This study examines the long-term record of lower stratospheric water vapor focusing on the 20-year data record from the Stratospheric Aerosol and Gas Experiment II (SAGE II). The SAGE II zonal monthly mean water vapor data was enhanced to include the aerosol heavy late 1980s through the use of aerosol extinction filtering of the data. Comparisons between the SAGE II lower stratospheric water vapor and the Limb Infrared Monitor of the Stratosphere (LIMS), the Microwave Limb Sounder (MLS), and HALogen Occultation Experiment (HALOE) are performed. This study further focuses on the minimum lower stratospheric water vapor (i.e., hygropause) and on the dehydration seen in the hygropause with examination of the transport barrier at both the tropical tropopause and the tropopause folding region between the tropics and extra-tropics that would account for this decadal variation. The effects of aerosol contamination on the SAGE II water vapor retrievals from four volcanic eruptions from 1984 to 1992 were examined, leading to a four level filtering of the SAGE II water vapor data to allow retention of good data from early in the data record. With the improved filtered water vapor data, monthly and seasonal time series analyses show a significant decadal variation in the lower stratosphere for all months where the satellite coverage provided data from the late 1980s to the early 2000s. This decadal variation documents a decrease in the water vapor from below approximately 25 km to below the tropopause with this decrease seen in the hygropause from the tropics to the poles. Analysis of the hygropause for all months provided a statistically significant consistent neutral or decreasing value in the long-term water vapor minimum. March was shown to be the seasonal minimum in the hygropause over this 20-year low aerosol record, followed by a discontinuity in the minimum abundance after 2000. Three transport pathways for transport of water vapor from the moist troposphere to the lower stratosphere include the tropical tropopause, isentropic transport at the sub-tropical jet locations, and meridional transport from the tropics to the midlatitudes above the hygropause. The tropical tropopause temperatures were examined using the new Modern Era Retrospective-analysis for Research and Applications (MERRA) data set. Analysis showed a significant decrease in the tropical and sub-tropical tropopause temperatures over the 20-year timeframe for the DJF season preceding the March minimum. The lower temperatures would provide a colder "cold trap" at the tropopause, further "freeze drying" the air seasonally transported from the upper troposphere to the lower stratosphere, providing the long-term dehydration in the hygropause and lower stratosphere. The Ertel's Potential Vorticity (EPV or PV) was examined as a proxy for the sub-tropical jet movement towards the poles over this long-term record. Changes in this pathway location may affect the efficiency of isentropic transport of moist tropospheric air into the lower stratosphere at these higher latitudes. Analysis using the MERRA zonal EPV and maximum zonal Uwind data showed a statistically significant shift in the locations of the contours towards the SH poles over this 20-year timeframe for the DJF, DJFM seasons and the month of December. The meridional winds above the tropopause show an increase over the 20-year record covered by SAGE II water vapor data. These increasing winds are consistent with the increase in the Brewer-Dobson circulation shown in other studies. The colder tropopause temperatures along with the increasing Brewer-Dobson circulation just above the tropopause, are the likely cause for the decreasing water vapor trend as seen in the SAGE II March hygropause over the 20-years from 1986-2005.

The classical problem of predicting the atmospheric circulation response to extratropical surface forcing is revisited in the context of the observed connection between autumn snow cover anomalies over Eurasia and the wintertime Northern Annular Mode (NAM). In general circulation model (GCM) simulations with prescribed autumn Siberian snow forcing, a vertically propagating Rossby wave train is generated, driving dynamical stratospheric warming and a negative NAM response that couples to the troposphere. It is shown that unexplained aspects of the evolution of this response can be clarified by examining the time evolution of the phasing, and hence the linear interference, between the wave response and the background climatological wave. When the wave response and background wave are in phase (out of phase), wave activity into the stratosphere is amplified (attenuated) and the zonal mean stratosphere-troposphere NAM response displays a negative (positive) tendency. This effect is probed further in a simplified GCM with imposed lower tropospheric cooling. As in the comprehensive GCM, linear interference strongly influences the NAM response. The transition from linear to nonlinear behaviour is shown to depend on forcing strength. Linear interference also plays a key role in the observed October Eurasian snow cover-NAM connection. It is shown that the time lag between October Eurasian snow anomalies and the peak wave activity flux arises because the Rossby wave train associated with the snow is out of phase with the climatological stationary wave from October to mid-November. Beginning in mid-November, the associated wave anomaly migrates into phase with the climatological wave, leading to constructive interference and anomalously positive upward wave activity fluxes. Current generation climate models do not capture this behaviour. Linear interference is not only associated with stratospheric warming due to Eurasian snow cover anomalies but is a general feature of both Northern and Southern Hemisphere stratosphere-troposphere interactions, and in particular dominated the negative NAM events of the fall-winter of 2009-2010. The interannual variability in upward wave activity flux during the season of strongest stratosphere-troposphere interactions is primarily determined by linear interference of quasi-stationary waves. The persistence of the linear interference component of this flux may help improve wintertime extratropical predictability.

