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In spite of their high abundance and importance, aqueous systems are enigmatic on the microscopic scale. In order to obtain information about their geometrical and electronic structure, simple aqueous solutions have been studied experimentally by photo- and Auger electron spectroscopy using the novel liquid micro-jet technique in conjunction with synchrotron radiation. The thesis is thematically divided into three parts. In the first part we utilize the surface sensitivity of photoelectron spectroscopy to probe the distributions of solutes near the water surface. In agreement with recent theoretical predictions we find that large polarizable anions, such as I- and ClO4-, display enhanced surface propensities compared to smaller rigid ions. Surface effects arising from ion-ion interactions at higher electrolyte concentrations and as function of pH are investigated. Studies of linear mono-carboxylic acids and benzoic acid show that the neutral molecular forms of such weak acids are better stabilized at the water surface than their respective conjugate base forms. The second part examines what type of information core-electron spectra can yield about the chemical state and hydration structure of small organic molecules in water. We demonstrate that the method is sensitive to the protonation state of titratable functional groups and that core-level lineshapes are dependent on local water hydration configurations. Using a combination of photoelectron and X-ray absorption spectroscopy we also show that the electronic re-arrangement upon hydrolysis of aldehydes yields characteristic fingerprints in core-level spectra. In the last part of this thesis we study ultrafast charge delocalization dynamics in aqueous solutions using resonant and off-resonant Auger spectroscopy. Intermolecular Coulombic decay (ICD) is found to occur in a number of core-excited solutions where excess energy is transferred between the solvent and the solute. The rate of ultrafast electron delocalization between hydrogen bonded water molecules upon oxygen 1s resonant core-excitation is found to decrease upon solvation of inorganic ions. The presented work is illustrative of how core-level photoelectron spectroscopy can be valuable in the study of fundamental phenomena in aqueous solutions.

This thesis describes the investigation of three aspects of the formation of secondary organic aerosol (SOA): * Aerosol formation from mixed precursors * Global modelling of SOA formation * Modelling of dynamics of SOA formation based on empirical data collected from smog chamber experiments. The formation and growth processes of secondary organic aerosol were investigated using smog chamber experimentation and modelling techniques to gain a better understanding of the application of SOA yield values in modelling both SOA mass and dynamics. Published SOA yields from a range of volatile organic compounds (VOCs) are used to model SOA mass on a local, regional or global scale, based on the assumption that the SOA yield of a mixture is the sum of the yields of the components. Experimental investigations into SOA yield from mixtures of VOC revealed potential uncertainties that would result from applying these yields to systems containing multiple VOCs. SOA formation in systems of toluene or m-xylene, compared with systems of these VOCs and propene, have shown that the introduction of propene (which has a zero SOA yield) to smog chamber photo-oxidations of toluene or m-xylene delays the formation and suppresses the overall yield of SOA from 450 to 90 µg m-3 ppm-1 for the toluene system and from 325 to 125 µg m-3 ppm-1 for the mvxylene system compared with systems of individual species without propene. The SOA partitioning yield data also indicates that partitioning of species to existing aerosol is suppressed in the mixed systems. Gas-phase modelling of these experiments showed that potential SOA species were expected to be formed sooner due to the increased system reactivity provided by propene. The observed delay in SOA nucleation, similar consumption rates of toluene and m-xylene in both the single and mixed systems and the gas-phase modelling results suggest that the addition of propene to hydrocarbon SOA systems modifies the gas-phase chemistry leading to the formation of potential SOA species from toluene and m-xylene. This result calls into question the bulk and partitioning yield values that have been published for pure substances as well as the validity of applying individual VOC yields to VOC mixture. Application of SOA yields to the global scale provides estimates of annual global SOA formation, global contributions from various VOCs and regional SOA distributions. Two SOA modules, using bulk and partitioning yield methods, were added to a global atmospheric chemical transport model, MOZART-2. The bulk yield method, representing the maximum possible global SOA burden, gave an annual production of 24.5 Tg of SOA, which is slightly lower than previous estimates (30 - 270 Tg yr-1). The partitioning method, which gives a more realistic estimate of SOA formation, produced 15.3 Tg yr-1; the biogenic fraction (13.6 Tg yr-1) compares to a previous estimate of biogenic SOA of 18.5 Tg yr-1 and 2.5 to 44 Tg yr- 1 using the partitioning method. Anthropogenic SOA contributions of 1.1 Tg yr-1 from MOZART-2 compared to recent estimates of 0.05 -2.62 Tg yr-1. SOA production was found to be dependent on oxidant availability and VOC emissions in South America and Asia. The partitioning method produced significantly less SOA due to limited availability of OC. Thepartitioning method also produced a peak SOA concentration of 10 µg m-3 over South America in September and showed that SOA is at maximum production for most of the year in Asia and Europe. The two SOA formation methods