Atmospheric aerosol particles play an important role in global climate change, via direct and indirect radiative forcing. Elemental carbon (EC) and nitrate are important contributors to anthropogenic aerosol radiative forcing over Europe, since they strongly absorb and/or scatter solar radiation, respectively. However, the evaluation of their climate effects remains highly uncertain. Improvements on the simulation of particle number/mass size distribution (PSD) in modelling will help us to refine model assessments of climate change. The simulations were performed over Europe with a fully online-coupled regional air quality model (WRF-Chem) for the time period of September 10-20th, 2013. Measurements in the HOPE-Melpitz campaign and other datasets in Europe were adopted to evaluate the model uncertainties. The meteorological conditions were well reproduced by the simulations. However, a remarkable overestimation of coarse mode PSD was found in the simulations. The overestimation was mainly contributed by EC, sodium nitrate and sea salt (SSA), stemming from the inadequate emission of EC and SSA. The EC inventory overestimates EC point sources in Germany and the fractions of coarse mode EC emissions in Eastern Europe and Russia. Allocating too much EC emission into the coarse mode could shorten EC lifetime and reduce its long-range transport, thus partly (~20-40%) explaining the underestimation of EC in Germany, when air masses came from eastern direction in previous studies. Furthermore, WRF-Chem overestimated coarse mode SSA mass concentrations by factors of about 8-20 over northwestern and central Europe in this study, due to the shortcoming of its emission scheme. This could facilitate the coarse mode sodium nitrate formation and lead to ~140% overestimation of coarse mode nitrate. Under such circumstances, nitric acid was exhausted, and fine mode ammonium nitrate formation was inhibited. The overestimated SSA shaped the PSD of nitrate towards larger sizes, which might influence the optical properties, lifetime and climate effect of nitrate accordingly. A transport mechanism would broaden the influence of SSA on nitrate PSD to central Europe, where a considerable amount of nitrate precursors and ammonium nitrate is present.:Table of Contents List of Figures List of Tables Abbreviations 1. Introduction 1.1 Particle size distribution 1.2 Elemental carbon particle size distribution simulation 1.3 Chemical pathways for particulate nitrate 1.4 Influence of sea salt on nitrate particle mass size distribution 1.5 Objectives 2. Methodology 2.1. WRF-Chem model 2.1.1. General description 2.1.2. Model configuration 2.1.3 Anthropogenic source emissions 2.1.4 Natural source emissions 2.2 HOPE-Melpitz campaign 2.3 GUAN network over Germany 2.4 Other datasets 3. Results and Discussion 3.1 First publication 3.1.1 Evaluation of the size segregation of elemental carbon (EC) emission in Europe: influence on the simulation of EC long-range transportation 3.1.2 Supporting information 3.2 Second publication 3.2.1 Sea salt emission, transport and influence on size-segregated nitrate simulation: a case study in northwestern Europe by WRF-Chem 3.2.2 Supporting information 4. Summary and Conclusions 5. Outlook Appendix A Bibliography Acknowledgements

Single levitated microdroplets of sodium chloride, potassium chloride, and natural seawater are investigated under conditions similar to that in the troposphere by using the electrodynamic balance technique. The thermodynamics and the kinetics of liquid-to-solid phase transitions have been investigated as a function of temperature and humidity. The temperature dependence of the critical partial pressure of water vapor over aqueous supersaturated aerosol droplets allows us to determine negative values for the integral heat of solution of KCl, NaCl and Mediterranean Sea droplets. In addition, the rates of homogeneous nucleation from supersaturated solution droplets are reported, where the data are fitted with three exponential functions to give three values for the nucleation rates. The phase transition processes which occur on different time scales are identified. The investigation of natural sea salt aerosol droplets collected from the Mediterranean Sea, Atlantic Ocean, Pacific Ocean, North Sea, and Suez Canal show that the phase change (liquid-to-solid) can occur at relative humidities that are greater than 33% RH, where the deliquescence humidity of MgCl2 is known to occur. It is found that there are slight variations (either a decrease or an increase) in water vapor pressure over the supersaturated aerosol droplets due to the change in water salinity, organic components that are present in the water sample, the depth, where the water sample is gathered, and its geographic location. The experimental results show that the presence of the organic substances in the aerosol particles affects the crystallization process depending on the amount and the type of the organic substance. It is observed that adding 1-heptanol to a NaCl droplet increases the crystallization diameter, which is attributed to the formation of a layer of the organic substance on the droplet surface, so that water evaporation cannot efficiently occur.

