<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>

An Airborne Mobile Aerosol Lidar (AMALi) was constructed and built at Alfred-Wegener-Institute for Polar and Marine Research (AWI) in Potsdam, Germany for the lower tropospheric aerosol and cloud research under tough arctic conditions. The system was successfully used during two AWI airborne field campaigns, ASTAR 2004 and SVALEX 2005, performed in vicinity of Spitsbergen in the Arctic. The novel evaluation schemes, the Two-Stream Inversion and the Iterative Airborne Inversion, were applied to the obtained lidar data. Thereby, calculation of the particle extinction and backscatter coefficient profiles with corresponding lidar ratio profiles characteristic for the arctic air was possible. The comparison of these lidar results with the results of other in-situ and remote instrumentation (ground based Koldewey Aerosol Raman Lidar (KARL), sunphotometer, radiosounding, satellite imagery) allowed to provided clean contra polluted (Arctic Haze) characteristics of the arctic aerosols. Moreover, the data interpretation by means of the ECMWF Operational Analyses and small-scale dispersion model EULAG allowed studying the effects of the Spitsbergens orography on the aerosol load in the Planetary Boundary Layer. With respect to the cloud studies a new methodology of alternated remote AMALi measurements with the airborne in-situ cloud optical and microphysical parameters measurements was proved feasible for the low density mixed-phase cloud studies. An example of such approach during observation of the natural cloud seeding (feeder-seeder phenomenon) with ice crystals precipitating into the lower supercooled stratocumulus deck were discussed in terms of the lidar signal intensity profiles and corresponding depolarisation ratio profiles. For parts of the cloud system characterised by almost negligible multiple scattering the calculation of the particle backscatter coefficient profiles was possible using the lidar ratio information obtained from the in-situ measurements in ice-crystal cloud and water cloud. / Das Airborne Mobile Aerosol Lidar (AMALi) wurde am Alfred-Wegener-Institut für Polar- und Meeresforschung in Potsdam für die Untersuchung arktischer Aerosole und Wolken der unteren Troposphäre entwickelt und gebaut. Das AMALi wurde erfolgreich in zwei AWI Flugzeugmesskampagnen, der ASTAR 2004 und der SvalEx 2005, die in Spitzbergen in der Arktis durchgeführt wurden, eingesetzt. Zwei neue Lidar Datenauswertungsmethoden wurden implementiert: die Two-Stream Inversion und die Iterative Airborne Inversion. Damit erwies sich die Berechnung der Profile der Teilchen Rückstreu- und Extinktionskoeffizienten mit einem entsprechenden Lidar Verhältnis, das charakteristisch für arktische Luft ist, als möglich. Der Vergleich dieser Auswertungen mit den Resultaten, die mit verschiedenen Fernerkundungs- und In-situ Instrumenten gewonnen worden waren (stationäres Koldewey Aerosol Raman Lidar KARL, Sonnenphotometer, Radiosondierung und Satellitenbilder) ermöglichten die Interpretation der Lidar-Resultate und eine Charakterisierung sowohl der reinen als auch der verschmutzten Luft. Außerdem konnten die Lidardaten mit operationellen ECMWF Daten und dem kleinskaligen Dispersionsmodel EULAG verglichen werden. Dadurch konnte der Einfluss der Spitzbergener Orographie auf die Aerosolladung der Planetaren Grenzschicht untersucht werden. Für Wolkenmessungen wurde eine neue Methode der alternativen Fernerkundung mit dem AMALi und flugzeuggetragenen In-situ Messgeräten verwendet, um optische und mikrophysikalische Eigenschaften der Wolken zu bestimmen. Diese Methode wurde erfolgreich implementiert und auf Mixed-Phase Wolken geringer optischen Dicke angewendet. Ein Beispiel hier stellt das Besamen der Wolken (sogenannte Feeder-Seeder Effekt) dar, bei dem Eiskristalle in eine niedrige unterkühlte Stratokumulus fallen. Dabei konnten Lidarsignale, Intensitätsprofile und die Volumendepolarisation gemessen werden. Zusätzlich konnten in den weniger dichten Bereichen der Wolken, in denen Vielfachstreuung vernachlässigbar ist, auch Profile des Teilchen Rückstreukoeffizienten berechnet werden, wobei Lidarverhältnisse genommen wurden, die aus In-situ Messungen für Wasser- und Eiswolken ermittelt wurden.