The classical problem of predicting the atmospheric circulation response to extratropical surface forcing is revisited in the context of the observed connection between autumn snow cover anomalies over Eurasia and the wintertime Northern Annular Mode (NAM). In general circulation model (GCM) simulations with prescribed autumn Siberian snow forcing, a vertically propagating Rossby wave train is generated, driving dynamical stratospheric warming and a negative NAM response that couples to the troposphere. It is shown that unexplained aspects of the evolution of this response can be clarified by examining the time evolution of the phasing, and hence the linear interference, between the wave response and the background climatological wave. When the wave response and background wave are in phase (out of phase), wave activity into the stratosphere is amplified (attenuated) and the zonal mean stratosphere-troposphere NAM response displays a negative (positive) tendency. This effect is probed further in a simplified GCM with imposed lower tropospheric cooling. As in the comprehensive GCM, linear interference strongly influences the NAM response. The transition from linear to nonlinear behaviour is shown to depend on forcing strength. Linear interference also plays a key role in the observed October Eurasian snow cover-NAM connection. It is shown that the time lag between October Eurasian snow anomalies and the peak wave activity flux arises because the Rossby wave train associated with the snow is out of phase with the climatological stationary wave from October to mid-November. Beginning in mid-November, the associated wave anomaly migrates into phase with the climatological wave, leading to constructive interference and anomalously positive upward wave activity fluxes. Current generation climate models do not capture this behaviour. Linear interference is not only associated with stratospheric warming due to Eurasian snow cover anomalies but is a general feature of both Northern and Southern Hemisphere stratosphere-troposphere interactions, and in particular dominated the negative NAM events of the fall-winter of 2009-2010. The interannual variability in upward wave activity flux during the season of strongest stratosphere-troposphere interactions is primarily determined by linear interference of quasi-stationary waves. The persistence of the linear interference component of this flux may help improve wintertime extratropical predictability.

Le volcanisme plinien modifie le climat pendant plusieurs années en injectant de grandes quantités de dioxyde de soufre directement dans la stratosphère, oxydé ensuite en gouttelettes d'acide sulfurique qui réfléchissent les rayonnements solaires et changent les propriétés radiatives de l'atmosphère. L'étude de signaux volcaniques préservés dans les archives glaciaires, consistait jusqu'à présent à simplement mesurer les concentrations de sulfate. Nous proposons l'utilisation de nouveaux traceurs que sont les anomalies isotopiques de l'oxygène et du soufre de sulfate volcanique enregistré à Dôme C et Pôle Sud pour apporter de nouvelles informations sur le volcanisme passé.<br />Une étude de l'évolution temporelle des anomalies isotopiques de l'oxygène et du soufre dans les sulfates volcaniques de l'Agung (mars 1963) et du Pinatubo (juin 1991) a été menée. L'anomalie isotopique du soufre change de signe au cours du temps et passe d'une phase positive, au début du dépôt de sulfate à une phase négative à la fin. Ce changement de signe s'accompagne d'un appauvrissement en isotopes lourds avec le temps. L'anomalie isotopique du soufre est créée à partir d'une réaction d'oxydation photochimique de SO2 en acide sulfurique, suggérant un processus rapide qui dure un mois environ. L'anomalie isotopique de l'oxygène, quant à elle, a permis d'établir un lien avec l'oscillation quasi-biennale de la stratosphère.<br />Douze signaux volcaniques ont été étudiés dans leur globalité au cours du dernier millénaire. L'anomalie isotopique du soufre a permis d'identifier 6 éruptions volcaniques stratosphériques révélant l'utilité d'un tel traceur lorsque la nature des éruptions est méconnue.

