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Measurements of Atmospheric Ozone, NO2, OClO, and BrO at 80°N using UV Visible SpectroscopyAdams, Cristen 06 December 2012 (has links)
The motivation for this thesis was to study chemical and dynamical processes in the Arctic stratosphere, using data from two ground-based spectrometers (GBSs). The GBSs took atmospheric trace gas measurements at the Polar Environment Atmospheric Research Laboratory (PEARL), which is located at Eureka, Nunavut, Canada (80.05°N, 86.42°W) and operated by the Canadian Network for the Detection of Atmospheric Change. The University of Toronto GBS took measurements at Eureka on a campaign basis from 1999 2011. The PEARL GBS was installed permanently at Eureka in 2006 and has taken measurements during the sunlit part of the year since then.
GBS and other ground based ozone and NO2 column measurements were compared with Atmospheric Chemistry Experiment (ACE) and Optical Spectrograph and Infra Red Imaging System (OSIRIS) satellite measurements above Eureka. Ozone from all instruments agreed within 9.2%, while NO2 from most instruments, including the GBS, agreed to within 20%.
On 1 August 2008, a solar eclipse of 98% totality passed over Eureka. GBS NO2 increased to 1.84 times normal levels. This agrees with a ratio of 1.91 that was calculated using a photochemical model, adjusted for reduced sunlight during the eclipse.
In spring/winter 2011, up to 47% (250 DU) ozone loss was calculated using GBS and modeled passive ozone. This was the largest ozone loss in the 11 year GBS measurement record. GBS OClO was elevated, indicating chlorine activation and NO2 was low, suggesting denitrification. GBS, satellite, and chemical transport model data were used to investigate the 2011 vortex breakup. NOx transport led to middle stratosphere ozone loss within an anticyclone. Furthermore, isolated, or “frozen-in”, vortex and lower-latitude airmasses were observed following the vortex breakup.
Stratospheric BrO was retrieved from spring 2008 GBS zenith sky measurements, using an optimal estimation technique. GBS BrO was compared with OSIRIS and Ozone Monitoring Instrument (OMI) satellite data. Discrepancies are partly attributed to bromine explosions in the boundary layer. New off axis GBS measurements taken in spring 2010 are sensitive to boundary layer bromine. The combination of GBS stratospheric and tropospheric BrO measurements will be useful for future estimates of the Arctic bromine budget.
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Measurements of Atmospheric Ozone, NO2, OClO, and BrO at 80°N using UV Visible SpectroscopyAdams, Cristen 06 December 2012 (has links)
The motivation for this thesis was to study chemical and dynamical processes in the Arctic stratosphere, using data from two ground-based spectrometers (GBSs). The GBSs took atmospheric trace gas measurements at the Polar Environment Atmospheric Research Laboratory (PEARL), which is located at Eureka, Nunavut, Canada (80.05°N, 86.42°W) and operated by the Canadian Network for the Detection of Atmospheric Change. The University of Toronto GBS took measurements at Eureka on a campaign basis from 1999 2011. The PEARL GBS was installed permanently at Eureka in 2006 and has taken measurements during the sunlit part of the year since then.
GBS and other ground based ozone and NO2 column measurements were compared with Atmospheric Chemistry Experiment (ACE) and Optical Spectrograph and Infra Red Imaging System (OSIRIS) satellite measurements above Eureka. Ozone from all instruments agreed within 9.2%, while NO2 from most instruments, including the GBS, agreed to within 20%.
On 1 August 2008, a solar eclipse of 98% totality passed over Eureka. GBS NO2 increased to 1.84 times normal levels. This agrees with a ratio of 1.91 that was calculated using a photochemical model, adjusted for reduced sunlight during the eclipse.
