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.

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.

In the mid-1800s, monitoring networks were established to investigate atmospheric composition impacts, and the conditions giving rise to them. The development of these networks, in terms of coordination and standardisation between contributing sites, has resulted in large advances in knowledge of the nature of atmospheric composition. Currently thousands of sites collect high quality atmospheric composition measurements globally. This thesis contends that in order to maximise the information derived from these measurements, a further advancement in standardisation is required to encompass the interpretation of monitoring network data. Currently there are limited examples of a common interpretation of data applied across all sites in a monitoring network, especially in relation to specific atmospheric composition impacts. In this thesis, a ‘chemical climatology’ framework is outlined which provides a common basis for targeting analysis towards identifying the linkage between a specific atmospheric composition impact and its causal drivers. Case studies apply the chemical climatology framework to demonstrate its utility in deriving scientific and policy relevant conclusions using measurement data from the UK monitoring supersites located at Harwell and Auchencorth. Prior to this, the representativeness of each site is quantified through the application of cluster analysis to ozone data at 100 rural European sites to identify groupings of sites with similar ozone variation. Harwell was representative of rural locations within 120 km of London, while Auchencorth was representative of a larger, transboundary spatial domain including the remainder of the rural UK. The first case study links the impact of ozone on human health (quantified by SOMO10 and SOMO35 metrics) and vegetation (flux-based PODY) to meteorological and emissions drivers. Between 1990 and 2013 at Harwell, there was a significant decrease in the contribution of European ozone to determining the impacts. Improvement in the human health impact was heavily dependent on the choice of metric (SOMO35 decreased, no change in SOMO10), and the vegetation impacts had not improved as high ozone episodes frequently coincided with plant conditions which reduced ozone uptake. These chemical climates emphasise the need for ozone mitigation on larger (hemispheric) scales than currently implemented. Secondly, the impact of 27 measured VOCs on the extent of the regional ozone increment is assessed. The photochemical loss of VOCs is then linked to reported gridded VOC emissions using air mass back trajectory analysis. Ethene and m+p-xylene had the largest diurnal photochemical loss during maximum monthly regional ozone increment, but the key conclusion was the limitation introduced through the reporting of gridded VOC emissions in heavily aggregated source sectors. Finally, the conditions producing the long term health impact of particulate matter (quantified by annual average PM10 and PM2.5 concentrations) at each site are derived through integration of measurements of PM10 and PM2.5 with measurements of PM constituents. It is shown that the frequent, moderate PM10 and PM2.5 concentrations made a larger contribution to annual average values compared to the relatively infrequent high, episodic concentrations. The contribution of PM constituents and the contribution of local vs regional emissions to the range of PM concentrations is investigated. It was concluded that similar reductions in the contribution of secondary inorganic aerosol to the moderate PM10 and PM2.5 concentrations could be achieved from both the reduction of frequently traversed, smaller emissions sources, and less frequently traversed, larger emissions sources. The final chapter demonstrates the benefits from the extension of this framework to an entire monitoring network. It is envisioned that for each atmospheric composition impact, a standard set of statistics would be calculated which quantify the ‘impact’, ‘state’ and ‘drivers’ of that chemical climate. Calculation of ozone human health chemical climates across 100 European monitoring sites demonstrate this concept. This standardised interpretation of monitoring network data not only allows consistent comparison of an impact, but the common basis for determining how the impact is derived allows for the consideration of novel mitigation strategies and their spatial applicability.

The measurement of trace gases through remote sounding techniques has led to a better understanding of the processes controlling the structure and variability of the stratosphere. Differences between measurements over space and time are due to atmospheric variability and instrument errors: thus, comparison of measurements can be used to test our knowledge of both. Comparisons of measurements over long time periods are used to identify trends. Balloon-borne infrared emission radiometer instruments have been used to make measurements of midlatitude stratospheric HNO3 spanning a period of twelve years. The timing of the measurements is notable, since they occur before and well after the eruption of Mt. Pinatubo, which significantly perturbed HNO3 levels, complicating prior trend analyses. No significant differences are found between the HNO3 retrievals, although large measurement uncertainties preclude any conclusion concerning trends. Comparisons of measurements that are closely spaced in space and time are useful for satellite validation, where one aims to reduce the effect of atmospheric variability on the estimation of systematic and random errors. A novel technique for the estimation of systematic error, which differentiates between additive and multiplicative bias, is introduced. In a comparison of measurements by the ACE-FTS and Aura MLS instruments, significant multiplicative biases are identified and described. In order to validate the reported random errors (RREs) of measurements, satellite validation studies often focus on measurements in the tropical stratosphere, where variability is weak. The scatter in tropical measurements can then be used as an upper limit on instrument precision. In an analysis of tropical measurements by the ACE-FTS, scatter is found to be roughly consistent with the RREs for H2O and CO. The scatter in measurements of O3, HNO3, and N2O, while larger than the reported random errors, is roughly consistent with the variability simulated in the Canadian Middle Atmosphere Model. This work implies that the random error of the ACE-FTS measurements is smaller than the weak natural variability of the tropical stratosphere.

