Carbonyl sulfide (OCS) is emitted to the atmosphere through the outgassing of ocean surface waters. OCS is also the primary source of sulfur-containing compounds in the stratosphere and contributes to the formation of the stratospheric sulfate layer, an essential controller of the radiative balance of the atmosphere. During the 2016 Student Airborne Research Program (SARP), 15 whole air samples were collected on the NASA DC-8 aircraft over the Santa Barbara Channel. Five additional surface samples were taken at various locations along the Santa Barbara Channel. The samples were analyzed using gas chromatography in the Rowland-Blake lab at UC Irvine, and compounds associated with ocean emissions including OCS, dimethyl sulfide (DMS), carbon disulfide (CS2), bromoform (CHBr3), and methyl iodide (CH3I) were examined. Excluding OCS, the vertical distribution of marine tracers that were analyzed showed dilution with increasing altitude. For OCS, the surface samples all exhibited elevated concentrations of OCS in comparison to samples taken from the aircraft, with an average of 666 ± 26 pptv, whereas the average concentration of OCS in the aircraft samples was 581 ± 9 pptv. 2016 Surface samples were compared to surface samples from SARP campaigns between 2009-2015 taken near or within the 2016 study region. The 2009-2015 samples exhibited an average OCS concentration of 526 ± 8 pptv. It is evident that the 2016 surface samples measured higher concentrations of OCS than ever recorded during previous SARP campaigns and in comparison to global averages: 525 ± 17 pptv in the Northern hemisphere and 482 ± 13 pptv in the Southern hemisphere (Sturges et al., 2001). OCS emissions should be measured using surface samples if emission estimates from the ocean are to be evaluated since measurements from the aircraft (500 ft) are not sufficiently capturing surface concentrations. Additionally, OCS enhancements seen in 2016 had never before been detected by surface samples, revealing a potential phenomenon at work causing the elevation during this year’s campaign.

Gravity waves play a fundamental role in driving the large-scale circulation of the atmosphere. They are influenced both by the variation in their sources and the filtering effects of the winds they encounter as they ascend through the atmosphere. In this thesis we present new evidence that gravity waves play a key role in coupling the troposphere, stratosphere and mesosphere. In particular, we examine the connection of gravity waves to two important large-scale oscillations that occur in the atmosphere, namely the Madden-Julian Oscillation (MJO) in the troposphere and the Mesospheric Semi-Annual Oscillation (MSAO). We present the first ever demonstration that the MJO acts to modulate the global field of gravity waves ascending into the tropical stratosphere. We discover a significant correlation with the MJO zonal-wind anomalies and so suggest that the MJO modulates the stratospheric gravity-wave field through a critical-level wave-filtering mechanism. Strong evidence for this mechanism is provided by consideration of the winds encountered by ascending waves. The Ascension Island meteor radar is used for the first time to measure momentum fluxes over the Island. These measurements are then used to investigate the role of gravity-wave in driving a dramatic and anomalous wind event that was observed to occur during the first westward phase of the MSAO in 2002. Gravity waves are shown to play an important role in driving this event, but the observations presented here also suggest that the current theory of the mechanism describing these anomalous mesospheric wind events is not valid. Both of these studies highlight the critical importance of gravity waves to the dynamics of the atmosphere and highlight the need for further work to truly understand these waves, their processes and their variability.

Atmospheric mass is transported in and out of the stratospheric polar cap region by a wave-driven meridional circulation. Using composites of polar cap pressure anomalies, defined as deviations from the average annual cycle, it is shown that this stratospheric mass flux is accompanied by a similar mass flux near the surface. This 'tropospheric amplification' of the stratospheric signal is introduced as a new way to quantify stratosphere-troposphere coupling. Regression analysis is used to create a vertical profile of atmospheric pressure during a tropospheric amplification event, and the regression slope profile is used as a tool to quantify the amplification. Using data from 5 reanalysis datasets and 11 climate models, it is shown that high-top models, with a model lid of above 1 hPa, are significantly better at reproducing tropospheric amplification than low-top models, due to having more detailed parameterisations of stratospheric processes. However, the regression slope profiles of all models, bar one, are significantly different to the profile of reanalysis data at a 95% confidence level. Tropospheric amplification is also investigated in historical and future simulations from these models, and it is concluded that there is not expected to be a large change in the phenomenon over the next 100 years. The processes needed to reproduce tropospheric amplification can be identified by comparing idealised models of different complexity. A simple dry-core model is not able to reproduce tropospheric amplification, while a model with a comprehensive radiation scheme does produce the basic regression slope profile under certain configurations. The associations between pressure change and mass flux are further investigated using primitive equations. It is found that vertical and horizontal contributions to mass flux act to mostly cancel each other out, leaving a poorly-conditioned residual, and that the horizontal mass flux across the polar cap boundary has both geostrophic and ageostrophic components.