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 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.

L'aérosol atmosphérique a des effets sur le changement climatique global et un impact sanitaire non-négligeables. Dans l'aérosol atmosphérique terrestre, les composés organiques représentent une fraction importante. Du fait de l'extrême complexité de cette fraction organique et des processus dynamiques qui l'animent, une fraction non négligeable de celle-ci n'est pas clairement identifiée à ce jour malgré des techniques d'analyses toujours plus nombreuses. Dans cette thèse, nous avons voulu explorer la richesse d'information fournie par une technique innovante : la spectrométrie de masse à haute résolution (HRMS). La haute résolution du LTQ-Orbitrap fournit une extrême précision sur la masse des molécules analysées et permet d'en identifier les formules brutes. Tout d'abord, nous avons utilisé cette nouvelle méthode de caractérisation afin d'élucider en laboratoire des mécanismes de production de l'aérosol se déroulant en phase aqueuse. Associée à une caractérisation par RMN, la HRMS nous permet d'identifier des voies de fabrication de composés de faible poids moléculaires (acides carboxyliques, aldéhydes, cétone) ainsi que des composés à haut poids moléculaire : les oligomères formés se transforment en HULIS au cours de leur vieillissement. Le fait que la méthacroléine (MACR) et la méthyl-vinyl-cétone (MVK), les deux principaux produits d'oxydation de l'isoprène, forment des AOS en phase aqueuse avait été précédemment montré. Ce travail montre que les précurseurs des AOS sont différents selon l'isomère et que les séries d'oligomères formées atteignent 1400 Da.. L'étude HRMS des produits permet de proposer un mécanisme radicalaire d'oligomérisation de la MVK. L'analyse HRMS des produits de la MACR montre qu'en plus du mécanisme valable pour la MVK, la réactivité de la MACR engendre co-polymérisation et production d'Hulis. Une signature HRMS des Hulis a été mise en évidence. Ensuite, nous avons utilisé les méthodes de traitement de données HRMS pour tenter de les appliquer à l'identification d'aérosol ambiant. Les composés organiques représentent la fraction majeure des particules de l'aérosol atmosphérique ; une grande partie reste mal identifiée. Une compréhension détaillée des sources et des procédés de transformations est nécessaire. L'investigation de la composition chimique des particules de matière fine et ultrafine peut être apporter par HRMS. L'ESI-Orbitrap apporte une description moléculaire qui détermine les propriétés chimiques et physiques de l'aérosol organique. Les particules ont été échantillonnées selon leur taille respective. Les prélèvements ont été fait à Grenoble en été et en hiver. Une comparaison saisonnière permet d'identifier des signatures chimiques différentes. Enfin, une intercomparaison est établie avec des échantillons d'une troisième campagne prélevées en proximité routière: MOCOPO. / Atmospheric aerosol has an important impact on the radiative balance of Earth. Organics compounds represent the major fraction of atmospheric aerosol particles; a large part is still not well characterized. A detailed understanding of the sources, transformations processes and fates of organics aerosols is needed. This work investigates the ability of the ESI-Orbitrap to characterize organics molecules of aerosol. Firstly, experimental and analytical methods were developed to unveil mechanistic ambiguities that were previously shown. Methacrolein (MACR) and methyl vinyl ketone (MVK) (the two main gas phase atmospheric oxidation products of isoprene) were known to form oligomers and secondary organic aerosol (SOA) upon aqueous phase OHoxidation and subsequent water evaporation. For the two precursors, ESI-MS analysis of the reacting solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1400 Da.. Taking advantage of the regularities observed in the oligomer systems, the ESI-HRMS data were used to propose stoichiometries for more than 75% of the observed signal. Moreover, we show here that MACR oligomers aging give rise to HULIS production. In addition, global estimates of secondary organic aerosol (SOA) formation flux show that current descriptions miss a large fraction of the sources. This gaping underestimation has been linked to a poor understanding of aerosol functionalization in the atmosphere and lead to the formation of a new conceptual framework for the description of the aerosol, based on volatility versus polarity plots. This new framework is almost exclusively based on High Resolution Time of Flight Aerosol Mass Spectrometer(HR-Tof-AMS) data, as this instrument gives access to average H:C, N:C and O:C ratios for the bulk aerosol. The AMS estimates for O:C and H:C ratios are thus based on heavy fragmentation of organics followed by stoichiometry attribution on those fragments. Given the resolution of the HR-ToF-AMS, such an attribution is not feasible above a certain mass, making fragmentation a necessary aspect of the measurement. Conversely, Orbitrap-HRMS provide a resolution of 100,000 at m/z 400, with a mass range 50 – 2000 amu, enabling stoichiometry retrieval up to higher masses than the AMS. Coupled to a “soft” electrospray ionization method, Orbitrap-HRMS gives O:C and H:C ratios on entire molecules in the analysed mixture. We used samples from three contrasted field campaigns: the two first at an urban kerbside site in summer and in winter, the third one in the roadway vicinity (Grenoble, France). Accelerated Solvent Extraction provides a clear overview of the chemical composition of organic extracts from aerosol particles collected at different season at an urban site. The elemental composition was obtained within 2-5 ppm, on the range 150-300 m/z. However, this study shows that both ionization polarity were needed to get a complete picture of the chemical composition of the samples. We showed that Esi-Orbitrap-HRMS allows to compute a statistical distribution of the elementary ratios that is different from a simple average value. Keywords: HRMS, SOA.