The measurement of trace gases through remote sounding techniques has led to a better understanding of the processes controlling the structure and variability of the stratosphere. Differences between measurements over space and time are due to atmospheric variability and instrument errors: thus, comparison of measurements can be used to test our knowledge of both. Comparisons of measurements over long time periods are used to identify trends. Balloon-borne infrared emission radiometer instruments have been used to make measurements of midlatitude stratospheric HNO3 spanning a period of twelve years. The timing of the measurements is notable, since they occur before and well after the eruption of Mt. Pinatubo, which significantly perturbed HNO3 levels, complicating prior trend analyses. No significant differences are found between the HNO3 retrievals, although large measurement uncertainties preclude any conclusion concerning trends. Comparisons of measurements that are closely spaced in space and time are useful for satellite validation, where one aims to reduce the effect of atmospheric variability on the estimation of systematic and random errors. A novel technique for the estimation of systematic error, which differentiates between additive and multiplicative bias, is introduced. In a comparison of measurements by the ACE-FTS and Aura MLS instruments, significant multiplicative biases are identified and described. In order to validate the reported random errors (RREs) of measurements, satellite validation studies often focus on measurements in the tropical stratosphere, where variability is weak. The scatter in tropical measurements can then be used as an upper limit on instrument precision. In an analysis of tropical measurements by the ACE-FTS, scatter is found to be roughly consistent with the RREs for H2O and CO. The scatter in measurements of O3, HNO3, and N2O, while larger than the reported random errors, is roughly consistent with the variability simulated in the Canadian Middle Atmosphere Model. This work implies that the random error of the ACE-FTS measurements is smaller than the weak natural variability of the tropical stratosphere.

Atmospheres play an important role in the habitability of a planet, so understanding and modelling them is an important step in the search for life on other planets. This thesis presents a 1D frequency-dependent radiative-convective code that was written to help determine the temperature-pressure structure of potentially-habitable exoplanets. This code pairs with a chemistry model to determine the chemical composition of these planets' atmospheres. This code is applied to the planets in the TRAPPIST-1 system. The initial atmospheric compositions of the TRAPPIST-1 planets are determined through planet formation history and considered for both outgassed and accreted atmospheres. An interesting result is found when running these initial atmospheric compositions through the chemistry model: when the atmosphere equilibrates, it can change its C/O ratio from equal to that found in the accreted or outgassed volatiles to something lower, because, in temperate conditions, CO$_2$ is favoured over CO. This has the consequence that observed C/O ratios in terrestrial atmospheres cannot be relied on to infer the C/O ratio of the protoplanetary disc in which the planet formed. The initial results of atmospheric modelling for TRAPPIST-1 planets indicate that these planets are likely to have relatively warmer upper atmospheres due to the fact that their host star emits primarily in the infrared, and a portion of this radiation is then absorbed as it enters the top of the atmosphere. These initial results have not been seen in previous work. These initial results are the beginning of a database of potential atmospheres on the TRAPPIST-1 planets. It is hoped that these atmospheres can be compared with observations from future observing missions like the James Webb Space Telescope to help constrain the surface conditions of these potentially-habitable planets and ultimately, to help in the search for life. / Thesis / Master of Science (MSc)

Im Rahmen der vorliegenden Arbeit wurden die Eigenschaften von atmosphärischen Aerosolpartikeln im tropischen Regenwald des Amazonasgebietes bestimmt. Dazu wurden die Daten einer fast einjährigen Lidarmesskampagne ausgewertet und diskutiert. Die Messungen wurden mit einem automatischen Mehrwellenlängen-Polarisations-Raman-Lidar im zentralen Amazonasbecken nahe Manaus, Brasilien, im Zeitraum von Januar bis November 2008 durchgeführt. Somit konnten erstmalig optische und mikrophysikalische Aerosoleigenschaften im Amazonasgebiet während der Regenzeit (ca. Dezember-Mai) und Trockenzeit (ca. Juni-November) höhenaufgelöst charakterisiert werden. Einleitend werden die meteorologischen Bedingungen im Amazonasgebiet erläutert und eine Literaturübersicht über Aerosolforschung in dieser Region gegeben. Das Messgerät sowie verschiedene Kalibrier- und Korrekturschemen, die zur Datenauswertung notwendig sind, werden vorgestellt. Auch Vergleiche mit anderen Messgeräten werden diskutiert. Diese zeigen, dass die aus den Lidarmessungen abgeleiteten Parameter von hoher Qualität sind. Anhand von Fallstudien werden mit Hilfe von Rückwärtstrajektorien und Satellitenmessungen typische Aerosolbedingungen am Messstandort diskutiert. Um die generellen Unterschiede zwischen Regen- und Trockenzeit zu quantifizieren, wird eine statistische Auswertung aller analysierten Lidarmessungen präsentiert. Die Analyse der Lidardaten zeigt, dass während der Regenzeit im Amazonasgebiet in ca. der Hälfte aller