A high-resolution infrared Fourier Transform Spectrometer (FTS) has been operational at the Toronto Atmospheric Observatory (TAO)since May 2002. An optimal estimation retrieval technique is used to analyse the observed spectra and provide regular total and partial column measurements of trace gases in the troposphere and stratosphere as part of the Network for the Detection of Atmospheric Composition Change. The quality of these results were assessed through two ground-based validation campaigns, comparisons with three satellite instruments, and comparison with a three-dimensional chemical transport model. The two ground-based campaigns involved two lower-resolution FTS instruments: the University of Toronto FTS and the Portable Atmospheric Research Interferometric Spectrometer for the Infrared. The first campaign took place over the course of four months and is the longest side-by-side intercomparison of ground-based FTS instruments, to date. The second campaign was more focused and involved all three instruments measuring over a two-week period. Simultaneous measurements of O3, HCl, N2O, and CH4 were recorded and average total column differences were all < 3.7% in the extended campaign, and < 4.5% in the focused campaign. Satellite-based comparisons were done with the SCanning and Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY), the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and the Optical Spectrograph and InfraRed Imager System (OSIRIS). Total column CO, CH4, and N2O compared with SCIAMACHY all had average differences < 10% with results from the TAO-FTS being as good as, or better, than that of other instruments. Validation with the ACE-FTS showed that average partial columns of O3, NO2, N2O, CH4, and HCl were within 10% while observations of CO and NO each had an average bias of about 25%. Comparisons of monthly average partial column O3 and NO2 with OSIRIS were highly correlated (R = 0.82-0.97) with monthly mean differences of < 3.1% for O3 and < 2.6% for NO2. Finally, comparisons with the GEOS-Chem chemical transport model revealed that the model consistently over-estimates tropospheric columns of CO and C2H6 observed at TAO. It was determined that the enhanced CO values were partially due to the North American emissions specified in the model, but more work must be done in the future if the source of this discrepancy is to be fully explained.

A brain-computer interface (BCI) allows individuals to communicate through the modulation of regional brain activity. Clinical near-infrared spectroscopy (NIRS) is used to monitor changes in cerebral blood oxygenation due to functional activation. It was hypothesized that visually-cued emotional induction tasks can elicit detectable activity in the prefrontal cortex. Data were collected from eleven participants as they performed positively and negatively-valenced emotional induction tasks. Baseline and activation trials were classified offline with accuracies from 75.0-96.7% after applying a feature selection algorithm to determine optimal performance parameters for each participant. Feature selection identified common discriminatory features across participants and relationships between performance parameters. Additionally, classification accuracy was used to quantify NIRS hemodynamic response latency. Significant increases in classification rates were found as early as 2.5 s after initial stimulus presentation. These results suggest the potential application of emotional induction as a NIRS-BCI control paradigm.

Near-infrared spectroscopy (NIRS) in an imaging technique that has gained much attention in brain-computer interfaces (BCIs). Previous NIRS-BCI studies have primarily employed temporal features, derived from the time course of hemodynamic activity, despite potential value contained in the spatial attributes of a response. In an initial offline study, we investigated the value of using joint spatial-temporal pattern classification with dynamic NIR topograms to differentiate intentional cortical activation from rest. With the inclusion of spatiotemporal features, we demonstrated a significant increase in achievable classification accuracies from those obtained using temporal features alone (p < 10-4). In a second study, we evaluated the feasibility of implementing joint spatial-temporal pattern classification in an online system. We developed an online system-paced NIRS-BCI, and were able to differentiate two cortical states with high accuracy (77.4±10.5%). Collectively, these findings demonstrate the value of including spatiotemporal features in the classification of functional NIRS data for BCI applications.