also provides data to analyse the restrictions to SOA formation in particular regions, based on the maximum amount of SOA able to form (bulk yield method) and the more realistic partitioning estimate from the same region. Limitations to SOA formation in a particular region can be attributed to deficiencies in OC availability or VOC oxidant concentrations. Comparisons to limited observational and modelled data suggest that the MOZART-2 SOA model provides a good representation of global averaged SOA. SOA mass concentrations, predicted by models such as MOZART-2, can be used in part to model the dynamics of an SOA population (e.g. size of particles, number concentrations etc.). Aerosol properties such as size and number concentration can then be used to estimate their effect on climate and health. The explicit representation of the processes that affect aerosol dynamics, such as nucleation, condensation, evaporation and coagulation can be complex and use significant computational resources. Simplification of the discrete coagulation equation and empirical coagulation coefficients for continuum and non-continuum regime diffusion kinetics provided a simplified method of coagulation capable of predicting the evolution of inert sodium chloride aerosol in chamber experiments. A variable coagulation coefficient (linked to the mean particle number concentration of each experiment) was developed. This method is an empirical surrogate for the standard coefficient corrections applied to Brownian based diffusion in the continuum regime to account for the different kinetic effects within the transition and free molecular diffusion regimes. This method removes the need for calculating individual coefficients for each particle interaction. Estimates of modeluncertainty show that within uncertainty limits the model provides a good representation of experimental data. Correlation and index of agreement (IOA) calculations revealed good statistical agreement between modelled and experimental. Some experiments showed degrees of coagulation under prediction using the variable coefficient technique. Investigations into the effect of aerosol type and size, temperature and humidity may be necessary to refine the variable coefficient calculation technique. The model showed little sensitivity to model time step and is capable of high resolution representation of the aerosol. Mass concentration is conserved within the model whereas some error due to numerical diffusion within the number concentrations results from the bin sectioning technique used. The simplicity of this sectioning method over other methods and the minimal effect of numerical diffusion establishes a simplified method of modelling relative to the high resolution of the aerosol distribution the model achieves. It is suggested that the efficiency improvements introduced by the approaches used in developing this model provide an efficient ultra-fine coagulation modelling for atmospheric models. A semi-empirical model for SOA dynamics (SPLAT) incorporating coagulation, nucleation, condensation and evaporation was developed. The aim of the model and the development process was to predict, with high resolution and minimal computational expense, the formation and growth of SOA given a SOA mass input as a function of time. The average size distribution profile from chamber experimental data was used as part of the nucleation module. This technique provided an alternative method of representing the particle distribution compared to those models that assume a single diameter of nucleated particle or a fixed log-normal mode for the entire evolution of SOA. All SPLAT simulations assume organic nucleation events within the experiments modelled, although it is stilluncertain whether they occur in the atmosphere. The modelled nucleation events have produced a single nucleation burst, a result of immediate domination of condensation as soon as nucleation occurs. This deficiency is likely to be a result of the assumption of free molecular diffusion for condensation. The rate of condensation, calculated at every time step, is based on the aerosol size distributed surface area and the particle-size-dependent saturation mass concentrations. The SPLAT coagulation module was a version of the model developed in Chapter 6. Comparisons between experimental and modelled data showed good agreement. These comparisons revealed the shortcomings in the nucleation module while a statistical analysis of the modelled and experimental data has shown SPLAT to be effective in modelling a range of SOA systems. The complexity introduced in modelling aerosol dynamics in high resolution is offset in SPLAT by efficiency improvements due to the insensitivity of the model to time step size and simplified methods of bin sectioning, nucleation, coagulation, condensation and evaporation. Published SOA yields can be applied to predict SOA mass at local, regional or global scales. Although previously unreported uncertainties in these yields have been shown to exist, the MOZART-2 global chemical transport model has shown that SOA mass concentration can be predicted with reasonable quality, considering the scale of the model and limited observational data. These global scale SOA mass predictions can be used purely for global burden and occurrence, or as the input for modelling the dynamics of an aerosol population, which is significant for estimating an aerosol population's effect on climate change and health. SOA mass concentrations from chamber experiments were used as input to a SOA dynamics model. This model (SPLAT) then predicted the evolution of particle number concentrations and size within these experiments based on this mass input. Application of the dynamics model to the output of the MOZART-2 model could then provide a comprehensive global scale SOA modelling package.