In this thesis, we have presented a systematic analysis of the change of cloud properties due to variation in aerosol concentration over Indian region using satellite observations, and Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) simulations. The Tropical Rainfall Measurement Mission (TRMM) based Microwave Imager (TMI) estimates (2A12) have been used to compare and contrast the characteristics of cloud liquid water and ice over the Indian land region and the surrounding oceans, during the pre-monsoon (May) and monsoon (June–September) seasons. Based on the spatial homogeneity of rainfall, we have selected five regions for our study (three over ocean, two over land). In general, we find that the mean cloud liquid water and cloud ice content of land and oceanic regions are different, with the ocean regions showing higher amount of CLW. A comparison across the ocean regions suggests that the cloud liquid water over the or graphically influenced Arabian Sea (close to the Indian west coast) behaves differently from the cloud liquid water over a trapped ocean (Bay of Bengal) or an open ocean (Equatorial Indian Ocean). Specifically, the Arabian Sea region shows higher liquid water for a lower range of rainfall, whereas the Bay of Bengal and the Equatorial Indian Ocean show higher liquid water for a higher range of rainfall. Apart from geographic differences, we also documented seasonal differences by comparing cloud liquid water profiles between monsoon and pre-monsoon periods, as well as between early and peak phases of the monsoon. We find that the cloud liquid water during the lean periods of rainfall (May or June) is higher than during the peak and late monsoon season (July-September) for raining clouds over central India. However, this is not true over the ocean. As active and break phases are important signatures of the monsoon progression, we also analyzed the differences in cloud liquid water during various phases of the monsoon, namely, active, break, active-to-break (a2b) and break-to-active (b2a) transition phases. We find that the cloud liquid water content during the b2a transition phase is significantly higher than that during the a2b transition phase over central India. We speculate that this could be attributed to higher amount of aerosol loading over this region during the break phase. We lend credence to this aerosol-liquid water/rain association by comparing the central Indian cloud liquid water with Southeast Asia (where the aerosol loading is significantly smaller) and find that in the latter region, there are no significant differences in cloud liquid water during the different phases of their monsoon. The second part of our study involves evaluating the ability of the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) to simulate the observed variation of cloud liquid water and rain efficiency. We have used no chemistry option, and the model was run with constant aerosol concentration. The model simulations (at 4.5 km resolution) are done for the month of June–July 2004 since this period was particularly favorable for the study of an active–break cycle of the monsoon. We first evaluate the sensitivity of the model to different parameterizations (microphysical, boundary layer, land surface) on the simulation of rain over central India and Bay of Bengal. This is done to identify an “optimal” combination of parameterizations which reproduces the best correlation with observed rain over these regions. In this default configuration (control run), where the aerosol concentration is kept constant throughout the simulation period, the model is not able to reproduce the observed variations of cloud liquid water during the different phases of an active-break cycle. To this end, we proceeded to modify the model by developing an aerosol-rain relation, using Aerosol Robotic Network (AERONET) and TRMM 3B42 data that realistically captures the variation of aerosol with rain. It is worth highlighting here that our goal was to primarily isolate the indirect effect of aerosols in determining the observed changes in cloud liquid water (CLW) during the active-break phases of the Indian monsoon, without getting into the complexity of a full chemistry model such as that incorporated in WRF-Chem. Moreover, the proposed modification (modified run) is necessitated by the lack of realistic emission estimates over the Indian region as well as the presence of inherent biases in monsoon simulation in WRF. The main differences we find between the modified and control simulations is in the mean as well as spatial variability of CLW. We find that the