In spring/winter 2011, up to 47% (250 DU) ozone loss was calculated using GBS and modeled passive ozone. This was the largest ozone loss in the 11 year GBS measurement record. GBS OClO was elevated, indicating chlorine activation and NO2 was low, suggesting denitrification. GBS, satellite, and chemical transport model data were used to investigate the 2011 vortex breakup. NOx transport led to middle stratosphere ozone loss within an anticyclone. Furthermore, isolated, or “frozen-in”, vortex and lower-latitude airmasses were observed following the vortex breakup.
Stratospheric BrO was retrieved from spring 2008 GBS zenith sky measurements, using an optimal estimation technique. GBS BrO was compared with OSIRIS and Ozone Monitoring Instrument (OMI) satellite data. Discrepancies are partly attributed to bromine explosions in the boundary layer. New off axis GBS measurements taken in spring 2010 are sensitive to boundary layer bromine. The combination of GBS stratospheric and tropospheric BrO measurements will be useful for future estimates of the Arctic bromine budget.
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Etude des émissions thermosphériques des planètes telluriques pour la caractérisation d'exoplanètes / Study of the thermospheric emissions of telluric planets fo the characterization of exoplanetary atmospheresBernard, David 27 June 2014 (has links)
Depuis la découverte de la première exoplanète en 1995 par Mayor et Queloz, le nombre de planètes extrasolaires découvertes n'a cessé d'augmenter, pour dépasser les 1000 planètes à la fin de l'année 2013. Depuis le début des années 2000, la détection s'est accompagnée d'une volonté de caractérisation de l'atmosphère des exoplanètes. Les méthodes utilisées jusqu'ici sont la spectroscopie de transit primaire et l'étude des émissions thermiques en transit secondaire ou via l'étude des courbes de phase. L'objet de cette thèse s'inscrit dans cette recherche de caractérisation des atmosphères exoplanétaires, en s'intéressant à une méthode jusqu'ici inexplorée : l'analyse des émissions thermosphériques, i.e. les émissions de la haute atmosphère induites par les entrées énergétiques, flux extrême UV de l'étoile hôte et précipitations électroniques principalement. La première partie de cette thèse s'intéresse aux émissions thermosphériques de la Terre primitive avec une approche basée sur la modélisation. Le but étant la détermination des différentes émissions de la Terre à travers son histoire, afin de disposer de proxies pour la recherche et la caractérisation d'exoplanètes telluriques. Dans un premier temps nous avons calculé l'émission de l'atmosphère primordiale de la Terre irradiée par le Soleil jeune dans la raie Lyman Alpha. Nous avons montré que la raie planétaire, principalement formée par diffusion cohérente, montre un rapport d'émission avec le Soleil de l'ordre de 10-8, inaccessible aux observations, avec les instruments actuels ou de prochaine génération. Ce premier résultat nous à conduit à étudier la faisabilité d'une méthode indirecte de détection d'une couronne dense d'hydrogène autour d'une planète tellurique possédant une atmosphère de CO2 par les émissions des sous-produits de dissociation et d'ionisation de CO2. Les calculs menés sur la raie verte de l'oxygène (état O1S) et le doublet UV de CO2+ (état B2Σu+) ont montré que ces émissions présentaient des contrastes de l'ordre de 10^-12 avec le Soleil dans le cas d'une Terre primitive, et de l'ordre de 10^-6-10^-8 pour une planète tellurique proche d'une naine M. La conclusion générale des ces investigations est que les raies fines (atomiques ou moléculaires) des émissions thermosphériques sont trop faibles pour être détectées par les instruments actuels. Une voie possible serait l'étude des bandes d'émission moléculaires, qui nécessite une meilleure compréhension de la distribution en intensité des différentes bandes à travers