[Truncated abstract] This thesis examines the bonding interactions and chemical processes associated with irradiated water (H2O) and ammonia (NH3) molecules. The experiments conducted in the present study are designed to replicate the surface chemistry of outer Solar System bodies, particularly the icy surfaces of Saturn's inner moons. Infrared (IR) spectroscopy is used to identify the H2ONH3 complex isolated in an argon (Ar) matrix. An electric discharge is then applied to the H2O and NH3 species to produce the hydroxyl-ammonia (OHNH3) complex and the water-amidogen (H2ONH2) complex. Finally, the ammonia-oxygen (NH3O2) complex is formed in an Ar matrix, complementing previous studies performed by the Quickenden research group, which investigated the conversion of OH radicals into molecular O2 on icy planetary surfaces. ... An electric discharge is applied to the NH3 in Ar mixture, producing the NH2 radical subunit of the complex. Two absorption bands are assigned to the H2O subunit vibrational frequencies of the complex; at 1616.1 cm-1 for the ¿2 HOH bending fundamental and at 3532.1 cm-1 for the ¿1 OH bonded stretching fundamental. Two absorption bands are also assigned to the NH2 radical subunit vibrational frequencies of the complex; at 1498.5 cm-1 for the ¿2 HNH bending fundamental and at 3260.8 cm-1 for the ¿3 NH asymmetric stretching fundamental. These assignments are verified by the isotope substitution method, involving the formation of the deuterated D2OND2 complex analogue in an Ar matrix and the measurement of the isotope induced shifts in peak position in the IR region. The isotopic shifts displayed by the IR absorption bands are in good agreement with the theoretically calculated shifts in vibration frequency when going from the H2ONH2 complex fundamentals to the D2OND2 complex fundamentals. The theoretical calculations also derived an interaction energy of 5.2 kcal mol-1 for the HOHNH2 structure of the H2ONH2 complex. This HOHNH2 structure is also confirmed as the preferred structure of the H2ONH2 complex in the IR experiments, by the observation of a large shift in position of the absorption band associated with the H2O subunit ¿1 OH stretching fundamental, away from the position of the H2O monomer ¿1 OH stretching fundamental. This indicates that the H2O subunit donates a hydrogen for the complex bond in the HOHNH2 complex. The NH3O2 complex is identified in solid Ar matrices at 10.5 K by IR analysis. The NH3O2 complex is formed by the co-deposition of gaseous NH3 in Ar mixtures with O2 in Ar gas mixtures. An absorption band is assigned to the ¿1 OO stretching fundamental for the O2 subunit of the NH3O2 complex at 1552.0 cm-1. This assignment is verified by the isotope substitution method, involving the formation of the deuterated ND3O2 complex analogue in an Ar matrix and the measurement of the isotope induced shift in peak position in the IR region. The isotopic shift displayed by the IR absorption band is in good agreement with the theoretically calculated shift in vibration frequency when going from the NH3O2 complex fundamental to the ND3O2 complex fundamental. The theoretical calculations also derived an interaction energy of 0.28 kcal mol-1 for the NH3O2 complex.

Thesis (Ph. D.)--Massachusetts Institute of Technology and Woods Hole Oceanographic Institution Joint Program in Oceanography/Applied Ocean Science and Engineering, 1997. / "September 1997." "Funding was provided by National Science Foundation Grant OCE-9201286, National Science Foundation Graduate Fellowship Program, and the JOI/USSAC Ocean Drilling Graduate Fellowship Program." Includes bibliographical references (p. 152-153).