proposed modification (i.e., rate of change of aerosol concentration as a function of rain rate) leads to a realistic variation in the CLW during the active-break cycle of Indian monsoon. Specifically, the peak value of CLW in the b2a (a2b) phase is larger (smaller) in the modified as compared to the control run. These results indicate a stronger change in CLW amount in the upper levels between the two transition phases in the modified scheme as compared to the control simulation. More significantly, we also observe a change in sign at the lower levels of the atmosphere, i.e., from a strong positive difference in the control run to a negative difference in the modified simulation, similar to that observed. Additionally, we investigated the impact of the proposed modification, via CLW changes, on cloud coverage, size of clouds and their spatial variability. We find that the transformation of optically thin clouds to thick clouds during the break phase was associated with larger cloud size in modified compared to the control simulation. Moreover, the higher rate of decay of the spatial variability of CLW with grid resolution, using the modified scheme, suggests that clusters of larger clouds are more in the modified compared to control simulation. Taken together, the interactive aerosol loading proposed in this thesis yields model simulations that better mimic the observed CLW variability between the transition phases.

Im Rahmen der vorliegenden Arbeit wurde der Zusammenhang zwischen heterogener Eisbildung und Temperatur auf Basis eines 11-Jahres Lidardatensatzes untersucht, wobei besonders der potenzielle Einfluss von Wüstenstaubaerosol auf die heterogene Gefriertemperatur von unterkühlten Wasserwolken überprüft wurde. Der zugrundeliegende Lidardatensatz entstand im Rahmen von zwischen 1997 und 2008 am Leibniz-Institut für Troposphärenforschung (IfT) in Leipzig durchgeführten Lidarmessungen. Mehr als 2300 zeitlich und räumlich defifinierte Wolkenschichten wurden anhand des gemessenen linearen Depolarisationsverhältnisses als Flüssigwasserwolken oder als eisbeinhaltende Wolken klassifiziert. Dazu war es nötig, den störenden Einfluss von spiegelnden Reflektionen horizontal ausgerichteter Eiskristalle auf das gemessene Depolarisationsverhältnis zu charakterisieren. Die für die Auswertung benötigten Wolkenoberkantentemperaturen wurden aus Modelldaten oder, falls zeitnah verfügbar, aus Radiosondenprofifilen ermittelt. Die statistische Auswertung des Wolkendatensatzes ergab, dass der Anteil an eisbeinhaltenden Wolken mit abnehmender Temperatur stark zunimmt. Wurde in Wolken mit Oberkantentemperaturen zwischen 0 und -5 °C in nur 1% aller Fälle Eis detektiert, enthielten zwischen -10 und -15 °C bereits 40% der in dem Temperaturbereich beobachteten Wolken Eis. Bei Wolkenoberkantentemperaturen unterhalb von -25 °C wurde in nahezu 100% aller Fälle Eis in den Wolken beobachtet. Ein ähnlicher Zusammenhang zwischen Temperatur und dem Anteil an eisbeinhaltenden Wolken wurde bereits in zahlreichen auf Flugzeugmessungen basierenden Studien gefunden. In einem weiteren Schritt wurde der Wolkendatensatz mittels drei verschiedener Ansätze in einen staubbelasteten sowie einen staubfreien Teil getrennt. Dies geschah Anhand einer Trajektorien-Clusteranalyse sowie der Trennung bezüglich der von einem Mineralstaubvorhersagemodell berechneten Mineralstaubbelastung in Wolkenhöhe beziehungsweise in der gesamten Luftsäule über Leipzig. Die Trennung ergab, dass staubbelastete Wolken im Temperaturbereich zwischen -5 und -25 °C 10-30% mehr Eis beinhalten als staubfreie Wolken. Die Ergebnisse dieser Untersuchung legen deshalb nahe, dass Mineralstaub Eisbildung in unterkühlten Wolken maßgeblich fördert. Der Vergleich des Leipziger Wolkendatensatzes mit einem auf den Kapverden gesammelten Datensatz tropischer Wolken zeigte, dass trotz vergleichbarem Einfluss von Mineralstaubaerosol Eisbildung in den Tropen erst bei um 10 K tieferen Temperaturen einsetzt. Als mögliche Einflussfaktoren wurden Unterschiede in der atmosphärischen Dynamik und die Wirkung effektiverer Eiskeime über Mitteleuropa diskutiert.:1 Introduction 2 Ice formation 2.1 Homogeneous nucleation 2.2 Heterogeneous nucleation 2.2.1 Heterogeneous nucleation processes 2.2.2 Studies of heterogeneous nucleation 2.3 Dynamical processes and ice multiplication 3 Motivating questions for the present study 4 IfT Earlinet lidar MARTHA 4.1 IfT lidar system MARTHA 4.2 Lidar equation 4.3 Particle backscatter coefficient 4.3.1 Klett-Fernald method 4.3.2 Raman method 4.4 Particle extinction coefficient 4.5 Depolarization ratio 4.5.1 Depolarization