Fälle sehr saubere Bedingungen mit einer Aerosol Optischen Dicke (AOD) von weniger als 0.05 (bei 532 nm) vorherrschen können. Allerdings wurde in ca. 30% aller analysierten Fälle im Zeitraum von Januar bis Mai auch afrikanisches Aerosol, vornehmlich Saharastaub und Biomasseverbrennungsaerosol (BBA), am Messstandort detektiert. Dabei dominierte meist BBA die Aerosolpopulation, wie die Depolarisationsmessungen zeigten. In der Trockenzeit ist die Atmosphäre im Amazonasbecken hauptsächlich mit BBA aus Südamerika belastet. Daher ist die AOD im Durchschnitt um einen Faktor drei größ er als in der Regenzeit. BBA wurde zu dieser Jahreszeit regelmäßig bis zu einer Höhe von 4-6 km detektiert. Basierend auf den vorgestellten Langzeitmessungen werden erstmalig die optischen Eigenschaften von südamerikanischem BBA statistisch analysiert und diskutiert. / Continuous lidar measurements were performed in the Amazon rain forest for almost one year in 2008. The results of the automated multiwavelength-Raman-polarization lidar observations were presented in this dissertation. These measurements are the first long-term observations of the vertical aerosol structure ever made in the Amazon Basin. The advanced lidar observations were conducted 60 km north of Manaus in the central northern part of Amazonia. The area is widely covered with pristine rain forest. A HYSPLIT backward-trajectory analysis showed that the observations were representative on a regional scale for the central northern part of the Amazon rain forest. The general weather conditions in this region are characterized by a wet (December-June) and a dry season (July-November). During the dry season, a high fire activity occurs in Amazonia, which heavily influences the atmospheric conditions. With the lidar instrument, vertical profiles of the particle backscatter coefficient at 355, 532, and 1064 nm, of the particle extinction coefficient at 355 and 532 nm, and of the particle linear depolarization ratio at 355 nm can be determined. The results from the long-term lidar observations performed in Brazil contain a lot of new information about the aerosol conditions in the central northern Amazon Basin and corroborate certain findings from former aerosol measurements in Amazonia. It was shown for the first time that advection of Saharan dust together with biomass burning aerosol (BBA) from Africa occurred regularly throughout the wet season. In about one third (32%) of all lidar observations during the wet season, African aerosol was dominating the optical aerosol properties in Amazonia. The analysis of the vertical aerosol structure during such events revealed that the African aerosol arriving in the central northern Amazon Basin was usually trapped in the lowermost 3-3.5 km of the troposphere. To quantify the amount of Saharan dust and African smoke transported towards the lidar site, the dust contribution to the measured optical aerosol properties was separated by means of the measured particle depolarization ratio. This study led to the result that in about one half of the cases with African aerosol advection, smoke particles contributed to more than 50% to the total Aerosol Optical Depth (AOD). The smoke transport from Africa towards Amazonia occurred predominantly between January and April when the fire activity in Central Africa was highest. BBA is thus a major constituent of the aerosol plumes that are regularly transported from Africa towards Amazonia. This is a key finding of the presented study. During clean conditions, an AOD (532 nm) of less than 0.05 was observed and the aerosol was trapped in the lowermost 2 km of the troposphere. However, the analysis of the long-term data set revealed that these clean atmospheric conditions occurred in only 48% of all wet-season cases. One example for such background conditions was intensively discussed and it was shown that a major meso-scale rain event occurred in the Amazon region at the same time. This precipitation event was possibly partly responsible for the very low aerosol load. Two case studies from the dry season were presented for which BBA dominated the optical properties. In the first case, a comparable high aerosol load (AOD of 0.41) prevailed while in the second one, a medium aerosol load (AOD of 0.15) was observed. Aged BBA advected from regions south of the lidar site were identified to be the dominant aerosol species for both cases. However, very different geometrical, optical and microphysical properties of BBA (e.g., vertical layering, lidar ratio, Ångström exponent, effective radius, SSA) were observed on both days. In the first case, aerosol was present up to about 4.5 km. Extinction-related Ångström exponent s of about 1 and lidar ratios between 70 and 90 sr were found at different heights for the smoke aerosol. The BBA was highly absorbing (SSA of 0.81) at heights of the highest RH (85%), whereas above under dry conditions (RH=50%) only moderate absorption (SSA of 0.93) was detected. In the second case, smoke was detected up to 4.5 km, and Ångström exponent of about 2 and lidar ratios of 45-55 sr were measured in the aerosol layers. The BBA was only moderately absorbing indicated by SSA values between 0.92 and 0.94. The reason for the differences in the smoke properties could be the shorter travel time to the lidar site (<24 h), different aging processes (e.g., cloud/rain processing), or different burning conditions. In both cases, no depolarizing effects of the BBA could be observed. The strong contrast between the aerosol conditions in the dry season and the wet season were confirmed by the statistical analysis of all