le spectre, compréhension qui passe par l'étude expérimentale de ces émissions. C'est dans ce cadre que se situe la deuxième partie de cette thèse, qui s'intéresse à l'analyse spectroscopique de la Planeterrella, simulateur d'aurores boréales initialement développé à des fins pédagogiques. Nous avons réalisé une étude spectroscopique à basse et haute résolution de l'air, afin de caractériser les émissions présentes dans l'expérience d'une part, et aussi de disposer d'un spectre de référence qui servira à terme de test pour un code Monte Carlo développé pour étudier le dispositif expérimental, la caractérisation du dispositif constituant une étape nécessaire pour faire de la Planeterrella un objet d'étude scientifique. Enfin, la spectroscopie basse résolution du CO2 a été réalisée, avec des applications potentielles à Mars. / Since the discovery of the first exoplanet in 1995 by Mayor and Queloz, the number of extrasolar planets discovered has continuously grown up, to overtake 1000 planets at the end of 2013. Since the beginning of the 2000's, came with the detection the will to characterize the atmospheres of these exoplanets. Until now, the methods used are the primary transit spectroscopy and the study of the thermal emissions in secondary transit or using phase curves. The purpose of this thesis belongs to that search for characterizing exoplanetary atmospheres, by looking at a method unexplored until now: the study of the thermospheric emissions, i.e. emissions from the upper atmosphere induced by the energetic entries, mainly the extreme UV flux and the electronic precipitations. The first part of this thesis concerns the thermospheric emissions of the primitive Earth with an approach based on modeling. The goal is the determination of the several emissions of the Earth through its history in order to have proxies for the search and the characterization of telluric exoplanets. Initially we calculated the emission of the primary atmosphere of the early Earth under the young Sun in the Lyman Alpha line. We showed that the planetary line in mainly due to coherent diffusion and that the emission ratio between the planet and the Sun in this line is of about 10-8, far from the capabilities of current or next generation instruments. This first result lead us to study the feasibility of an indirect method to infer the presence of dense hydrogen corona surrounding a telluric planet with a CO2-dominated atmosphere, by studying its influence on the emissions of two CO2 by-products. The calculations carried out on the oxygen green line (O1S state) and the UV doublet of CO2+ (B2Σu+ state) showed that theses emissions present contrasts of about 10^-12 with the young Sun in the case of a primitive Earth, and of about 10^-6-10^-8 for a close-in telluric planet around a M dwarf. The general conclusion of the investigations is that the thermospheric emissions of thin (atomic or molecular) lines are too weak to be detected. A possible way could be the study of the molecular bands, of which emissions need to be better understood, especially concerning the intensity distribution of the several bands through the spectrum. This comprehension implies experimental studies of these emissions. The second part of this thesis lies in this scope and concerns the spectroscopic analysis of the Planeterrella, an aurora borealis simulator initially designed for outreach purpose. We made a spectroscopic study at low and high resolution with air, in order to characterize the emissions existing in the experiment, and also to have a reference spectrum which will be a final test for a Monte Carlo code developed to study the experimental device, the characterization of this device being a necessary step for the Planeterrella to become suitable for scientific purpose. Finally, we made a low resolution spectroscopic study of carbon dioxide, with potential applications to Mars.