<p>Fluorochlorozirconate (FCZ) glasses are a member of heavy metal fluoride glasses, and are derived from a well known ZBLAN glass. In this work, halogen salts of europium (Eu²⁺) and samarium (Sm³⁺) are used as dopants in FCZ glasses. FCZ glasses doped with Eu²⁺ and Sm³⁺ can be used in high resolution x-ray imaging for tissue scanning, and have been shown to behave as storage phosphors and/or x-ray scintillators.</p> <p>Glass transition (T_g), heat capacity (C_p) and glass crystallization (T_c) properties of Eu²⁺ and Sm³⁺ doped and undoped FCZ glasses with different amounts of relative Cl concentration, that is, with respect to the total Cl and F concentration have been investigated by conventional differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC) techniques. MDSC experiments were performed at different heating rates to analyze the complex transitions and to get a better resolution of any overlapping transitions. The crystallization kinetics have also been studied by applying the Kissinger technique to multiple DSC scans in order to determine the thermal stability of FCZ glass samples used in this work. The apparent activation energy for the crystallization process was obtained by the crystallization peak temperature shift method in the conventional DSC mode. The specific heat capacity (C_p) has been measured as a function of composition, and the glass transition temperature (T_g) is evaluated from the smooth change in the heat capacity curve during the glass transformation. The observation of two possible glass transitions points to the presence of two phases in these FCZ glasses with higher relative Cl content.</p> <p>Optical transmission spectra of both doped and undoped FCZ glass samples have been measured by infrared spectroscopy and optical band gaps corresponding to an absorption coefficient of 10³ cm^-1 have been determined. A good correlation between X-ray luminescence and the glass structure is observed. While the integrated photoluminescence intensity increases linearly with the Sm³⁺ concentration, the integrated X-ray luminescence increases sublinearly. The importance of appropriate annealing conditions, such as temperature, time and ambient atmosphere, and their effect on the X-ray luminescence of rare earth (RE) doped FCZ glass samples have been investigated. Annealing conditions influence the formation of BaCl₂ nanocrystals in the glass and the properties of the resulting FCZ glass ceramics.</p>

A brain-computer interface (BCI) allows individuals to communicate through the modulation of regional brain activity. Clinical near-infrared spectroscopy (NIRS) is used to monitor changes in cerebral blood oxygenation due to functional activation. It was hypothesized that visually-cued emotional induction tasks can elicit detectable activity in the prefrontal cortex. Data were collected from eleven participants as they performed positively and negatively-valenced emotional induction tasks. Baseline and activation trials were classified offline with accuracies from 75.0-96.7% after applying a feature selection algorithm to determine optimal performance parameters for each participant. Feature selection identified common discriminatory features across participants and relationships between performance parameters. Additionally, classification accuracy was used to quantify NIRS hemodynamic response latency. Significant increases in classification rates were found as early as 2.5 s after initial stimulus presentation. These results suggest the potential application of emotional induction as a NIRS-BCI control paradigm.

A high-resolution infrared Fourier Transform Spectrometer (FTS) has been operational at the Toronto Atmospheric Observatory (TAO)since May 2002. An optimal estimation retrieval technique is used to analyse the observed spectra and provide regular total and partial column measurements of trace gases in the troposphere and stratosphere as part of the Network for the Detection of Atmospheric Composition Change. The quality of these results were assessed through two ground-based validation campaigns, comparisons with three satellite instruments, and comparison with a three-dimensional chemical transport model. The two ground-based campaigns involved two lower-resolution FTS instruments: the University of Toronto FTS and the Portable Atmospheric Research Interferometric Spectrometer for the Infrared. The first campaign took place over the course of four months and is the longest side-by-side intercomparison of ground-based FTS instruments, to date. The second campaign was more focused and involved all three instruments measuring over a two-week period. Simultaneous measurements of O3, HCl, N2O, and CH4 were recorded and average total column differences were all < 3.7% in the extended campaign, and < 4.5% in the focused campaign. Satellite-based comparisons were done with the SCanning and Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY), the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and the Optical Spectrograph and InfraRed Imager System (OSIRIS). Total column CO, CH4, and N2O compared with SCIAMACHY all had average differences < 10% with results from the TAO-FTS being as good as, or better, than that of other instruments. Validation with the ACE-FTS showed that average partial columns of O3, NO2, N2O, CH4, and HCl were within 10% while observations of CO and NO each had an average bias of about 25%. Comparisons of monthly average partial column O3 and NO2 with OSIRIS were highly correlated (R = 0.82-0.97) with monthly mean differences of < 3.1% for O3 and < 2.6% for NO2. Finally, comparisons with the GEOS-Chem chemical transport model revealed that the model consistently over-estimates tropospheric columns of CO and C2H6 observed at TAO. It was determined that the enhanced CO values were partially due to the North American emissions specified in the model, but more work must be done in the future if the source of this discrepancy is to be fully explained.