lidar observations in 2008. Due to the high BBA concentration in the atmosphere, the mean AOD of the dry season was found to be a factor of 3 higher than the mean AOD of the wet season (0.26 compared to 0.08 at 532 nm). Maximum AOD values were less than 0.55 (at 532 nm) and hence show that the lidar location was not in the direct vicinity of fire events. In only 7% of all cases in the dry season 2008, an AOD below 0.1 was observed. Also the maximum extinction and backscatter coefficient values in the dry season 2008 were 2-3 times higher than during the wet season of this year. The vertical aerosol distributions differ also significantly between the two seasons. In the wet season, the aerosol was mostly trapped in the lowermost 2.5 km, while in the dry season aerosol typically reached up to 4.5 km. Aerosol was occasionally detected up to 6.14 km in the dry season. The majority of the aerosol (95% of the AOD), however, was found to be on average below 2.3 km in the wet season and below 3 km in the dry season. During the wet season, lofted aerosol layers and multiple aerosol stratification was less frequent than in the dry season. The extent of BBA plumes during the dry season showed no correlation to the ML top height. Virtually uniform smoke haze layers were observed up to the AL top. Thus, pyro-convection and/or cloud-related mixing seem to be the major processes for the vertical distribution of BBA.

L’objectif principal de cette thèse est de caractériser l’atmosphère de Jupiters chaudes par spectroscopie de transmission à haute résolution, dans l’infrarouge proche, avec l’instrument SPIRou. L’historique de formation, d’évolution et de migration des planètes est empreint dans leur composition chimique, et de retrouver cette composition permet d’en élucider le mystère. La spectroscopie de transit et d’émission a prouvé être fortement efficace à cette tâche, autant pour la détermination de la composition que pour la détermination d’autres caractéristiques atmosphériques comme le profil de température et la dynamique, accessibles à haute résolution. Les Jupiter Chaudes, planètes géantes gazeuses qui orbitent très près de leur étoile, offrent des conditions d’observations très favorables pour ce type d’étude. Encore beaucoup d’éléments nous échappent quant aux processus physiques, chimiques et dynamiques qui gouvernent l’atmosphère de ces objets astronomiques. Des études détaillées de ceux-ci, telles que celles présentées dans cette thèse, sont nécessaires pour mieux comprendre ces mécanismes. Dans un premier temps, nous avons fait l’étude de deux transits de HD 189733 b, une des exoplanètes les plus étudiées. Cela nous a permis de valider nos méthodes d’analyse avec des données provenant du spectropolarimètre infrarouge à haute résolution SPIRou, installé au télescope Canada-France-Hawaii, représentant d’ailleurs la première caractérisation d’une atmosphère en spectroscopie de transit pour le SPIRou Legacy Survey. Nous avons confirmé la présence d’un signal d’eau à un niveau de signification de plus de 5σ, basé sur les résultats de test-t. Nous présentons la première analyse de spectroscopie de transit haute résolution faite par méthode de récupération, basée sur l’inférence bayésienne et appliquée à une grille de modèles SCARLET interpolée. Celle-ci a permis d’inférer une abondance de log_10[H2O] ≃ −4.4. Les résultats obtenus sont cohérents avec la littérature et indiquent que l’atmosphère de HD 189733 b est relativement claire (sans nuages) et possède un C/O super-solaire (correspondant à une formation au-delà de la ligne de glace de l’eau). Un fort décalage vers le bleu de l’absorption par l’eau a été observé, indiquant la présence de forts vents allant du côté jour vers le côté nuit ou un signal dominé par le côté soir du terminateur (limbe arrière), ou une combinaison des deux. Dans un second temps, nous présentons la première analyse à haute résolution dans l’infrarouge proche de trois transits de la très peu dense sous-Saturne WASP-127 b. Une étude récente à basse résolution a montré un spectre de transmission riche et une abondance super-solaire de CO2 dans son atmosphère. La contribution de CO et de CO2 n’a cependant pu être démêlée étant donné la couverture spectrale et la résolution limitée des données HST et de Spitzer utilisées, menant à des scénarios équiprobables de faible et fort C/O. La couverture de la bande de CO à 2.3 μm par SPIRou a permis de faire cette différenciation, et nos résultats ont exclu la présence de CO en abondance supérieure à log_10[CO] = −4.3, impliquant que le signal détecté à 4.5μm dans les données Spitzer provient majoritairement du CO2. De plus, un calcul de test-t sur les données SPIRou a confirmé la détection de H2O à un niveau ajusté de 4.9σ, mais également une détection potentielle de OH, à 2.4σ. Cette présence extrêmement inattendue de OH pourrait potentiellement être expliquée si la température du côté jour est assez grande, aidée par l’irradiation amplifiée de l’étoile qui quitte la séquence principale, ou encore par du mélange vertical. Nous présentons également la première méthode de récupération complète appliquée à la spectroscopie de transit à haute résolution, en utilisant la suite de modèles petitRADTRANS, et sur trois ensembles de données différents : les données SPIRou, les données HST et Spitzer de l’étude initiale, et les deux ensembles de données combinés. Une comparaison des différents résultats obtenus confirme que l’analyse conjointe permet d’avoir de meilleures contraintes sur les paramètres atmosphériques. Alors que l’étude initiale favorisait un fort C/O, nos résultats