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Dégradation de pesticides organochlorés par procédés d'oxydation avancée utilisant différents types de rayonnements / Degradación de pesticidas organoclorados por diferentes procesos avanzados de oxidación utilizando diferentes tipos de radiación / Degradation of organochlorine pesticides by advanced oxidation processes using different types of radiationCruz-González, Germán 20 July 2018 (has links)
Ce travail s’intéresse à évaluer l’efficacité de procédés d’oxydation avancée pour l’élimination de pesticides dans l’eau, plus particulièrement l’acide 2,4-dichlorophénoxyacétique (2,4-D), un herbicide largement répandu, qui a été récemment classé comme cancérogène possible pour l’homme. Ces procédés utilisent différents types de rayonnement – UV/visible, ultrasons, rayons gamma –, seuls ou en combinaison avec des oxydants et/ou catalyseurs (ozone, peroxyde d’hydrogène, réactif de Fenton). L'influence du pH, de la dose d'oxydant, du type et de la concentration du catalyseur, du spectre d'irradiation lumineuse, de la dose de rayons gamma et de la fréquence ultrasonore est également analysée, de façon à déterminer par plans d’expériences les plages de fonctionnement optimales pour la conversion et la minéralisation du polluant. Parmi les procédés individuels, seules l’ozonation et l’oxydation Fenton homogène d’une part, la photolyse et l’irradiation gamma d’autre part permettent d’éliminer plus de 25% du carbone organique total en 1 heure. La sonolyse (à haute fréquence) apparaît comme le traitement moins performant, avec une dégradation du 2,4-D inférieure à 15% sur la même durée. Par ailleurs, des effets synergiques marqués sont mis en évidence en associant les différents types de rayonnement avec H2O2 ou le réactif de Fenton. Dans le dernier cas, le polluant est décomposé en moins de 10 minutes, tandis que le rendement de minéralisation est plus que doublé par rapport aux procédés séparés. Il en est de même pour le procédé couplé UV/O3 par rapport à l’ozonation et la photolyse seules. Ramenés à leur consommation énergétique, les traitements les plus efficaces sont, respectivement en termes de conversion et de minéralisation, l’oxydation radio-Fenton et l’oxydation photo-Fenton utilisant une lampe UV à basse pression de mercure. Par ailleurs, contrairement à la photolyse, ce dernier procédé est également activé par une lampe à arc Xenon, dont le spectre d’émission est proche de celui de la lumière du soleil. Sur la base de ces résultats, un photo-réacteur solaire à recirculation est mis en oeuvre pour traiter par oxydation photo-Fenton homogène des solutions de 2,4-D, préparées dans l’eau du robinet ou une eau résiduaire en entrée de station d’épuration. Dans les deux cas, la conversion du pesticide dépasse 95% en 1 heure et sa minéralisation 75% en 5 heures. Par ailleurs, l’eau ainsi traitée respecte tous les paramètres de qualité établis par la norme cubaine de rejet des eaux usées, en incluant une étape successive de neutralisation avec Ca(OH)2 et de filtration. Enfin, plusieurs parmi les meilleurs procédés sont évalués pour éliminer deux autres pesticides organochlorés, particulièrement toxiques et persistants dans l’environnement : le chlordécone et le bêta-hexachlorocyclohexane. Des résultats encourageants sont obtenus, avec une dégradation pratiquement totale des polluants en cinq heures, ce qui démontre l’intérêt des méthodes étudiées pour cette problématique. / This work investigates the efficacy of advanced oxidation processes for the remediation of pesticidesin water, more particularly 2,4-dichlorophenoxyacetic acid (2,4-D), a widely used herbicide that hasrecently been classified as a possible carcinogen to humans. These methods use different types ofradiation - UV / visible, ultrasound, gamma rays - alone or in combination with oxidants and / orcatalysts (ozone, hydrogen peroxide, Fenton’s reagent). The influence of pH, oxidant dose, catalysttype and concentration, light irradiation spectrum, gamma radiation dose and ultrasound frequencyis also analyzed, in order to determine by experimental design the optimal operating ranges for theconversion and mineralization of the pollutant. Of individual processes, only ozonation andhomogeneous Fenton oxidation on the one hand, photolysis and gamma irradiation on the otherhand, achieve the abatement of more than 25% of total organic carbon in one hour. (High frequency)sonolysis appears as the less efficient treatment, resulting in less than 15% of 2,4-D being degradedover the same duration.In addition, marked synergistic effects are