Regional tissue temperature dynamics in the brain are determined by the balance of the metabolic heat production rate and heat exchange with blood flowing through capillaries embedded in the brain tissue, the surrounding tissues and the environment. Local changes in blood flow and metabolism during functional activity can upset this balance and induce transient temperature changes. Invasive experimental studies in animal models have estab- lished that the brain temperature changes during functional activity are observable and a definitive relationship exists between temperature and brain activity. We present a theoreti- cal framework that links tissue temperature dynamics with hemodynamic activity allowing us to non-invasively estimate brain temperature changes from experimentally measured blood- oxygen level dependent (BOLD) signals. With this unified approach, we are able to pinpoint the mechanisms for hemodynamic activity-related temperature increases and decreases. In addition to these results, the potential uses and limitations of optical measurements are dis- cussed.

<p>Fluorochlorozirconate (FCZ) glasses are a member of heavy metal fluoride glasses, and are derived from a well known ZBLAN glass. In this work, halogen salts of europium (Eu²⁺) and samarium (Sm³⁺) are used as dopants in FCZ glasses. FCZ glasses doped with Eu²⁺ and Sm³⁺ can be used in high resolution x-ray imaging for tissue scanning, and have been shown to behave as storage phosphors and/or x-ray scintillators.</p> <p>Glass transition (T_g), heat capacity (C_p) and glass crystallization (T_c) properties of Eu²⁺ and Sm³⁺ doped and undoped FCZ glasses with different amounts of relative Cl concentration, that is, with respect to the total Cl and F concentration have been investigated by conventional differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC) techniques. MDSC experiments were performed at different heating rates to analyze the complex transitions and to get a better resolution of any overlapping transitions. The crystallization kinetics have also been studied by applying the Kissinger technique to multiple DSC scans in order to determine the thermal stability of FCZ glass samples used in this work. The apparent activation energy for the crystallization process was obtained by the crystallization peak temperature shift method in the conventional DSC mode. The specific heat capacity (C_p) has been measured as a function of composition, and the glass transition temperature (T_g) is evaluated from the smooth change in the heat capacity curve during the glass transformation. The observation of two possible glass transitions points to the presence of two phases in these FCZ glasses with higher relative Cl content.</p> <p>Optical transmission spectra of both doped and undoped FCZ glass samples have been measured by infrared spectroscopy and optical band gaps corresponding to an absorption coefficient of 10³ cm^-1 have been determined. A good correlation between X-ray luminescence and the glass structure is observed. While the integrated photoluminescence intensity increases linearly with the Sm³⁺ concentration, the integrated X-ray luminescence increases sublinearly. The importance of appropriate annealing conditions, such as temperature, time and ambient atmosphere, and their effect on the X-ray luminescence of rare earth (RE) doped FCZ glass samples have been investigated. Annealing conditions influence the formation of BaCl₂ nanocrystals in the glass and the properties of the resulting FCZ glass ceramics.</p>

The application of a hollow waveguide (HW) was investigated as a gas cell for analytical infrared analysis. The analysis was the measurement of carbon monoxide (CO) and nitric oxide (NO) in sidestream cigarette smoke. An FT-IR analysis system was setup with a 3m multi-pass gas cell and a 55cm by 2mm i.d. Ag/AgI coated HW in tandem with individual CO and NO gas analyzers. The HW demonstrated response times an order of magnitude less than the larger volume multi-pass gas cell and slightly faster than the single analyte gas analyzer. Furthermore, it has been demonstrated that the HW provides up to approx. 60% greater sensitivity on a per meter optical path basis than the multi-pass gas cell of the analytes investigated due to increased optical efficiency maximizing the light concentration within the gaseous sample volume. Simulations in 3-D showed the sensitivity could theoretically improve by more than an order of magnitude if the IR beam was coupled more efficiently into the waveguide. Both FT-IR configurations gave statistically equivalent results for CO to the independent analyzers. With the HW increased temporal resolution, inter-puff measurements comparable to the gas analyzer were achieved at a lower spectral resolution. The HW optical configuration was modeled for ray tracing in MATLAB. Simulations in 2-D and 3-D were accomplished. The simulations show a major drawback to HW optimization is the coupling of the infrared beam into the waveguide. As demonstrated in a 3-D simulation, approximately 97% of the rays are rejected when an off-axis parabolic mirror with 25.4mm focal length is used to focus the IR beam into the 2mm i.d. waveguide. Repeating the simulation with longer focal length mirrors showed improved in IR coupling into the waveguide from 3% to 85%. Simulations applying a compound parabolic concentrator show comparable performance to the traditional design of two OAP mirrors to collect rays from the HW and focus onto the detector, but in a much smaller configuration. The simulation routines can be used to further improve the design of this and other optical sensing systems and enhanced by incorporating a spectral component to the simulation.

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