It is the future of the stratospheric ozone layer, which protects life at Earth’s surface from harmful ultraviolet (UV) radiation, that is the focus of the present work. Fundamental changes in the composition and structure of the stratosphere in response to anthropogenic climate forcing may lead to catastrophic ozone loss under current, and even reduced, stratospheric halogen loading. In particular, the evolution toward a colder, wetter stratosphere, threatens to enhance the heterogeneous conversion of inorganic halogen from its reservoir species to its catalytically active forms, and thus promote in situ ozone loss. Water vapor concentrations control the availability of reactive surface area, which facilitates heterogeneous chemistry. Furthermore, the rates of the key heterogeneous processes are tightly controlled by the ambient humidity. Thus, credible predictions of UV dosage require a quantitative understanding of both the sensitivity of these chemical mechanisms to water vapor concentrations, and an elucidation of the processes controlling stratospheric water vapor concentrations. Toward this end, we present a set of four case studies utilizing high resolution in situ data acquired aboard NASA aircraft during upper atmospheric research missions over the past two decades. 1) We examine the broad scale humidity structure of the upper troposphere and lower stratosphere from the midlatitudes to the tropics, focusing on cirrus formation and dehydration at the cold-point tropical tropopause. The data show evidence for frequent supersaturation in clear air, and sustained supersaturation in the presence of cirrus. These results challenge the strict thermal control of the tropical tropopause. 2) We investigate the likelihood of cirrus-initiated activation of chlorine in the midlatitude lower stratosphere. At midlatitudes the transition from conditions near saturation below the local tropopause to undersaturated air above greatly reduces the probability of heterogeneous activation and in situ ozone loss in this region. 3) We probe the details of heterogeneous processing in the wintertime Arctic vortex, and find that in situ measurements of OH provide incontrovertible evidence for the heterogeneous reaction of HOCl with HCl. This reaction is critical to sustaining catalytically active chlorine and prolonging ozone loss in the springtime vortex. 4) We revisit the topic of midlatitude ozone loss with an emphasis upon the response of ozone in this region to changes in the chemical composition and thermal structure of the lower stratosphere induced by anthropogenic climate change. Specifically, we show evidence for episodic moisture plumes in the overworld stratosphere generated by the rapid evaporation of ice injected into this region by deep convection, and find that these high water vapor plumes have the potential to alter the humidity of the lower stratosphere, and drastically increase the rate of heterogeneous chemistry and in situ ozone loss, given sufficient reactive surface. / Earth and Planetary Sciences

Stratospheric water vapor plays an important role in the Earth system, both through its role in stratospheric ozone destruction and as a greenhouse gas contributing to radiative forcing of the climate. Highly accurate water vapor measurements are critical to understanding how stratospheric water vapor concentrations will respond to a changing climate. However, the past disagreement among water vapor instruments on the order of 1 – 2 ppmv hinders understanding of the mechanisms which control stratospheric humidity, and the reliable detection of water vapor trends. In response to these issues, we present a new dual axis water vapor instrument that combines the heritage Harvard Lyman-\(\alpha\) hygrometer with the newly developed Harvard Herriott Hygrometer (HHH). The Lyman-\(\alpha\) instrument utilizes ultraviolet photo-fragment fluorescence detection, and its accuracy has been demonstrated though rigorous laboratory calibrations and in situ diagnostic procedures. HHH employs a tunable diode near-IR laser to measure water vapor via direct absorption in a Herriott cell; it demonstrated in-flight precision of 0.1 ppmv (1-sec) with accuracy of 5%±0.5 ppmv. We describe these two measurement techniques in detail along with our methodology for calibration and details of the measurement uncertainties. We also examine the recent flight comparison of the two instruments with several other in situ hygrometers during the 2011 MACPEX campaign, in which five independent instruments agreed to within 0.7 ppmv, a significant improvement over past comparisons. Water vapor measurements in combination with simultaneous in situ measurements of \(O_3\), CO, \(CO_2\), HDO, and HCl are also used to investigate transport in the Tropical Tropopause Layer (TTL). Data from the winter 2006 CR-AVE campaign and the summer 2007 TC4 campaign are analyzed in a one-dimensional mixing model to explore the seasonal importance of transport within the TTL via slow upward ascent, convective injection, and isentropic transport from the midlatitude stratosphere. The model shows transport from midlatitudes to be significant in summer and winter, affecting ozone concentrations and therefore the radiative balance of the TTL. It also shows significant convective influence up to 420 K potential temperature in both seasons, which appreciably increases the amount of water vapor above the tropopause. / Engineering and Applied Sciences