pointent vers un C/O très sous-solaire, produit par un C/H sous-solaire et un O/H plutôt stellaire. Les scénarios de formation qui supportent une telle composition sont ceux au-delà des lignes de glace de H2O et de CO2 (∼ 10ua), avec une accrétion supplémentaire de matériel riche en O via la migration et le croisement des lignes de glaces. L’accrétion du matériel est soit dominée par le gaz et tardive (après 5 à 7 millions d’années), ou encore, mixte (de gaz et de glaces) et plus précoce, avec un mélange cœur-enveloppe substantiel. Bien qu’il en reste beaucoup à faire, ces travaux de recherche ont démontré que la spectroscopie de transit à haute résolution dans l’infrarouge proche est utile pour explorer les conditions atmosphériques des Jupiter et sous-Saturne chaudes, et plus spécifiquement, avec l’instrument SPIRou. La combinaison de données à faible et à haute résolution s’avère un outil très puissant pour l’étude des atmosphères, et le sera encore plus avec les capacités révolutionnaires de JWST. / The main objective of this thesis is to characterize the atmosphere of hot Jupiters with high resolution transmission spectroscopy in the near-infrared with the SPIRou instrument. The formation, evolution and migration history of exoplanets is imprinted in their chemical composition, and finding this composition makes it possible to trace back this history. Transit and emission spectroscopy have proven to be highly effective for this task, in the determination of the composition, but also of other atmospheric characteristics such as the temperature profile and the dynamics, accessible at high resolution. Hot Jupiters -- gas giant planets orbiting very close to their star -- offer highly favourable observation conditions for this type of study. Many pieces of the puzzle are still missing regarding the physical, chemical and dynamical processes that govern the atmospheres of these astronomical objects, and detailed studies, such as the ones presented in this thesis, are necessary to better understand those mechanisms. First, we present the results of our analysis of two HD189733b transits, one of the most studied exoplanets to date. This study allowed to validate our analysis method with SPIRou data, a high-resolution near-infrared spectro-polarimeter installed at the Canada-France-Hawaii Telescope. It also represents the first characterization of an atmosphere with transit spectroscopy as part of the SPIRou Legacy Survey. Our results confirmed the H2O detection in the planet's atmosphere at a 5 sigma level, based on a $t$-test. We present the first analysis of a Bayesian retrieval framework applied to high-resolution transmission spectroscopy, using a grid of SCARLET models. We constrained the H2O abundance to log_10[H2O] ~ -4.4$. The results are consistent with the literature and agree on the atmosphere of HD189733b being relatively clear (without clouds) and having a super-solar C/O (corresponding to a formation beyond the H2O ice line). A strong blue shift of the water absorption signal was observed, indicative of strong day-to-night winds or a signal dominated by the terminator's evening side (trailing limb), or a combination of both. Second, we present the first high-resolution analysis in the near-infrared of three transits of the super low-density sub-Saturn WASP-127b. A recent low-resolution study showed a rich transmission spectrum and super-solar abundance of CO2 in its atmosphere. However, the contribution of CO and CO2 could not be disentangled given the limited spectral coverage and resolution of the HST and Spitzer data, leading to equiprobable low and high C/O scenarios. The coverage of the CO band at 2.3um by SPIRou made it possible to differentiate between the two cases, and our results excluded CO abundances greater than 10^(-4.3), implying that the signal at 4.5um seen in the Spitzer data mostly comes from CO2. Moreover, a t-test analysis on the SPIRou data confirmed the detection of H2O at an adjusted level of 4.9 sigma, but also a tentative detection of OH, at 2.4 sigma. The presence of OH, although extremely unexpected, could potentially be explained from a high enough dayside temperature, increased by the amplified irradiation of the star leaving the main sequence, or from vertical mixing. We also present the first full-retrieval framework applied to transmission spectroscopy at high resolution, using the petitRADTRANS model suite on three different datasets: on the SPIRou data, on the HST and Spitzer data from the original study, and on both datasets combined. A comparison of the different results obtained confirms that the joint analysis provides better constraints on the atmospheric parameters. While the initial study favored a high C/O, our results point toward a highly subsolar C/O, produced by a sub-stellar C/H and a roughly stellar O/H. Formation scenarios that support such a composition are those beyond the H2O and CO2 ice lines (~ 10ua), with further accretion of O-rich material via migration and ice lines crossing. The primordial/bulk accretion was either gas-dominated and late (after 5-7 Myr), or earlier and mixed (with gas and ice), with substantial core-enveloppe mixing. Although much remains to be done, this research work has demonstrated that high-resolution near-infrared transit spectroscopy is useful for exploring the atmospheric conditions of hot Jupiters and sub-Saturns, and more specifically, with the SPIRou instrument. The combination of low and high resolution data has shown to be a very powerful tool for such studies, and will be even more so with the revolutionary capabilities of JWST.