demonstrated by combining the different types of radiationwith H2O2 or Fenton’s reagent. In the latter case, the pollutant is decomposed in less than 10 minutes,while the mineralization yield more than doubles compared to the separate processes. It is the samefor UV/O3 coupled process with respect to ozonation and photolysis alone. When accounting for theirenergy consumption, the most effective treatments are, respectively in terms of conversion andmineralization, radio-Fenton oxidation and photo-Fenton oxidation using a low-pressure mercuryvaporUV lamp. Moreover, unlike photolysis, the latter method is also activated by a Xenon arc lamp,whose emission spectrum is close to that of sunlight. Bases on these results, a solar photoreactoroperating in closed loop is used to treat 2,4-D solutions, prepared with tap water or inlet stream ofwastewater treatment plant, by homogeneous photo-Fenton oxidation. In both cases, the conversionof the pesticide exceeds 95% in 1 hour and its mineralization 75% in 5 hours. Moreover, the treatedwater complies with all the quality parameters established by the Cuban norm for wastewaterdischarge, when including a subsequent step of neutralization with Ca(OH)2 and filtration.Finally, several of the best processes are evaluated to eliminate two other organochlorine pesticides,particularly toxic and persistent in the environment: chlordecone and beta-hexachlorocyclohexane.Encouraging results are obtained, with an almost complete degradation of the pollutants in fivehours, which demonstrates the value of the investigated methods for this issue. / En este trabajo se estudió la factibilidad de diferentes procesos avanzados de oxidación para laeliminación de plaguicidas en aguas, específicamente el ácido 2,4-diclorofenoxiacético (2,4-D), unode los herbicidas más utilizados a nivel mundial y que recientemente ha sido clasificado comocancerígeno para el hombre. Estos procesos utilizan diferentes tipos de irradiación – UV/Visible,ultrasonido, radiación gamma – solos o en combinación con oxidantes y/o catalizadores (ozono,peróxido de hidrógeno, reactivo de Fenton). Con el objetivo de determinar las condiciones óptimaspara la degradación y mineralización del contaminante, se analizó la influencia del pH, la dosis deoxidante, el tipo y la concentración del catalizador, el espectro de irradiación luminosa, la dosis deirradiación gamma y la frecuencia y potencia ultrasónicas. Entre los procesos individuales,solamente la oxidación Fenton homogénea, la ozonización, la fotólisis y la radiación gamma lograroneliminar más de un 25% del carbono orgánico total en una hora. La sonólisis (a alta frecuencia)resultó el proceso menos eficiente, con una degradación del 2,4-D inferior al 15% en el mismotiempo.Al asociar los diferentes tipos de irradiación con el H2O2 o el reactivo de Fenton, se observaronefectos sinérgicos importantes. Para este último, el contaminante se degradó totalmente en menosde 10 minutos, mientras que la mineralización fue superior al doble de la obtenida para los procesospor separado. Lo mismo ocurrió para el proceso combinado UV/O3, respecto a los procesos defotólisis y ozonización solos. Teniendo en cuenta el consumo energético asociado a la degradacióny mineralización respectivamente, los tratamientos más eficientes fueron el radio-Fenton y el foto-Fenton utilizando una lámpara de baja presión de mercurio. Por otra parte, al contrario de la fotólisis,este último proceso se activó con una lámpara de arco de Xenon, la cual posee un espectro deemisión cercano a la luz solar. Teniendo en cuenta estos resultados, se realizó un grupo deexperimentos a escala de banco utilizando un foto-reactor solar, donde se trataron por oxidaciónfoto-Fenton homogénea disoluciones de 2,4-D preparadas con agua técnica y agua residualobtenida a la entrada de una planta de tratamiento de aguas. En los dos casos, la degradación delpesticida supera el 95% en 1 hora y su mineralización en 75% en 5 horas. Además, al incluir unaetapa de neutralización con Ca(OH)2, el agua residual tratada logra cumplir las normas de calidadestablecidas por la norma cubana de vertimiento de aguas residuales.Finalmente, algunos de los procesos con mejores resultados se evaluaron para la eliminación otrosdos pesticidas organoclorados de mayor toxicidad y persistencia en el medio ambiente: laclordecona y el beta hexaclorociclohexano. Al aplicar las técnicas de tratamiento a estoscompuestos se lograron buenos resultados, cercanos a la degradación total de ambos plaguicidasen cinco horas, lo que demuestra el interés de los métodos estudiados en esta tesis.