<p>The Earth's middle atmosphere at about 10-100 km has shown a substantial sensitivity to human activities. First, the ozone layer has been reduced since the the early 1980s due to man-made emissions of halogenated hydrocarbons. Second, the middle atmosphere has been identified as a region showing clear evidence of climate change due to increased emissions of greenhouse gases. While increased CO₂abundances are expected to lead to a warmer climate near the Earth's surface, observations show that the middle atmosphere has been cooling by up to 2-3 degrees per decade over the past few decades. This is partly due to CO₂ increases and partly due to ozone depletion.</p><p>Predicting the future development of the middle atmosphere is problematic because of strong feedbacks between temperature and ozone. Ozone absorbs solar ultraviolet radiation and thus warms middle atmosphere, and also, ozone chemistry is temperature dependent, so that temperature changes are modulated by ozone changes.</p><p>This thesis examines the middle atmospheric response to a doubling of the atmospheric CO₂ content using a coupled chemistry-climate model. The effects can be separated in the intrinsic CO₂-induced radiative response, the radiative feedback through ozone changes and the response due to changes in the climate of the underlying atmosphere and surface. The results show, as expected, a substantial cooling throughout the middle atmosphere, mainly due to the radiative impact of the CO₂ increase. Model simulations with and without coupled chemistry show that the ozone feedback reduces the temperature response by up to 40%. Further analyses show that the ozone changes are caused primarily by the temperature dependency of the reaction O+O₂+M->O₃+M. The impact of changes in the surface climate on the middle atmosphere is generally small. In particular, no noticeable change in upward propagating planetary wave flux from the lower atmosphere is found. The temperature response in the polar regions is non-robust and thus, for the model used here, polar ozone loss does not appear to be sensitive to climate change in the lower atmosphere as has been suggested recently. The large interannual variability in the polar regions suggests that simulations longer than 30 years will be necessary for further analysis of the effects in this region.</p><p>The thesis also addresses the long-standing dilemma that models tend to underestimate the ozone concentration at altitudes 40-75 km, which has important implications for climate change studies in this region. A photochemical box model is used to examine the photochemical aspects of this problem. At 40-55 km, the model reproduces satellite observations to within 10%, thus showing a substantial reduction in the ozone deficit problem. At 60-75 km, however, the model underestimates the observations by up to 35%, suggesting a significant lack of understanding of the chemistry and radiation in this region.</p>

<p>This thesis concerns the fate of the meteoric smoke in the Middle Atmosphere, and its effect on ice phenomena such as noctilucent clouds (NLC) and polar stratospheric clouds (PSC). </p><p>The potential role of NLC as tracer for mesospheric processes and variability, and as a tool for monitoring this remote and inaccessible region, has generated substantial interest within the scientific community. The nucleation of ice in such a dry environment is not trivial. Supersaturation is considered too low for homogeneous nucleation. Hence, pre-existing condensation nuclei are deemed necessary, with smoke particles having long been considered the most likely candidate. Here we show that the atmospheric circulation transports meteoric smoke particles away from the polar region before they coagulate large enough to efficiently act as ice condensation nuclei. We also show that the charging of meteoric smoke, in combination with deviations from the mean thermal state, may solve this dilemma by significantly altering the ice nucleation properties of smoke. Thus, while it is highly questionable whether neutral smoke can provide sufficient amounts of condensation nuclei for ice formation at the polar summer mesopause, charged meteoric smoke proves to be a promising candidate to explain mesospheric ice phenomena as we observe them.</p><p> We further show that the bulk of the meteoric material is transported to the Arctic winter stratosphere, yielding significantly higher concentrations of meteoric smoke in the region of PSC nucleation than has previously been believed. Our new predictions of meteoric smoke in this region may thus shed new light on open questions relating to PSC nucleation.</p>