La prévision de l'intensité des cyclones tropicaux est aujourd'hui un enjeu scientifique majeur. Parmi de nombreux facteurs multi-échelle, l'impact de la microphysique nuageuse et des aérosols sur les variations d'intensité a été récemment mis en évidence. Cette problématique a motivé l'évaluation du schéma microphysique à 2-moments LIMA en milieu tropical et le développement d'un couplage avec le schéma d'aérosols ORILAM au sein du modèle atmosphérique Meso-NH. L'intérêt de ce développement numérique est d'inclure l'émission des aérosols marins en fonction des vents cycloniques et des paramètres océaniques. L'application de ce couplage aérosols-microphysique à la simulation du cyclone tropical Dumile (2013) montre que le modèle couplé tend à améliorer la représentation de l'intensité, la trajectoire, la structure microphysique du cyclone tropical et les précipitations associées, en comparaison avec les observations. La production secondaire des cristaux de glace est également un thème de recherche actif en microphysique nuageuse. Ainsi, une paramétrisation du processus de rupture collisionnelle de la glace a été implémentée dans le schéma microphysique LIMA. L'impact de ce processus a été testé sur le développement d'un orage des moyennes latitudes et sur le cyclone tropical Dumile. Les deux cas d'étude ont des réponses similaires vis-à-vis de ce processus : une augmentation de la concentration et de la masse des cristaux de glace et une diminution des cumuls de précipitations. La poursuite de ces travaux pourrait permettre de déterminer si ce processus de formation secondaire peut améliorer la modélisation de la couverture cirriforme des cyclones tropicaux. / Intensity forecast of tropical cyclones is a major scientific issue. Among many factors, the impact of cloud microphysics and aerosols on intensity variations has been recently underlined. This issue motivated the evaluation of the 2-moment microphysical scheme LIMA in a tropical context and the development of a coupling with the aerosol scheme ORILAM into the atmospheric model Meso-NH. The interest of this numerical development is to represent the emission of sea salt aerosols depending on cyclonic winds and oceanic parameters. The application of this aerosols-microphysics coupling to the simulation of tropical cyclone Dumile (2013) shows that the coupled model tends to improve the representation of the intensity, the track, the microphysical structure of the tropical cyclone and the associated precipitation, when comparing with observations. The secondary production of ice crystals is also an active research topic in cloud microphysics. A parameterization of the collisional ice break-up process is thus implemented into the microphysical scheme LIMA. The impact of this process has been analyzed on a mid-latitude storm and on tropical cyclone Dumile. Both case studies display similar results regarding this process: an increase of ice crystals concentration and mass, and a decrease of precipitation. The continuation of this work could allow to determine if this process of secondary formation could improve the cirrus modelling in tropical cyclones.