Title: Coupling atmospheric chemistry/aerosols to regional climate models Author: Peter Huszár Department: Department of Meteorology and Environment Protection Supervisor: doc. RNDr. Tomáš Halenka, CSc. Supervisor's e-mail address: tomas.halenka@mff.cuni.cz Abstract: In this thesis, the connections between air quality and climate are studied. For this purpose, regional climate model RegCM3 and chemistry transport model CAMx has been coupled offline with one- and two-way interaction. Our work represents a first attempt to connect RegCM3 not only with CAMx, but with any other chemistry transport model. As a first step, an offline one way couple of RegCM3 and CAMx has been developed, meaning that the climate model drives the transport, emission, chemical transformation and deposition of species while the radiative feedbacks of gases and aerosols are not considered. A meteorological interface has been developed at our department in order to convert the meteorological data generated by RegCM3 to fields required by CAMx. For those parameters that are essential for CAMx but the regional climate model does not supply them, diagnostic methods were implemented into this interface. Further, it is used to calculate biogenic emissions. Regarding anthropogenic emissions, a simple utility has been developed to...

Suite à la signature du Protocole de Montréal en 1987, la concentration atmosphérique des substances destructrices d’ozone (ODS) est en baisse. La couche d’ozone montre des signes de récupération (Morgenstern et al. 2008a). Toutefois, l’émission des gaz à effet de serre (GHG) est en augmentation et devrait affecter au cours du 21ème siècle la distribution et les niveaux d’ozone dans l’atmosphère terrestre. En particulier, la modélisation du climat futur montre des signes d’accélération de la circulation de Brewer-Dobson transportant l’ozone de l’équateur vers les pôles. L’ozone est un constituant chimique important de l’atmosphère. Bien que nocif dans la troposphère, il est essentiel à la vie sur Terre grâce à sa capacité d’absorption d’une grande partie du rayonnement ultraviolet (UV) provenant du Soleil. Des modifications dans sa variabilité temporelle ou géographique impliqueraient des changements d’intensité du rayonnement UV à la surface de la Terre (Hegglin et al. (2009), Bais et al. (2011)). Le rayonnement UV à la surface affecte toute la biosphère. Les interactions entre rayonnement UV et écosystèmes terrestres et aquatiques sont nombreuses. Ces interactions ont des effets sur les cycles biogéochimiques et engendrent des rétroactions positives et négatives sur le climat (Erickson III et al., 2015a). La capture du CO2 atmosphérique par photosynthèse des plantes terrestres en est un exemple (Zepp et al., 2007a). Dans l’océan la pompe biologique du CO2 par la photosynthèse du phytoplancton est aussi directement affecté par la variabilité du rayonnement UV (Hader et al., 2007a). Pour l’homme le rayonnement UV est nécessaire car il participe à la photosynthèse de la vitamine D (Holick et al., 1980), mais une surexposition à des niveaux d’intensité élevés du rayonnement UV est la cause principale du développement de cancer de la peau (Matsumura and Ananthaswamy, 2004). L’objectif de ce travail de thèse est d’analyser l’évolution possible du rayonnement UV au cours du 21ème siècle, en particulier aux tropiques sud, dans le cadre des modifications climatiques attendues. Une première partie de ce travail consiste à modéliser le rayonnement UV en ciel clair dans les tropiques grâce au modèle TUV (Madronich et al., 1998) et à comparer les résultats aux mesures sols réalisées à la Réunion. Cette première partie permet l’utilisation future du modèle aux tropiques avec un bon niveau de confiance. La sensibilité du modèle de transfert radiatif en fonction de différents paramètres d’entrée est analysée (section efficace d’absorption de l’ozone,spectre extraterrestriel du soleil, ...). Les sorties du modèle sont ensuite validées à partir de mesures UV spectral au sol obtenues grâce à un spectromètre BENTHAM DM300n. Un filtrage ciel-clair des données au sol est opéré à partir de mesures de flux et de l’algorithme de Long and Ackerman (2000). Les projections climatiques des indices UV (Mc Kinlay and Diffey, 1987) sont réalisées par la suite. Pour cela, on utilise les sorties de plusieurs modèles de Chimie-Climat participant à l’exercice d’inter-comparaison CCMI (Chemistry Climate Model Initiative), couplées aux modèle TUV, validé en première partie dans les tropiques. L’exercice CCMI consiste à projeter le climat et la chimie Terrestre jusqu’en 2100 selon différents scénarios. Ces sorties décrivant la chimie et physique de l’atmosphère servent d’entrée au modèle de transfert radiatif, on obtient alors le