<p>Water vapour is the most important greenhouse gas and plays a fundamental role in the climate system and for the chemistry of the Earth's atmosphere. This thesis presents observations of water vapour in the middle atmosphere with a particular focus on the mesosphere. The majority of these observations presented in this thesis have been performed by the Swedish satellite Odin, providing global observations since 2001. Further observations come from the Hygrosonde-2 campaign in December 2001 based on balloon and rocket-borne measurements. A general overview of Odin's water vapour measurements in the middle atmosphere is given. The optimisation of the mesospheric water vapour retrieval is presented in detail.</p><p>The analysis of the observations has focused mainly on different dynamical aspects utilising the characteristic of water vapour as a dynamical tracer in the middle atmosphere. One application is the mesospheric part of the semi-annual oscillation (SAO). The observations reveal that this oscillation is the dominant pattern of variability between 30°S and 10°N in the mesosphere up to an altitude of 80 km. Above 90 km the SAO is dominating at all latitudes in the tropics and subtropics. It is shown that the SAO exhibits a distinct phase change between 75 km and 80 km in the tropical region.</p><p>This thesis also presents the first satellite observations of water vapour in the altitude range between 90 km and 110 km, extending the observational database up into the lower thermosphere. In the polar regions water vapour exhibits the annual maximum during winter time above 95 km, mainly caused by upwelling during this season. This behaviour is different from that observed in the subjacent part of the mesosphere where the annual maximum occurs during summer time.</p><p>The Hygrosonde-2 campaign provided a high resolution measurement of water vapour in the vicinity of the polar vortex edge. This edge prevents horizontal transport causing different water vapour characteristics inside and outside the polar vortex. The observations show that this separating behaviour extends high up into the mesosphere. Small scale transitions in the Hygrosonde-2 profile between conditions inside and outside the vortex coincided with wind shears caused by gravity waves.</p>