ratio for idealized systems 4.5.2 Depolarization ratio for non-idealized systems 5 Cloud detection with MARTHA 5.1 Cloud geometrical properties 5.2 Meteorological data 5.3 Aerosol information 5.4 Cloud phase determination 5.5 Multiple scattering 5.6 Specular reflection 5.6.1 Instrumentation 5.6.2 WiLi and MARTHA observations 5.6.3 PollyXT and MARTHA observations 5.7 Liquid/Ice-containing layer discrimination scheme for MARTHA 6 Observations 6.1 20 June 2007: Cloud development in Saharan dust 6.2 3 November 2003 and 24 November 2006: Cloud development at aerosol background conditions 6.3 26 May 2008 and 26 December 2008: Indications for deposition nucleation 7 The MARTHA 1997-2008 cloud data set 7.1 Statistical basis 7.2 Geometrical cloud properties 7.3 Relationship between heterogeneous ice formation and temperature 7.4 Impact of Saharan dust on heterogeneous ice nucleation 7.4.1 Trajectory cluster analysis 7.4.2 Dust-model-based investigations 7.5 Discussion 8 Summary, conclusions, and outlook 8.1 Summary and conclusions 8.2 Outlook Bibliography List of abbreviations / The formation and presence of ice crystals in clouds strongly determines meteorological processes as precipitation formation but also climatological parameters as the radiation budget of the atmosphere. The process of ice formation, however, is not straightforward because ice crystals and liquid water droplets can coexist at temperatures from -38 °C to 0 °C. In this temperature range, aerosol particles, so-called ice nuclei, must be present to trigger ice formation in a supercooled droplet. From laboratory studies it is known that mineral dust particles are efficient ice nuclei. We present a statistical analysis of lidar-based observations of 2300 free-tropospheric clouds that was used to investigate the effect of mineral dust particles on the ice-formation temperature. The observations were performed at Leipzig, Germany (51° N, 12 °E). The time and height as well as the phase state (ice, liquid-water) of the observed clouds can easily be derived from the lidar data. The dust load in every observed cloud layer was determined by means of model data. From the analysis it was found that dust-affected clouds produce ice 50% more frequently than dust-free clouds at temperatures between -20 and -10 °C. In a last step we compared the relationship between ice-containing clouds and temperature of the Leipzig dataset with a similar data set from Cape Verde (15 °N, 23.5 °W). Even though dust is omnipresent in the troposphere at this location, the study of more than 200 spatially well-defined altocumulus clouds did not show a significant number of ice clouds at temperatures above -15 °C. Possible explanations for the observed differences between the Leipzig and the Cape Verde data set are contrasts in atmospheric dynamics over Central Europe and western Africa or the presence of anthropogenic aerosol over Europe that may provide additional effective ice nuclei besides Saharan dust.:1 Introduction 2 Ice formation 2.1 Homogeneous nucleation 2.2 Heterogeneous nucleation 2.2.1 Heterogeneous nucleation processes 2.2.2 Studies of heterogeneous nucleation 2.3 Dynamical processes and ice multiplication 3 Motivating questions for the present study 4 IfT Earlinet lidar MARTHA 4.1 IfT lidar system MARTHA 4.2 Lidar equation 4.3 Particle backscatter coefficient 4.3.1 Klett-Fernald method 4.3.2 Raman method 4.4 Particle extinction coefficient 4.5 Depolarization ratio 4.5.1 Depolarization ratio for idealized systems 4.5.2 Depolarization ratio for non-idealized systems 5 Cloud detection with MARTHA 5.1 Cloud geometrical properties 5.2 Meteorological data 5.3 Aerosol information 5.4 Cloud phase determination 5.5 Multiple scattering 5.6 Specular reflection 5.6.1 Instrumentation 5.6.2 WiLi and MARTHA observations 5.6.3 PollyXT and MARTHA observations 5.7 Liquid/Ice-containing layer discrimination scheme for MARTHA 6 Observations 6.1 20 June 2007: Cloud development in Saharan dust 6.2 3 November 2003 and 24 November 2006: Cloud development at aerosol background conditions 6.3 26 May 2008 and 26 December 2008: Indications for deposition nucleation 7 The MARTHA 1997-2008 cloud data set 7.1 Statistical basis 7.2 Geometrical cloud properties 7.3 Relationship between heterogeneous ice formation and temperature 7.4 Impact of Saharan dust on heterogeneous ice nucleation 7.4.1 Trajectory cluster analysis 7.4.2 Dust-model-based investigations 7.5 Discussion 8 Summary, conclusions, and outlook 8.1 Summary and conclusions 8.2 Outlook Bibliography List of abbreviations

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.