Im Rahmen der vorliegenden Arbeit wurden die Eigenschaften von atmosphärischen Aerosolpartikeln im tropischen Regenwald des Amazonasgebietes bestimmt. Dazu wurden die Daten einer fast einjährigen Lidarmesskampagne ausgewertet und diskutiert. Die Messungen wurden mit einem automatischen Mehrwellenlängen-Polarisations-Raman-Lidar im zentralen Amazonasbecken nahe Manaus, Brasilien, im Zeitraum von Januar bis November 2008 durchgeführt. Somit konnten erstmalig optische und mikrophysikalische Aerosoleigenschaften im Amazonasgebiet während der Regenzeit (ca. Dezember-Mai) und Trockenzeit (ca. Juni-November) höhenaufgelöst charakterisiert werden. Einleitend werden die meteorologischen Bedingungen im Amazonasgebiet erläutert und eine Literaturübersicht über Aerosolforschung in dieser Region gegeben. Das Messgerät sowie verschiedene Kalibrier- und Korrekturschemen, die zur Datenauswertung notwendig sind, werden vorgestellt. Auch Vergleiche mit anderen Messgeräten werden diskutiert. Diese zeigen, dass die aus den Lidarmessungen abgeleiteten Parameter von hoher Qualität sind. Anhand von Fallstudien werden mit Hilfe von Rückwärtstrajektorien und Satellitenmessungen typische Aerosolbedingungen am Messstandort diskutiert. Um die generellen Unterschiede zwischen Regen- und Trockenzeit zu quantifizieren, wird eine statistische Auswertung aller analysierten Lidarmessungen präsentiert. Die Analyse der Lidardaten zeigt, dass während der Regenzeit im Amazonasgebiet in ca. der Hälfte aller Fälle sehr saubere Bedingungen mit einer Aerosol Optischen Dicke (AOD) von weniger als 0.05 (bei 532 nm) vorherrschen können. Allerdings wurde in ca. 30% aller analysierten Fälle im Zeitraum von Januar bis Mai auch afrikanisches Aerosol, vornehmlich Saharastaub und Biomasseverbrennungsaerosol (BBA), am Messstandort detektiert. Dabei dominierte meist BBA die Aerosolpopulation, wie die Depolarisationsmessungen zeigten. In der Trockenzeit ist die Atmosphäre im Amazonasbecken hauptsächlich mit BBA aus Südamerika belastet. Daher ist die AOD im Durchschnitt um einen Faktor drei größ er als in der Regenzeit. BBA wurde zu dieser Jahreszeit regelmäßig bis zu einer Höhe von 4-6 km detektiert. Basierend auf den vorgestellten Langzeitmessungen werden erstmalig die optischen Eigenschaften von südamerikanischem BBA statistisch analysiert und diskutiert. / Continuous lidar measurements were performed in the Amazon rain forest for almost one year in 2008. The results of the automated multiwavelength-Raman-polarization lidar observations were presented in this dissertation. These measurements are the first long-term observations of the vertical aerosol structure ever made in the Amazon Basin. The advanced lidar observations were conducted 60 km north of Manaus in the central northern part of Amazonia. The area is widely covered with pristine rain forest. A HYSPLIT backward-trajectory analysis showed that the observations were representative on a regional scale for the central northern part of the Amazon rain forest. The general weather conditions in this region are characterized by a wet (December-June) and a dry season (July-November). During the dry season, a high fire activity occurs in Amazonia, which heavily influences the atmospheric conditions. With the lidar instrument, vertical profiles of the particle backscatter coefficient at 355, 532, and 1064 nm, of the particle extinction coefficient at 355 and 532 nm, and of the particle linear depolarization ratio at 355 nm can be determined. The results from the long-term lidar observations performed in Brazil contain a lot of new information about the aerosol conditions in the central northern Amazon Basin and corroborate certain findings from former aerosol measurements in Amazonia. It was shown for the first time that advection of Saharan dust together with biomass burning aerosol (BBA) from Africa occurred regularly throughout the wet season. In about one third (32%) of all lidar observations during the wet season, African aerosol was dominating the optical aerosol properties in Amazonia. The analysis of the vertical aerosol structure during such events revealed that the African aerosol arriving in the central northern Amazon Basin was usually trapped in the lowermost 3-3.5 km of the troposphere. To