Der frühwinterliche Ozongehalt ist ein Indikator für den Ozongehalt im Spätwinter/Frühjahr. Jedoch weist dieser aufgrund von Absinkprozessen, chemisch bedingten Ozonabbau und Wellenaktivität von Jahr zu Jahr starke Schwankungen auf. Die vorliegende Arbeit zeigt, dass diese Variabilität weitestgehend auf dynamische Prozesse während der Wirbelbildungsphase des arktischen Polarwirbels zurückgeht. Ferner wird der bisher noch ausstehende Zusammenhang zwischen dem früh- und spätwinterlichen Ozongehalt bezüglich Dynamik und Chemie aufgezeigt. Für die Untersuchung des Zusammenhangs zwischen der im Polarwirbel eingeschlossenen Luftmassenzusammensetzung und Ozonmenge wurden Beobachtungsdaten von Satellitenmessinstrumenten und Ozonsonden sowie Modellsimulationen des Lagrangschen Chemie/Transportmodells ATLAS verwandt. Die über die Fläche (45–75°N) und Zeit (August-November) gemittelte Vertikalkomponente des Eliassen-Palm-Flussvektors durch die 100hPa-Fläche zeigt eine Verbindung zwischen der frühwinterlichen wirbelinneren Luftmassenzusammensetzung und der Wirbelbildungsphase auf. Diese ist jedoch nur für die untere Stratosphäre gültig, da die Vertikalkomponente die sich innerhalb der Stratosphäre ändernden Wellenausbreitungsbedingungen nicht erfasst. Für eine verbesserte Höhendarstellung des Signals wurde eine neue integrale auf der Wellenamplitude und dem Charney-Drazin-Kriterium basierende Größe definiert. Diese neue Größe verbindet die Wellenaktivität während der Wirbelbildungsphase sowohl mit der Luftmassenzusammensetzung im Polarwirbel als auch mit der Ozonverteilung über die Breite. Eine verstärkte Wellenaktivität führt zu mehr Luft aus niedrigeren ozonreichen Breiten im Polarwirbel. Aber im Herbst und Frühwinter zerstören chemische Prozesse, die das Ozon ins Gleichgewicht bringen, die interannuale wirbelinnere Ozonvariablität, die durch dynamische Prozesse während der arktischen Polarwirbelbildungsphase hervorgerufen wird. Eine Analyse in Hinblick auf den Fortbestand einer dynamisch induzierten Ozonanomalie bis in den Mittwinter ermöglicht eine Abschätzung des Einflusses dieser dynamischen Prozesse auf den arktischen Ozongehalt. Zu diesem Zweck wurden für den Winter 1999–2000 Modellläufe mit dem Lagrangesche Chemie/Transportmodell ATLAS gerechnet, die detaillierte Informationen über den Erhalt der künstlichen Ozonvariabilität hinsichtlich Zeit, Höhe und Breite liefern. Zusammengefasst, besteht die dynamisch induzierte Ozonvariabilität während der Wirbelbildungsphase länger im Inneren als im Äußeren des Polarwirbels und verliert oberhalb von 750K potentieller Temperatur ihre signifikante Wirkung auf die mittwinterliche Ozonvariabilität. In darunterliegenden Höhenbereichen ist der Anteil an der ursprünglichen Störung groß, bis zu 90% auf der 450K. Innerhalb dieses Höhenbereiches üben die dynamischen Prozesse während der Wirbelbildungsphase einen entscheidenden Einfluss auf den Ozongehalt im Mittwinter aus. / The ozone amount in early winter provides an indication of the ozone amount in late winter/early spring. The early winter amount is highly variable from year to year due to modification by subsidence, chemical loss and wave activity. This thesis shows that this variability is mainly caused by the dynamics during the Arctic polar vortex formation. Furthermore, it explains the still missing link between early and late winter ozone amount due to dynamics and chemistry. Observational ozone data from satellite based instruments, ozone probes and simulations are used for the investigation of the connection between the composition of the air and the ozone enclosed in the polar vortex. The simulations are calculated with the Lagrangian chemistry/transport model ATLAS. The over area (45–75°N) and time (August-November) averaged vertical component of the Eliassen-Palm flux at 100hPa points to a link between the early winter composition of the air enclosed in the polar vortex and the vortex formation phase. This is only valid for the lower stratosphere, because the component does not satisfy changing conditions for wave propagation throughout the stratosphere by itself. Due to this deficit a new integral quantity based on wave amplitude and properties of the Charney-Drazin criterion is defined to achieve an improvement with height. This new quantity connects the wave activity during vortex formation to the composition of air inside the vortex as well as the distribution of ozone over latitude. An enhanced wave activity leads to a higher proportion of ozone rich air from lower latitudes inside the polar vortex. But chemistry in autumn and early winter removes the interannual variability in the amount of ozone enclosed in the vortex induced by dynamical processes during the formation phase of the Artic polar vortex because ozone relaxes towards equilibrium. An estimation of how relevant these variable dynamical processes are for the Arctic winter ozone abundances is obtained by analysing which fraction of dynamically induced anomalies in ozone persists until mid winter. Model runs with the Lagrangian Chemistry-Transport-Model ATLAS for the winter 1999–2000 are used to assess the fate of ozone anomalies artificially introduced during the vortex formation phase. These runs provide detailed information about the persistence of the induced ozone variability over time, height and latitude. Overall, dynamically induced ozone variability from the vortex formation phase survives longer inside the polar vortex compared to outside and can not significantly contribute to mid-winter variability at levels above 750K potential temperature level. At lower levels increasingly larger fractions of the initial perturbation survive, reaching 90% at 450K potential temperature level. In this vertical range dynamical processes during the vortex formation phase are crucial for the ozone abundance in mid-winter.