Die Entwicklung eines Emissionsmoduls für primäres marines Aerosol (PMA; bestehend aus Meersalz und organischem Material) war Hauptgegenstand der vorliegenden Arbeit. Dieses wurde in das Chemie-Transportmodell „COSMO-MUSCAT“ eingebaut und löste dort das vorherige einfach gehaltene Modul (nur Meersalz) ab, welches entsprechend früherer Studien zu hohe Meersalzkonzentrationen berechnete. Das neue Emissionsmodul wurde umfangreich getestet und gegen die Messdaten von verschiedenen Stationen in Europa, einem Bernerimpaktor auf São Vicente (Kap Verden) und einem Aerosolmassenspektrometer sowie einem Digitelfilter während der Fahrt ANT-XXVII/4 des Forschungsschiffes Polarstern validiert. Bei den Untersuchungen kristallisierte sich die Emissionsparametrisierung von Long et al. (2011) als die am Besten geeignete für COSMO-MUSCAT heraus. Weiterhin wurde der Einfluss der Wassertemperatur an der Meeresoberfläche auf die PMA-Emission untersucht. Dabei konnte gezeigt werden, dass dieser Effekt insbesondere für größere Aerosolpartikel (2,5 µm < Dp) relevant ist. Die Nichtbeachtung der Temperaturkorrektur würde in diesem Größenbereich zu einer Überschätzung der Emissionsflüsse und folgend der Konzentration von PMA über kalten Gewässern führen. Beim erstmaligen Vergleich verschiedener Funktionen zur Beachtung des Temperatureffektes erzielte die Funktion von Sofiev et al. (2011) die besten Ergebnisse. Als weitere Neuerung wurde das mit dem PMA emittierte organische Material in das Emissionsmodul eingebaut. Auch hierfür erfolgten Vergleichsstudien verschiedener Parametrisierungen und Ansätze. Allerdings standen nur unzureichende Messungen zur Verfügung, da sie keine Aufteilung in primäres (mit PMA emittiert) und sekundäres (in Gasphase gebildet) organisches Material lieferten. Daher war eine Aussage zur Güte der Funktionen kaum möglich. Die Simulationen zeigten jedoch die Bedeutung der verschiedenen Ansätze zur Berechnung der Emissionsflüsse von organischem Material. So kann bspw. der Einfluss der Emissionsfunktion den Einfluss der Parametrisierung zur Aufteilung in Meersalz und organisches Material deutlich übersteigen. Letztlich bleibt die Frage der richtigen Eingangsdaten für die Emission von primärem organischen Material offen. Es zeigte sich, dass die Abhängigkeit der Anreicherung von organischem Material im PMA von der Chlorophyll a-Konzentration im Oberflächenwasser nicht zwingend gegeben sein muss. Daher ist es notwendig sie in der Berechnung der Emissionsflüsse durch weitere/andere Parameter zu ergänzen/ersetzen. Dies ist Gegenstand eines neuen Forschungsprojektes, bei dem das neue Emissionsmodul angewendet und weiterentwickelt wird.

Die Entwicklung eines Emissionsmoduls für primäres marines Aerosol (PMA; bestehend aus Meersalz und organischem Material) war Hauptgegenstand der vorliegenden Arbeit. Dieses wurde in das Chemie-Transportmodell „COSMO-MUSCAT“ eingebaut und löste dort das vorherige einfach gehaltene Modul (nur Meersalz) ab, welches entsprechend früherer Studien zu hohe Meersalzkonzentrationen berechnete. Das neue Emissionsmodul wurde umfangreich getestet und gegen die Messdaten von verschiedenen Stationen in Europa, einem Bernerimpaktor auf São Vicente (Kap Verden) und einem Aerosolmassenspektrometer sowie einem Digitelfilter während der Fahrt ANT-XXVII/4 des Forschungsschiffes Polarstern validiert. Bei den Untersuchungen kristallisierte sich die Emissionsparametrisierung von Long et al. (2011) als die am Besten geeignete für COSMO-MUSCAT heraus. Weiterhin wurde der Einfluss der Wassertemperatur an der Meeresoberfläche auf die PMA-Emission untersucht. Dabei konnte gezeigt werden, dass dieser Effekt insbesondere für größere Aerosolpartikel (2,5 µm < Dp) relevant ist. Die Nichtbeachtung der Temperaturkorrektur würde in diesem Größenbereich zu einer Überschätzung der Emissionsflüsse und folgend der Konzentration von PMA über kalten Gewässern führen. Beim erstmaligen Vergleich verschiedener Funktionen zur Beachtung des Temperatureffektes erzielte die Funktion von Sofiev et al. (2011) die besten Ergebnisse. Als weitere Neuerung wurde das mit dem PMA emittierte organische Material in das Emissionsmodul eingebaut. Auch hierfür erfolgten Vergleichsstudien verschiedener Parametrisierungen und Ansätze. Allerdings standen nur unzureichende Messungen zur Verfügung, da sie keine Aufteilung in primäres (mit PMA emittiert) und sekundäres (in Gasphase gebildet) organisches Material lieferten. Daher war eine Aussage zur Güte der Funktionen kaum möglich. Die Simulationen zeigten jedoch die Bedeutung der verschiedenen Ansätze zur Berechnung der Emissionsflüsse von organischem Material. So kann bspw. der Einfluss der Emissionsfunktion den Einfluss der Parametrisierung zur Aufteilung in Meersalz und organisches Material deutlich übersteigen. Letztlich bleibt die Frage der richtigen Eingangsdaten für die Emission von primärem organischen Material offen. Es zeigte sich, dass die Abhängigkeit der Anreicherung von organischem Material im PMA von der Chlorophyll a-Konzentration im Oberflächenwasser nicht zwingend gegeben sein muss. Daher ist es notwendig sie in der Berechnung der Emissionsflüsse durch weitere/andere Parameter zu ergänzen/ersetzen. Dies ist Gegenstand eines neuen Forschungsprojektes, bei dem das neue Emissionsmodul angewendet und weiterentwickelt wird.