rayonnement UV jusqu’en 2100 pour différents scénarios. Une première analyse comparative de l’UV obtenue pour quatre scénarios d’émissions (RCP2.6/4./6.0/8.5, Meinshausen et al., 2011) est effectuée. La fin du travail consiste à étudier l’impact des ODS, GHG et aérosols sur l’évolution du rayonnement UV au cours du 21ème siècle, avec un focus particulier sur les tropiques de l’hémisphère sud. / Following the 1987 Montreal Protocol, atmospheric concentrations of ozone-depleting substances are decreasing. The ozone layer shows signs of recovery. Nonetheless, greenhouse gases emissions (GHG) are rising et should affect the ozone distribution in the atmosphere. Ozone is an important due to his ability to absorb ultraviolet (UV) radiation. The goal of this work is to analyse the possible evolution of UV radiation through the 21st century, particularly in the tropics, for possible climate modification. The first part of this work is to UV in clear-sky in the tropics with the TUV (Madronich et al., 1998) model and to compare against ground-based observations made on Reunion Island. This validation allows the utilisation of TUV in the tropics with a good confidence level. The sensitivity of the model is analysed for multiple parameters. Modelling output is validated against spectral ground-based measurement. Climate Projection of UVI (Mc Kinlay and Diffey, 1987) are then realized with the use of output from model participating in the CCMI ( Model Initiative) exercise and the TUV model. CCMI output describes the chemistry and physics of the atmosphere through the 21st century for four climate scenarios (RCP2.6/4.5/6.0/8.5), they are used as input for the TUV model in order to obtain UV radiation. ODS, GHG and aerosols impact on UVI evolution is analysed.

L’objectif de ce travail consiste à étudier, d’une part, les réactions des nitrates d’alkyles avec OH qui ont un intérêt atmosphérique, et d’autre part, les réactions des radicaux OH avec les alcanes et des atomes d’oxygène avec les oléfines qui ont un intérêt pour la combustion. Toutes les réactions ont été étudiées dans des réacteurs à écoulement à basse pression, y compris le réacteur à écoulement à haute température mis en place dans le cadre de la thèse, couplés à un spectromètre de masse quadripolaire à ionisation par impact électronique. Pour les réactions OH + nitrate d’alkyle, la dépendance en température de la constante de vitesse a été mesurée pour dix nitrates d'alkyles, dont pour huit nitrates pour la première fois, sur une large plage de température. Pour six nitrates, les produits de la voie réactionnelle menant au recyclage direct de NO₂, arrachement d’atome H de carbone α, ont été observés et leur rendements mesurés. La grande quantité de données obtenues dans ce travail a été utilisée pour une mise à jour de la relation structure-activité (SAR) pour les réactions d'alkyles nitrates avec OH et a permis d'améliorer les modèles atmosphériques actuels. Les études de réactions de radicaux OH avec les trois alcanes et de l'atome O avec l’éthylène et le propène ont permis de déterminer les constantes de vitesse respectives sur une large gamme de température allant de 220 à 900 K. De plus, la distribution des produits de réactions multivoies O + oléfine en fonction de la température a été déterminée pour la première fois. Ces résultats permettront d’améliorer les modèles de combustion actuellement utilisés. / The objective of this work was to study the reactions of alkyl nitrates with OH radicals relevant to atmosphere and reactions of OH radical with alkanes and oxygen atoms with olefins of interest for combustion chemistry. All reactions were studied in low pressure flow reactors (including high temperature flow reactor developed during the thesis) coupled to a quadrupole mass spectrometer with electron impact ionization. For OH reaction with nitrates, the temperature dependence of the rate constant was measured in an extended temperature range for ten alkyl nitrates, for eight of them for the first time. For six nitrates, the products of reaction pathway leading to direct recycling of NO₂ (H atom abstraction from α carbon) were observed and their yields were measured. The large amount of data obtained in this work has been used for an update of the structure-activity relation (SAR) for the reactions of alkyl nitrates with OH and will improve existing atmospheric models. For the reactions of OH radicals with three alkanes and O atoms with ethene and propene the rate constants were measured over a wide temperature range, 220-900 K. Moreover, the distribution of the products of the multichannel reactions O + olefin was determined as a function of temperature for the first time. These results are expected to improve current combustion models.