This thesis aims to clarify the sources of, and mechanisms associated with, the generation of ozone maxima over the southern African region. Inasmuch as, tropospheric ozone concentration is a function of both chemistry and meteorology, this thesis concentrates on the role of atmospheric dynamics. Firstly, a statistical analysis of the relationship between total ozone and meteorological parameters revealed a generally weak negative relationship between total ozone and the height of the 500, 300 and 100 hPa geopotential surfaces. The relationship is best expressed by the passage of a mid-latitude cyclone while anticyclonic conditions exhibited a weak relationship. An examination of the spatial distribution of total ozone and potential vorticity (PV), during the passage of westerly troughs, prompted a more thorough investigation of the exchange of ozone between the stratosphere and troposphere. The relationship between tropospheric ozone, and low pressure and anticyclonic systems is investigated further using data obtained during the South African Fire-Atmospheric Research Initiative (SAFARI) conducted in 1992. Ozone concentrations, as expressed by ozonesonde data, reveal different characteristic profiles for the two scenarios. Explanations for the differences observed are sought in the observed circulation patterns during the experiment. Case studies at Okaukuejo (Namibia), Irene (South Africa) and Brazzaville (Congo), which were utilised as ground stations during SAFARI, are presented in an attempt to gain insight into the vertical distribution of ozone over the entire expanse of the study region. The role of convective systems in the generation of short-lived upper tropospheric ozone maxima at tropical latitudes is illustrated while the different vertical ozone signatures, expressed under cyclonic and anticyclonic systems as described earlier, are reconfirmed by the Okaukuejo and Irene data. An attempt is made to investigate dynamic links between the troposphere and stratosphere and the concomitant exchange of ozone during the passage of westerly trough systems. Particularly deep troughs or cut off low pressure systems are identified as important mechanisms in the generation of upper tropospheric ozone maxima. An examination of the vertical distribution of ozone at Irene during the passage of a COL, using data obtained from the SA'ARI 1994 experiment, suggests concurrence with Danielsen's (1968) model of tropopause folding. The intrusion of high PV and dry stratospheric air, coupled with downward flow near the tropopause, in the vicinity of the upper tropospheric disturbance, promotes the transport of ozone-rich air to tropospheric altitudes. The limited availability of data has severely hampered the understanding of tropospheric ozo~e in southern Africa in the past. This study demonstrates the value of daily vertical ozone data, even for very short periods. / Thesis (Ph.D.)-University of Natal, 1995.

An examination of the seasonal and spatial distribution of Polar Stratospheric Clouds (PSCs) inferred from standard temperature profiles in the lower-middle atmosphere above Antarctica, as derived from the Earth Observing System (EOS) Aura Microwave Limb Sounder (MLS) satellite observations and NCEP/NCAR assimilations, is provided. Chemical volume mixing ratio (VMR) observations of EOS Aura MLS v2.2 hydrogen chloride (HCl) were used to show the interannual variability of PSC formation with respect to stratospheric chlorine partitioning during five Southern Hemisphere Antarctic seasons from 2005 to 2009. A remarkable first set of results, obtained from an algorithm developed for modelling HCl depletion areas in the Antarctic polar vortex region, and based on satellite observations, is presented. In particular, the analysis of HCl concentration data obtained from 2006 indicated that the area processed for HCl was larger than the area of PSC during some periods of Antarctic winter, and that this result was robust with respect to the various PSC formation and HCl depletion thresholds utilized. The results suggest that an underestimation in chlorine activation area can occur when temperature thresholds for PSC formation thresholds are employed. The work presented here also evaluated chlorine activation via sulfate aerosol (SA) in the Southern Hemisphere 2006 stratosphere, based on satellite measurements of water vapor (H2O) and constant values of SA, by implementing the TACL formula of Drdla and Müller [2010] in contrast to the TNAT formula of Hanson and Mauersberger [1988]. The results indicated that the former formula was not completely sufficient for accurately modeling areas of depleted HCl and chlorine deactivation for all pressure surfaces in the Antarctic stratosphere. Based on the results of this study, the role of SA in chlorine activation appears to be more important at lower altitudes than for areas higher in the stratosphere.