The Earth's middle atmosphere at about 10-100 km has shown a substantial sensitivity to human activities. First, the ozone layer has been reduced since the the early 1980s due to man-made emissions of halogenated hydrocarbons. Second, the middle atmosphere has been identified as a region showing clear evidence of climate change due to increased emissions of greenhouse gases. While increased CO2 abundances are expected to lead to a warmer climate near the Earth's surface, observations show that the middle atmosphere has been cooling by up to 2-3 degrees per decade over the past few decades. This is partly due to CO2 increases and partly due to ozone depletion. Predicting the future development of the middle atmosphere is problematic because of strong feedbacks between temperature and ozone. Ozone absorbs solar ultraviolet radiation and thus warms middle atmosphere, and also, ozone chemistry is temperature dependent, so that temperature changes are modulated by ozone changes. This thesis examines the middle atmospheric response to a doubling of the atmospheric CO2 content using a coupled chemistry-climate model. The effects can be separated in the intrinsic CO2-induced radiative response, the radiative feedback through ozone changes and the response due to changes in the climate of the underlying atmosphere and surface. The results show, as expected, a substantial cooling throughout the middle atmosphere, mainly due to the radiative impact of the CO2 increase. Model simulations with and without coupled chemistry show that the ozone feedback reduces the temperature response by up to 40%. Further analyses show that the ozone changes are caused primarily by the temperature dependency of the reaction O+O2+M-&gt;O3+M. The impact of changes in the surface climate on the middle atmosphere is generally small. In particular, no noticeable change in upward propagating planetary wave flux from the lower atmosphere is found. The temperature response in the polar regions is non-robust and thus, for the model used here, polar ozone loss does not appear to be sensitive to climate change in the lower atmosphere as has been suggested recently. The large interannual variability in the polar regions suggests that simulations longer than 30 years will be necessary for further analysis of the effects in this region. The thesis also addresses the long-standing dilemma that models tend to underestimate the ozone concentration at altitudes 40-75 km, which has important implications for climate change studies in this region. A photochemical box model is used to examine the photochemical aspects of this problem. At 40-55 km, the model reproduces satellite observations to within 10%, thus showing a substantial reduction in the ozone deficit problem. At 60-75 km, however, the model underestimates the observations by up to 35%, suggesting a significant lack of understanding of the chemistry and radiation in this region.

This thesis concerns the fate of the meteoric smoke in the Middle Atmosphere, and its effect on ice phenomena such as noctilucent clouds (NLC) and polar stratospheric clouds (PSC). The potential role of NLC as tracer for mesospheric processes and variability, and as a tool for monitoring this remote and inaccessible region, has generated substantial interest within the scientific community. The nucleation of ice in such a dry environment is not trivial. Supersaturation is considered too low for homogeneous nucleation. Hence, pre-existing condensation nuclei are deemed necessary, with smoke particles having long been considered the most likely candidate. Here we show that the atmospheric circulation transports meteoric smoke particles away from the polar region before they coagulate large enough to efficiently act as ice condensation nuclei. We also show that the charging of meteoric smoke, in combination with deviations from the mean thermal state, may solve this dilemma by significantly altering the ice nucleation properties of smoke. Thus, while it is highly questionable whether neutral smoke can provide sufficient amounts of condensation nuclei for ice formation at the polar summer mesopause, charged meteoric smoke proves to be a promising candidate to explain mesospheric ice phenomena as we observe them. We further show that the bulk of the meteoric material is transported to the Arctic winter stratosphere, yielding significantly higher concentrations of meteoric smoke in the region of PSC nucleation than has previously been believed. Our new predictions of meteoric smoke in this region may thus shed new light on open questions relating to PSC nucleation.

Water vapour is the most important greenhouse gas and plays a fundamental role in the climate system and for the chemistry of the Earth's atmosphere. This thesis presents observations of water vapour in the middle atmosphere with a particular focus on the mesosphere. The majority of these observations presented in this thesis have been performed by the Swedish satellite Odin, providing global observations since 2001. Further observations come from the Hygrosonde-2 campaign in December 2001 based on balloon and rocket-borne measurements. A general overview of Odin's water vapour measurements in the middle atmosphere is given. The optimisation of the mesospheric water vapour retrieval is presented in detail. The analysis of the observations has focused mainly on different dynamical aspects utilising the characteristic of water vapour as a dynamical tracer in the middle atmosphere. One application is the mesospheric part of the semi-annual oscillation (SAO). The observations reveal that this oscillation is the dominant pattern of variability between 30°S and 10°N in the mesosphere up to an altitude of 80 km. Above 90 km the SAO is dominating at all latitudes in the tropics and subtropics. It is shown that the SAO exhibits a distinct phase change between 75 km and 80 km in the tropical region. This thesis also presents the first satellite observations of water vapour in the altitude range between 90 km and 110 km, extending the observational database up into the lower thermosphere. In the polar regions water vapour exhibits the annual maximum during winter time above 95 km, mainly caused by upwelling during this season. This behaviour is different from that observed in the subjacent part of the mesosphere where the annual maximum occurs during summer time. The Hygrosonde-2 campaign provided a high resolution measurement of water vapour in the vicinity of the polar vortex edge. This edge prevents horizontal transport causing different water vapour characteristics inside and outside the polar vortex. The observations show that this separating behaviour extends high up into the mesosphere. Small scale transitions in the Hygrosonde-2 profile between conditions inside and outside the vortex coincided with wind shears caused by gravity waves.