quantify the amount of Saharan dust and African smoke transported towards the lidar site, the dust contribution to the measured optical aerosol properties was separated by means of the measured particle depolarization ratio. This study led to the result that in about one half of the cases with African aerosol advection, smoke particles contributed to more than 50% to the total Aerosol Optical Depth (AOD). The smoke transport from Africa towards Amazonia occurred predominantly between January and April when the fire activity in Central Africa was highest. BBA is thus a major constituent of the aerosol plumes that are regularly transported from Africa towards Amazonia. This is a key finding of the presented study. During clean conditions, an AOD (532 nm) of less than 0.05 was observed and the aerosol was trapped in the lowermost 2 km of the troposphere. However, the analysis of the long-term data set revealed that these clean atmospheric conditions occurred in only 48% of all wet-season cases. One example for such background conditions was intensively discussed and it was shown that a major meso-scale rain event occurred in the Amazon region at the same time. This precipitation event was possibly partly responsible for the very low aerosol load. Two case studies from the dry season were presented for which BBA dominated the optical properties. In the first case, a comparable high aerosol load (AOD of 0.41) prevailed while in the second one, a medium aerosol load (AOD of 0.15) was observed. Aged BBA advected from regions south of the lidar site were identified to be the dominant aerosol species for both cases. However, very different geometrical, optical and microphysical properties of BBA (e.g., vertical layering, lidar ratio, Ångström exponent, effective radius, SSA) were observed on both days. In the first case, aerosol was present up to about 4.5 km. Extinction-related Ångström exponent s of about 1 and lidar ratios between 70 and 90 sr were found at different heights for the smoke aerosol. The BBA was highly absorbing (SSA of 0.81) at heights of the highest RH (85%), whereas above under dry conditions (RH=50%) only moderate absorption (SSA of 0.93) was detected. In the second case, smoke was detected up to 4.5 km, and Ångström exponent of about 2 and lidar ratios of 45-55 sr were measured in the aerosol layers. The BBA was only moderately absorbing indicated by SSA values between 0.92 and 0.94. The reason for the differences in the smoke properties could be the shorter travel time to the lidar site (<24 h), different aging processes (e.g., cloud/rain processing), or different burning conditions. In both cases, no depolarizing effects of the BBA could be observed. The strong contrast between the aerosol conditions in the dry season and the wet season were confirmed by the statistical analysis of all lidar observations in 2008. Due to the high BBA concentration in the atmosphere, the mean AOD of the dry season was found to be a factor of 3 higher than the mean AOD of the wet season (0.26 compared to 0.08 at 532 nm). Maximum AOD values were less than 0.55 (at 532 nm) and hence show that the lidar location was not in the direct vicinity of fire events. In only 7% of all cases in the dry season 2008, an AOD below 0.1 was observed. Also the maximum extinction and backscatter coefficient values in the dry season 2008 were 2-3 times higher than during the wet season of this year. The vertical aerosol distributions differ also significantly between the two seasons. In the wet season, the aerosol was mostly trapped in the lowermost 2.5 km, while in the dry season aerosol typically reached up to 4.5 km. Aerosol was occasionally detected up to 6.14 km in the dry season. The majority of the aerosol (95% of the AOD), however, was found to be on average below 2.3 km in the wet season and below 3 km in the dry season. During the wet season, lofted aerosol layers and multiple aerosol stratification was less frequent than in the dry season. The extent of BBA plumes during the dry season showed no correlation to the ML top height. Virtually uniform smoke haze layers were observed up to the AL top. Thus, pyro-convection and/or cloud-related mixing seem to be the major processes for the vertical distribution of BBA.