Corrosion represents the single most frequent cause for product replacement or loss of product functionality with a 5% coat to the industrial revenue generation of any country in this dissertation the efficacy of using filled coatings as a protection coating are investigated. Fillers disrupt the polymer-substrate coating interfacial area and lead to poor adhesion. Conflicting benefits of increasing surface hardness and corrosion with long term durability through loss of adhesion to the substrate are investigated. The effects of filler type, filler concentration and exposure to harsh environments such as supercritical carbon dioxide on salt water corrosion are systematically investigated. The constants maintained in the design of experiments were the substrate, AISI-SAE 1018 steel substrate, and the corrosive fluid synthetic sea salt solution (4.2 wt%) and the polymer, Bismaleimide (BMI). Adhesion strength through pull-off, lap shear and shear peel tests were determined. Corrosion using Tafel plots and electrochemical impedance spectroscopy was conducted. Vickers hardness was used to determine mechanical strength of the coatings. SEM and optical microscopy were used to examine dispersion and coating integrity. A comparison of fillers such as alumina, silica, hexagonal boron nitride, and organophilic montmorillonite clay (OMMT) at different concentrations revealed OMMT to be most effective with the least decrease in adhesion from filler-substrate contact. Subsequently examining filler concentration, a 3 wt% OMMT was found to be most effective. A comparison of unmodified and modified BMI with 3 wt% OMMT exposed and not exposed to supercritical carbon dioxide showed that the BMI provided better corrosion protection; however, OMMT provided better wear, shear, and hardness performance.

Marine aerosols have attracted increasing attention over the past 15 years because of their potential significance for global climate modelling. The size distribution of these aerosols extends from super-micrometer sea salt mode particles down through 150 nm accumulation mode particles, 40 nm Aitken mode particles and nucleation mode particles which extend from 25 nm right down to clusters of a few molecules. The process by which the submicrometer modes form and grow and their composition have remained topics of debate throughout this time in large part because of the difficulties associated with determining their composition and relating it to proposed models of the formation process. The work compared the modality of marine aerosol influencing the South-east-Queensland region with that of other environmental aerosols in the region. The aerosol was found to be consistent with marine aerosols observed elsewhere with concentrations below 1000 cm-3 and frequently exhibiting the distinct bimodal structure associated with cloud processing, consisting of an Aitken mode at approximately 40 nm, an accumulation mode in the range 100-200 nm and a coarse mode attributed to sea salt between 600 and 1200 nm. This work included the development of two new techniques for aerosol research. The first technique measures aerosol density using a combination of aerosol size distribution and gravimetric mass concentration measurements. This technique was used to measure the density of a number of submicrometer aerosols including laboratory generated NaCl aerosol and ambient aerosol. The densities for the laboratory generated aerosols were found to be similar to those for the bulk materials used to produce them. The technique, extended to super-micrometer particle size range may find application in ambient aerosol research where it could be used to discriminate between periods when the aerosol is dominated by NaCl and periods when the density is more representative of crustal material or sulfates. The technique may also prove useful in laboratory or industrial settings for investigating particle density or in case where the composition is known, morphology and porosity. The second technique developed, integrates the existing physicochemical techniques of volatilisation and hygroscopic growth analysis to investigate particle composition in terms of both the volatilisation temperatures of the chemical constituents and their contribution to particle hygroscopic behaviour. The resulting volatilisation and humidification tandem differential mobility analyser or VH-TDMA, has proven to be a valuable research tool which is being used in ongoing research. Findings of investigations relating the composition of the submicrometer marine aerosol modes to candidate models for their formation are presented. Sea salt was not found in the numerically dominant particle type in coastal nucleation mode or marine Aitken and accumulation modes examined on the Southeast Queensland coast during periods where back trajectories indicated marine origin. The work suggests that all three submicrometer modes contain the same four volatile chemical species and an insoluble non-volatile residue. The volatility and hygroscopic behaviours of the particles are consistent with a composition consisting of a core composed of sulfuric acid, ammonium sulfate and an iodine oxide coated with a volatile organic compound. The volume fraction of the sulfuric acid like species in the particles shows a strong dependence on particle size.