The ionosphere-thermosphere can be considered to a certain degree as a system, which is externally-driven by the extreme-ultraviolet solar radiation. The main components in the regular variation are connected to the solar cycle, solar rotation and the diurnal cycle. However, anomalies and periodicities of several days, which cannot be related to changes in the solar activity at all times, were detected in ionospheric parameters. It is assumed that the total variation in the ionosphere is partly forced by waves coming from below. This thesis provides a clearer picture of the seasonal changes of wave phenomena observed in the ionosphere and its possible relation to lower atmospheric structures. Since such global disturbances in the middle atmosphere are termed as planetary waves (PW), such features in the ionosphere are declared as planetary wave type oscillations (PWTO), although a direct connection is excluded.Northern hemispheric maps of the Total Electron Content (TEC) derived from GPS-signals that are currently used for monitoring the ionospheric F-region in relation to space weather provide a basis for investigating PWTO applying space-time analysis methods to separate stationary and traveling wave components from the data. Compared to analyses of PW obtained by regular stratospheric reanalyses the seasonal behavior and possible coexisting wave activities during the considered period of time (2002-2008) are presented. Such a climatological consideration has revealed that recurring events in the course of the solar cycle are rare, but it seems that the westward propagating quasi 16-day wave with zonal wavenumber 1, analysed from stratospheric MetO reanalyses, and the ionosphere are indirectly coupled. Generally, the correspondence of other components are restricted around the solar maximum 2002-2005. There are some suggestions, how the middle and upper atmosphere are connected by PW. Sounding of the middle atmosphere by remote sensing techniques from satellites (e.g. SABER on TIMED) deliver a suitable basis to investigate the coupling by the modulation of gravity waves (GW). By calculating the potential energy for a certain wave spectrum, characterized by vertical wavelength shorter than 6 km, and determining proxies of traveling waves permits to investigate a possible mechanism. The results reveal that GW partly penetrate the lower thermosphere carrying a modulation by PW. In some cases, especially during the first three winter, near solar maximum, stratospheric PW show a good correlation to indirect signals in the lower thermosphere and to PWTO in the ionospheric F-region near 300 km.

A new retrieval algorithm has been developed based on the Optimal Estimation (OE) approach, which retrieves lognormal aerosol size distribution parameters from multiwavelength aerosol extinction data, as measured by the Stratospheric Aerosol and Gas Experiment (SAGE) II in the lower stratosphere. Retrieving these aerosol properties becomes increasingly more difficult under aerosol background conditions, when tiny particles (« 0.1 µm) prevail, to which the experiment is nearly or entirely insensitive. A successful retrieval algorithm must then be able (a) to fill the 'blind spot' with suitable information about the practically invisible particles, and (b) to identify 'the best' of many possible solutions. The OE approach differs from other previously used aerosol retrieval techniques by taking a statistical approach to the multiple solution problem, in which the entire range of possible solutions are considered (including the smallest particles) and characterized by probability density functions. The three main parts of this thesis are (1) the development of the new OE retrieval algorithm, (2) the validation of this algorithm on the basis of synthetic extinction data, and (3) application of the new algorithm to SAGE II measurements of stratospheric background aerosol. The validation results indicate that the new method is able to retrieve the particle size of typical background aerosols reasonably well, and that the retrieved uncertainties are a good estimate of the true errors. The derived surface area densities (A), and volume densities (V ) tend to be closer to the correct solutions than the directly retrieved number density (N), median radius (R), and lognormal distribution width (S). Aerosol properties as retrieved from SAGE II measurements (recorded in 1999) are observed to be close to correlative in situ data. In many cases the OE and in situ data agree within the (OE and/or the in situ ) uncertainties. The retrieved error estimates are of the order of 69% (σN), 33% (σR), 14% (σS), 23% (σA), 12% (σV), and 13% (σReff ). The OE number densities are generally larger, and the OE median particle sizes are generally smaller than those N and R retrieved by Bingen et al. (2004a), who suggest that their results underestimate (N) or overestimate (R) correlative in situ data due to the 'small particle problem'. The OE surface area estimates are generally closer to correlative in situ profiles (courtesy of T. Deshler, University of Wyoming), and larger than Principal Component Analysis (PCA) retrieval solutions of A (courtesy of L. W. Thomason, NASA LaRC) that have been observed to underestimate correlative in situ data by 40-50%. These observations suggest that the new OE retrieval algorithm is a successful approach to the aerosol retrieval problem, which is able to add to the current knowledge by improving current estimates of aerosol properties in the lower stratosphere under low aerosol loading conditions.