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DNA PHOTO-CLEAVAGE AND INTERACTIONS BY QUINOLINE CYANINE DYES; TOWARDS IMPROVING PHOTODYNAMIC CANCER THERAPYFatemipouya, Tayebeh 14 December 2016 (has links)
Photodynamic therapy (PDT) is a cancer treatment method in which a photosensitizer, light of a particular wavelength, and also oxygen are used to destroy cancerous cells. Cancer cells absorb the photosensitizing agent which is injected into the body, and it is triggered to cause cell destruction upon absorption of light. This occurs because of the excitation of the photosensitizer produces reactive oxygen species that induce a cascade of cellular and molecular events in the body. Photosensitizing agents that can photo-cleave DNA at long wavelengths are highly demanded in PDT, because the long wavelengths of light can penetrate through tissue deeply compared to visible light. While most of the photosensitizers are activated at wavelengths less than 690 nm, penetration of light continues to increase at increasing wavelengths. In this thesis, photosensitizers that can be activated to oxidize DNA with long wavelengths of light will be discussed. Using quinoline cyanine dyes, here we report the first example of DNA photocleavage at a wavelength of light above 800 nm.
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Dégradation de pesticides organochlorés par procédés d'oxydation avancée utilisant différents types de rayonnementsCruz-González, Germán 20 July 2018 (has links) (PDF)
Ce travail s’intéresse à évaluer l’efficacité de procédés d’oxydation avancée pour l’élimination de pesticides dans l’eau, plus particulièrement l’acide 2,4-dichlorophénoxyacétique (2,4-D), un herbicide largement répandu, qui a été récemment classé comme cancérogène possible pour l’homme. Ces procédés utilisent différents types de rayonnement – UV/visible, ultrasons, rayons gamma –, seuls ou en combinaison avec des oxydants et/ou catalyseurs (ozone, peroxyde d’hydrogène, réactif de Fenton). L'influence du pH, de la dose d'oxydant, du type et de la concentration du catalyseur, du spectre d'irradiation lumineuse, de la dose de rayons gamma et de la fréquence ultrasonore est également analysée, de façon à déterminer par plans d’expériences les plages de fonctionnement optimales pour la conversion et la minéralisation du polluant. Parmi les procédés individuels, seules l’ozonation et l’oxydation Fenton homogène d’une part, la photolyse et l’irradiation gamma d’autre part permettent d’éliminer plus de 25% du carbone organique total en 1 heure. La sonolyse (à haute fréquence) apparaît comme le traitement moins performant, avec une dégradation du 2,4-D inférieure à 15% sur la même durée. Par ailleurs, des effets synergiques marqués sont mis en évidence en associant les différents types de rayonnement avec H2O2 ou le réactif de Fenton. Dans le dernier cas, le polluant est décomposé en moins de 10 minutes, tandis que le rendement de minéralisation est plus que doublé par rapport aux procédés séparés. Il en est de même pour le procédé couplé UV/O3 par rapport à l’ozonation et la photolyse seules. Ramenés à leur consommation énergétique, les traitements les plus efficaces sont, respectivement en termes de conversion et de minéralisation, l’oxydation radio-Fenton et l’oxydation photo-Fenton utilisant une lampe UV à basse pression de mercure. Par ailleurs, contrairement à la photolyse, ce dernier procédé est également activé par une lampe à arc Xenon, dont le spectre d’émission est proche de celui de la lumière du soleil. Sur la base de ces résultats, un photo-réacteur solaire à recirculation est mis en œuvre pour traiter par oxydation photo-Fenton homogène des solutions de 2,4-D, préparées dans l’eau du robinet ou une eau résiduaire en entrée de station d’épuration. Dans les deux cas, la conversion du pesticide dépasse 95% en 1 heure et sa minéralisation 75% en 5 heures. Par ailleurs, l’eau ainsi traitée respecte tous les paramètres de qualité établis par la norme cubaine de rejet des eaux usées, en incluant une étape successive de neutralisation avec Ca(OH)2 et de filtration. Enfin, plusieurs parmi les meilleurs procédés sont évalués pour éliminer deux autres pesticides organochlorés, particulièrement toxiques et persistants dans l’environnement : le chlordécone et le bêta-hexachlorocyclohexane. Des résultats encourageants sont obtenus, avec une dégradation pratiquement totale des polluants en cinq heures, ce qui démontre l’intérêt des méthodes étudiées pour cette problématique.