<p>The uncertainty of the climate and health effects of aerosols is still large, one important reason being lack of knowledge of the primary emissions. This thesis combines laboratory and field experiments, and process modelling in an effort to better quantify the submicrometre aerosol emissions and to understand some of the processes in the atmosphere.</p><p>A parameterisation was derived for the source flux of sea salt particles (particles m^-2s^-1) in the size range 0.02-2.8 µm dry diameter (D_p), it is the first parameterisation to almost cover two full decades of the submicrometre sea salt aerosol production, and to include the effect of water temperature. This sea salt parameterisation was validated for temperate water in the 0.1-1.1 μm D_p range using in situ size resolved emissions of marine aerosol particles, which were measured with the eddy covariance (EC) method. For periods sampled air was heated to 300ºC in order to evaporate semi-volatile organics and isolate the sea salt fraction. Comparisons with the total aerosol emissions suggest that in these emissions organic carbon and sea salt are internally mixed in the same particles. Finally an aerosol dynamics model was modified for marine conditions. In the model parameterised emissions of sea salt was included together with aerosol dynamics, chemistry and clouds representative for the marine boundary layer. The sea salt emissions are together with secondary sulphate, and cloud processing able to reproduce a typical marine aerosol size distribution and cloud condensation nuclei population.</p><p>Measurements with the EC method of the road traffic related aerosol source number flux for D_p>0.011 µm show that the major part of the aerosol fluxes is due to road traffic emissions. Both an emission factor for the whole fleet mix in Stockholm (1.4x10¹⁴ vehicle^-1 km^-1) and separate emission factors for light- and heavy-duty vehicles (HDV) were deduced. The result shows that during weekdays 70-80% of the emissions come from HDV.</p>

The uncertainty of the climate and health effects of aerosols is still large, one important reason being lack of knowledge of the primary emissions. This thesis combines laboratory and field experiments, and process modelling in an effort to better quantify the submicrometre aerosol emissions and to understand some of the processes in the atmosphere. A parameterisation was derived for the source flux of sea salt particles (particles m-2 s-1) in the size range 0.02-2.8 µm dry diameter (Dp), it is the first parameterisation to almost cover two full decades of the submicrometre sea salt aerosol production, and to include the effect of water temperature. This sea salt parameterisation was validated for temperate water in the 0.1-1.1 μm Dp range using in situ size resolved emissions of marine aerosol particles, which were measured with the eddy covariance (EC) method. For periods sampled air was heated to 300ºC in order to evaporate semi-volatile organics and isolate the sea salt fraction. Comparisons with the total aerosol emissions suggest that in these emissions organic carbon and sea salt are internally mixed in the same particles. Finally an aerosol dynamics model was modified for marine conditions. In the model parameterised emissions of sea salt was included together with aerosol dynamics, chemistry and clouds representative for the marine boundary layer. The sea salt emissions are together with secondary sulphate, and cloud processing able to reproduce a typical marine aerosol size distribution and cloud condensation nuclei population. Measurements with the EC method of the road traffic related aerosol source number flux for Dp&gt;0.011 µm show that the major part of the aerosol fluxes is due to road traffic emissions. Both an emission factor for the whole fleet mix in Stockholm (1.4x1014 vehicle-1 km-1) and separate emission factors for light- and heavy-duty vehicles (HDV) were deduced. The result shows that during weekdays 70-80% of the emissions come from HDV.

This master‘s thesis studies problems of chosen active substances in cosmetic emulsions and gels. There is their main characteristics – distribution and properties of cosmetic emulsions and gels, preparation of the active substances, effects on the skin and conditions, which could them influence. In experimental part, preparation of gels and emulsions bases was described which were than enriched by active substances - evening primrose oil, hemp oil, Salvia officinalis extract, Symphytum officinale extract and sea salt. Properties of these cosmetic gels and emulsions bases with the addition of active substances depend on temperature and method of storage, amount of light exposure, method of preparation and another conditions. Action of these factors can cause changes of the stability, thereby the cosmetics effects on the skin can be lost. On the bases of performed rheology measurements (oscillation and flow measurements), pH measurements and sensory analysis were determined, if the properties of examined samples were changed. The measurement was performed in the certain time intervals and the properties were evaluated like at laboratory temperature 23±2 °C, so after exposure to temperature regime 37 °C in thermoregulator. On the basis of performed measurements, there was determined, that gel base with addition of Symphytum officinale extract had the most stability properties.