Cette thèse présente une étude empirique et théorique approfondie de l'évolution spectrale des étoiles naines blanches, avec un accent particulier sur les naines blanches chaudes. La composition atmosphérique (et donc l'apparence spectrale) de ces cadavres stellaires peut changer drastiquement avec le temps à mesure qu'ils se refroidissent. Ce phénomène est généralement interprété comme le résultat d'une compétition entre divers mécanismes de transport des éléments dans l'enveloppe stellaire (tels que la diffusion, la convection, les vents et l'accrétion), mais demeure mal compris à plusieurs égards. Il est impératif de remédier à cette situation pour être en mesure d'exploiter le potentiel immense des naines blanches pour notre compréhension du passé de la Galaxie. Pour mieux caractériser l'incidence de l'évolution spectrale, nous effectuons tout d'abord une analyse spectroscopique exhaustive de près de 2000 naines blanches chaudes (Teff > 30,000 K) observées par le relevé SDSS. Nous déterminons les propriétés atmosphériques (notamment la température effective et la composition de surface) de ces objets à l'aide d'un nouvel ensemble de modèles d'atmosphère calculé spécifiquement à cet effet. En examinant la fréquence relative des étoiles riches en hydrogène et riches en hélium en fonction de la température, nous obtenons pour la première fois un portrait empirique détaillé de l'évolution spectrale des naines blanches chaudes. Plus spécifiquement, nous déduisons (1) qu'environ une étoile sur quatre arrive sur la séquence de refroidissement avec une atmosphère d'hélium, et (2) qu'environ deux tiers de ces objets développent ultérieurement une atmosphère d'hydrogène. En outre, nous accordons une attention particulière aux naines blanches hybrides (qui montrent à la fois des traces d'hydrogène et d'hélium) de notre échantillon et à ce que ces objets distinctifs nous apprennent sur l'évolution spectrale. Nous étudions ensuite l'évolution spectrale d'un point de vue théorique en modélisant les transformations chimiques qui s'opèrent dans les naines blanches. Pour ce faire, nous utilisons le code d'évolution stellaire STELUM, qui inclut un traitement cohérent et réaliste du transport des éléments et nous permet donc de réaliser les simulations numériques d'évolution spectrale les plus sophistiquées à ce jour. Nous modélisons la diffusion de l'hydrogène résiduel dans une enveloppe d'hélium à haute température, qui mène ultimement à la formation d'une atmosphère d'hydrogène. Nous simulons également le mélange convectif de cette couche superficielle d'hydrogène avec la couche sous-jacente d'hélium à basse température, qui produit à nouveau une surface dominée par l'hélium. En outre, nous étudions le transport du carbone dans les étoiles riches en hélium, incluant à la fois le tri gravitationnel à haute température et le dragage convectif à basse température. Ces calculs donnent lieu à plusieurs résultats astrophysiques d'intérêt. Nous obtenons notamment une contrainte inédite sur la quantité d'hydrogène résiduel contenue dans les naines blanches chaudes dominées par l'hélium. Nous démontrons aussi que la bifurcation observée dans le diagramme couleur-magnitude des naines blanches découvertes par le satellite Gaia est une signature du processus de mélange convectif à basse température. Par ailleurs, nos modèles fournissent de précieuses informations sur les propriétés des étoiles polluées par le carbone, en particulier sur leur masse et leur zone convective. Enfin, le résultat le plus important de cette thèse est la résolution définitive du problème le plus sérieux de la théorie de l'évolution spectrale, soit le problème de l'origine de l'hydrogène à la surface des naines blanches de type DBA. / This thesis presents an in-depth empirical and theoretical study of the spectral evolution of white dwarf stars, with a particular focus on hot white dwarfs. The atmospheric composition (and thus the spectral appearance) of these stellar remnants can change drastically over time as they cool. This phenomenon is generally interpreted as the result of an interplay between various element transport mechanisms in the stellar envelope (such as diffusion, convection, winds, and accretion), but remains poorly understood in several respects. It is imperative to remedy this situation to be able to exploit the immense potential of white dwarfs for our understanding of the past of the Galaxy. To better characterize the incidence of spectral evolution, we first carry out an exhaustive spectroscopic analysis of nearly 2000 hot white dwarfs (Teff > 30,000 K) observed by the SDSS survey. We determine the atmospheric properties (in particular the effective temperature and surface composition) of these objects using a new set of model atmospheres calculated specifically for this purpose. By examining the relative frequency of hydrogen-rich and helium-rich stars as a function of temperature, we obtain for the first time a detailed empirical picture of the spectral evolution of hot white dwarfs. More specifically, we infer (1) that about one in four stars enters the cooling sequence with a helium atmosphere, and (2) that about two-thirds of these objects eventually develop a hydrogen atmosphere. Furthermore, we pay special attention to the hybrid white dwarfs (which exhibit traces of both hydrogen and helium) in our sample and to what can be learned about spectral evolution from these distinctive objects. We then study spectral evolution from a theoretical point of view by modeling the chemical transformations that take place in white dwarfs. To do this, we use the stellar evolution code STELUM, which includes a consistent and realistic treatment of element transport and therefore allows us to perform the most sophisticated numerical simulations of spectral evolution to date. We model the diffusion of residual hydrogen in a helium envelope at high temperature, which ultimately leads to the formation of a hydrogen atmosphere. We also simulate the convective mixing of this superficial hydrogen layer with the underlying helium layer at low temperature, which once again produces a helium-dominated surface. Furthermore, we study the transport of carbon in helium-rich stars, including both gravitational settling at high temperature and convective dredge-up at low temperature. These calculations give rise to several astrophysical results of interest. In particular, we obtain an unprecedented constraint on the amount of residual hydrogen contained within hot helium-dominated white dwarfs. We also demonstrate that the bifurcation observed in the color-magnitude diagram of white dwarfs discovered by the Gaia satellite is a signature of the convective mixing process at low temperature. Furthermore, our models provide valuable information on the properties of carbon-polluted stars, in particular on their mass and convective zone. Finally, the most important result of this thesis is the definitive resolution of the most serious problem of the theory of spectral evolution, namely the problem of the origin of hydrogen at the surface of DBA-type white dwarfs.