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Arctic and Midlatitude Stratospheric Trace Gas Measurements Using Ground-based UV-visible SpectroscopyFraser, Annemarie 26 February 2009 (has links)
A ground-based, zenith-sky, UV-visible triple grating spectrometer was installed at the Polar Environment Atmospheric Research Laboratory (PEARL) in the Canadian High Arctic during polar springtime from 2004 to 2007 as part of the Canadian Arctic ACE (Atmospheric Chemistry Experiment) Validation Campaigns. From the solar spectra,
ozone, NO2, and BrO vertical column densities (VCDs) have been retrieved using the DOAS (Differential Optical Absorption Spectroscopy) technique. This spectrometer, the UT-GBS (University of Toronto Ground-Based Spectrometer), was also deployed as part of the fourth Middle Atmosphere Nitrogen TRend Assessment (MANTRA) campaign in Vanscoy, Saskatchewan in August and September 2004.
A near-identical spectrometer, the PEARL-GBS, was permanently installed at PEARL
in August 2006 as part of the refurbishment of the laboratory by CANDAC (Canadian
Network for the Detection of Atmospheric Change). Since then, the instrument has been
making continuous measurements, with the exception of during polar night. Vertical
columns of ozone and NO2 can be retrieved year-round. During the 2007 sunrise campaign,
differential slant column densities (DSCDs) of OClO and VCDs of BrO were also
retrieved.
Ozone and NO2 DSCDs and VCDs from the UT-GBS were compared to the DSCDs and VCDs from three other UV-visible, ground-based, grating spectrometers that also participated in the MANTRA and Eureka campaigns. Two methods developed by the UV-visible Working Group of the NDACC (Network for the Detection of Atmospheric Composition Change) were followed. During MANTRA, the instruments were found to partially meet the NDACC standards. The comparisons from Eureka were an improvement on the MANTRA comparisons, and also partially met the NDACC standards. In 2007, the columns from the UT-GBS and PEARL-GBS were compared, and were found to agree within the NDACC standards for both species.
Ozone and NO2 VCDs from the ground-based instruments were also compared to
integrated partial columns from the ACE-FTS (ACE-Fourier Transform Spectrometer)
and ACE-MAESTRO (ACE-Measurements of Aerosol Extinction in the Stratosphere
and Troposphere Retrieved by Occultation) on board the ACE satellite. ACE-FTS partial
columns were found to agree with the ground-based total columns, while the ACE-MAESTRO
partial columns were found to be smaller than expected for ozone and larger than expected for NO2.
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Arctic and Midlatitude Stratospheric Trace Gas Measurements Using Ground-based UV-visible SpectroscopyFraser, Annemarie 26 February 2009 (has links)
A ground-based, zenith-sky, UV-visible triple grating spectrometer was installed at the Polar Environment Atmospheric Research Laboratory (PEARL) in the Canadian High Arctic during polar springtime from 2004 to 2007 as part of the Canadian Arctic ACE (Atmospheric Chemistry Experiment) Validation Campaigns. From the solar spectra,
ozone, NO2, and BrO vertical column densities (VCDs) have been retrieved using the DOAS (Differential Optical Absorption Spectroscopy) technique. This spectrometer, the UT-GBS (University of Toronto Ground-Based Spectrometer), was also deployed as part of the fourth Middle Atmosphere Nitrogen TRend Assessment (MANTRA) campaign in Vanscoy, Saskatchewan in August and September 2004.
