck and Maxwell-Stefan equations, we do not assume local electroneutrality in the solution. Instead, we model the electrostatic potential as a continuously varying function, by way of Poisson’s equation. Importantly, we show that for a ternary electrolyte solution at high interfacial concentrations, the Maxwell-Stefan equations predict behaviour that is not recovered from the Nernst-Planck equations. The main difficulty in the application of the Maxwell-Stefan equations to charge transport in electrolyte solutions is knowledge of the transport parameters. In this work, we apply molecular dynamics simulations to obtain the required diffusivities, and thus we are able to incorporate microscopic behaviour into a continuum scale model. This is important due to the small size scales we are concerned with, as we are still able to retain the computational efficiency of continuum modelling. This approach provides an avenue by which the microscopic behaviour may ultimately be incorporated into a full device-scale model. The one-dimensional Maxwell-Stefan model is extended to two dimensions, representing an important first step for developing a fully-coupled interfacial charge transport model for electrochemical devices. It allows us to begin investigation into ambipolar diffusion effects, where the motion of the ions in the electrolyte is affected by the transport of electrons in the electrode. As we do not consider modelling in the solid phase in this work, this is simulated by applying a time-varying potential to one interface of our two-dimensional computational domain, thus allowing a flow field to develop in the electrolyte. Our model facilitates the observation of the transport of ions near the electrode/electrolyte interface. For the simulations considered in this work, we show that while there is some motion in the direction parallel to the interface, the interfacial coupling is not sufficient for the ions in solution to be "dragged" along the interface for long distances.

Deep Raman Spectroscopy in the analytical forensic investigation of concealed substances

Deep Raman Spectroscopy is a domain within Raman spectroscopy consisting of techniques that facilitate the depth profiling of diffusely scattering media. Such variants include Time-Resolved Raman Spectroscopy (TRRS) and Spatially-Offset Raman Spectroscopy (SORS). A recent study has also demonstrated the integration of TRRS and SORS in the development of Time-Resolved Spatially-Offset Raman Spectroscopy (TR-SORS). This research demonstrates the application of specific deep Raman spectroscopic techniques to concealed samples commonly encountered in forensic and homeland security at various working distances. Additionally, the concepts behind these techniques are discussed at depth and prospective improvements to the individual techniques are investigated. Qualitative and quantitative analysis of samples based on spectral data acquired from SORS is performed with the aid of multivariate statistical techniques. By the end of this study, an objective comparison is made among the techniques within Deep Raman Spectroscopy based on their capabilities. The efficiency and quality of these techniques are determined based on the results procured which facilitates the understanding of the degree of selectivity for the deeper layer exhibited by the individual techniques relative to each other. TR-SORS was shown to exhibit an enhanced selectivity for the deeper layer relative to TRRS and SORS whilst providing spectral results with good signal-to-noise ratio. Conclusive results indicate that TR-SORS is a prospective deep Raman technique that offers higher selectivity towards deep layers and therefore enhances the non-invasive analysis of concealed substances from close range as well as standoff distances.

The influence of temperature and introduction point on the detection of Rhyzopertha dominica in stored grain

The presence of insect pests in grain storages throughout the supply chain is a significant problem for farmers, grain handlers, and distributors world-wide. Insect monitoring and sampling programmes are used in the stored grains industry for the detection and estimation of pest populations. At the low pest densities dictated by economic and commercial requirements, the accuracy of both detection and abundance estimates can be influenced by variations in the spatial structure of pest populations over short distances. Geostatistical analysis of Rhyzopertha dominica populations in 2 and 3 dimensions showed that insect numbers were positively correlated over short (0.5 cm) distances, and negatively correlated over longer (.10 cm) distances. At 35 C, insects were located significantly further from the grain surface than at 25 and 30 C. Dispersion metrics showed statistically significant aggregation in all cases. The observed heterogeneous spatial distribution of R. dominica may also be influenced by factors such as the site of initial infestation and disturbance during handling. To account for these additional factors, I significantly extended a simulation model that incorporates both pest growth and movement through a typical stored-grain supply chain. By incorporating the effects of abundance, initial infestation site, grain handling, and treatment on pest spatial distribution, I developed a supply chain model incorporating estimates of pest spatial distribution. This was used to examine several scenarios representative of grain movement through a supply chain, and determine the influence of infestation location and grain disturbance on the sampling intensity required to detect pest infestations at various infestation rates. This study has investigated the effects of temperature, infestation point, and grain handling on the spatial distribution and detection of R. dominica. The proportion of grain infested was found to be dependent upon abundance, initial pest location, and grain handling. Simulation modelling indicated that accounting for these factors when developing sampling strategies for stored grain has the potential to significantly reduce sampling costs while simultaneously improving detection rate, resulting in reduced storage and pest management cost while improving grain quality.

Infrared and Raman spectroscopic characterization of the phosphate mineral fairfieldite – Ca2(Mn2+,Fe2+)2(PO4)2·2(H2O)

Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the phosphate mineral fairfieldite. The Raman phosphate (PO4)3- stretching region shows strong differences between the fairfieldite phosphate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists with multiple (PO4)2- antisymmetric stretching vibrations observed, indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 600 cm-1 are assigned to v4 phosphate bending modes. Multiple bands in the 400–450 cm-1 region assigned to m2 phosphate bending modes provide further evidence of symmetry reduction of the phosphate anion. Three broadbands for fairfieldite are found at 3040, 3139 and 3271 cm-1 and are assigned to OH stretching bands. By using a Libowitzky empirical equation hydrogen bond distances of 2.658 and 2.730 A are estimated. Vibrational spectroscopy enables aspects of the molecular structure of the fairfieldite to be ascertained.

Career-path analysis using optimal matching and self-organizing maps

This paper is devoted to the analysis of career paths and employability. The state-of-the-art on this topic is rather poor in methodologies. Some authors propose distances well adapted to the data, but are limiting their analysis to hierarchical clustering. Other authors apply sophisticated methods, but only after paying the price of transforming the categorical data into continuous, via a factorial analysis. The latter approach has an important drawback since it makes a linear assumption on the data. We propose a new methodology, inspired from biology and adapted to career paths, combining optimal matching and self-organizing maps. A complete study on real-life data will illustrate our proposal.