A near-identical spectrometer, the PEARL-GBS, was permanently installed at PEARL
in August 2006 as part of the refurbishment of the laboratory by CANDAC (Canadian
Network for the Detection of Atmospheric Change). Since then, the instrument has been
making continuous measurements, with the exception of during polar night. Vertical
columns of ozone and NO2 can be retrieved year-round. During the 2007 sunrise campaign,
differential slant column densities (DSCDs) of OClO and VCDs of BrO were also
retrieved.
Ozone and NO2 DSCDs and VCDs from the UT-GBS were compared to the DSCDs and VCDs from three other UV-visible, ground-based, grating spectrometers that also participated in the MANTRA and Eureka campaigns. Two methods developed by the UV-visible Working Group of the NDACC (Network for the Detection of Atmospheric Composition Change) were followed. During MANTRA, the instruments were found to partially meet the NDACC standards. The comparisons from Eureka were an improvement on the MANTRA comparisons, and also partially met the NDACC standards. In 2007, the columns from the UT-GBS and PEARL-GBS were compared, and were found to agree within the NDACC standards for both species.
Ozone and NO2 VCDs from the ground-based instruments were also compared to
integrated partial columns from the ACE-FTS (ACE-Fourier Transform Spectrometer)
and ACE-MAESTRO (ACE-Measurements of Aerosol Extinction in the Stratosphere
and Troposphere Retrieved by Occultation) on board the ACE satellite. ACE-FTS partial
columns were found to agree with the ground-based total columns, while the ACE-MAESTRO
partial columns were found to be smaller than expected for ozone and larger than expected for NO2.
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Porphyrin complexation: an approach in porphyria therapyAkinwumi, Bolanle C. 20 August 2012 (has links)
Porphyria is a rare metabolic disease which occurs as a result of accumulation of endogenous porphyrins due to specific enzyme deficiency in the biosynthetic pathway of heme. Chloroquine is currently used in the treatment of cutaneous porphyria, although its mechanism of action is not yet well understood. It is believed that chloroquine works in porphyria by forming complexes with excess porphyrin molecules and thus enhancing their elimination from the body. Previous reports of porphyrin-chloroquine complexes have been done mostly in aqueous models. In this study, UV/Visible optical absorbance difference spectroscopy was used to study the complexation of protoporphyrin IX with chloroquine and a range of acceptor molecules in hydrophobic models. The results show that chloroquine, mefloquine, amodiaquine, quinacrine, and pyronaridine formed relatively stronger complexes compared to other molecules such as quinine, duroquinone and caffeine. Therefore, relative to chloroquine, some of the molecules with comparable or greater binding affinity to protoporphyrin IX might also be useful in the treatment of porphyria.
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Porphyrin complexation: an approach in porphyria therapyAkinwumi, Bolanle C. 20 August 2012 (has links)
Porphyria is a rare metabolic disease which occurs as a result of accumulation of endogenous porphyrins due to specific enzyme deficiency in the biosynthetic pathway of heme. Chloroquine is currently used in the treatment of cutaneous porphyria, although its mechanism of action is not yet well understood. It is believed that chloroquine works in porphyria by forming complexes with excess porphyrin molecules and thus enhancing their elimination from the body. Previous reports of porphyrin-chloroquine complexes have been done mostly in aqueous models. In this study, UV/Visible optical absorbance difference spectroscopy was used to study the complexation of protoporphyrin IX with chloroquine and a range of acceptor molecules in hydrophobic models. The results show that chloroquine, mefloquine, amodiaquine, quinacrine, and pyronaridine formed relatively stronger complexes compared to other molecules such as quinine, duroquinone and caffeine. Therefore, relative to chloroquine, some of the molecules with comparable or greater binding affinity to protoporphyrin IX might also be useful in the treatment of porphyria.
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