The aim of the study was to determine the 13 health risk PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene, ideno(1,2,3-cd)perylene and coronene; c-PAU highlighted) in the fractions of size-segregated aerosol of the urban air in Ostrava (2012, 2014) and Mlada Boleslav (2013) at low temperatures in winter, and to verify experimentally a sampling artifact, i.e., to quantify PAHs in the gas phase. For the particle size separation high-volume cascade impactor Hi-Vol BGI 900 was used. PAHs were determined by HPLC-FLD/PDA. In Ostrava in 2012 during the winter inversion (up to -25 řC), mean concentration of 13 PAHs in aerosol was 432 ng.m-3 ; in fraction 10 - 1 µm 119 ng.m-3 , 1 - 0,5 µm 185 ng.m-3 , 0,5 - 0,17 µm 91 ng.m-3 , in fraction < 0,17 µm 37 ng.m-3 and in the gaseous phase of min. 40 ng.m-3 . In the most unfavorable day 2. 2. 2012 (-18.6 ř C) reached the 24-hour average of 13 PAHs 890 ng.m-3 , the sum of carcinogenic PAHs 237 ng.m-3 and benzo(a)pyrene 32.3 ng.m-3 . An irregular and different decline of PAHs concentrations after inversion was measured: in fraction 1 - 10 µm 2.8 times, 0.5 - 1 µm 4.2 times, 0.5 - 0.17 µm 4 times and for <0.17 µm up to 7.6 times....

No presente trabalho, é avaliada a qualidade do ar interno com ênfase na concentração de aerodispersóides presentes em edifícios comerciais e residenciais com sistema de ventilação natural ou condicionamento de ar. De fato, algumas doenças de origem ocupacional são causadas pela inalação de aerodispersóides nocivos à saúde. O método utilizado para avaliar a qualidade do ar interno nos edifícios comerciais e residenciais consistiu primeiramente em caracterizar os medidores de aerodispersóides e em seguida passou-se para a análise das concentrações e das características ambientais. A pesquisa mediu a concentração de aerodispersóides em edifícios com sistemas de ventilação diferentes (1a fase), e identificou as principais fontes de emissão de aerodispersóides em um apartamento residencial (2a fase). Observou-se que as concentrações obtidas na pesquisa estão acima dos valores recomendados na RE n° 9 (ANVISA, 2003) e por Morawska et al. (1999) que atribuem valores de 80 µg/m³ e 7.400 part./cm³, para concentrações médias em massa e em número, respectivamente. Com base nas observações acima, chegou à conclusão que as concentrações médias em massa e em número de aerodispersóides, durante as atividades domésticas (cozimento, reforma, limpeza, entre outras), foram várias vezes maiores do que as concentrações obtidas em ambientes com atividades profissionais ou com menor ocupação durante o dia. / This paper is the result of quality evaluation of indoor air quality with emphasis on the concentration of aerodispersoid in commercial and residential buildings with natural ventilation or air conditioning systems. In fact, some of the occupational diseases are caused by the inhalation of aerodispersoids hazardous to health. The method applied to evaluate the indoor air quality in commercial and residential buildings consisted firstly of characterizing the aerodispersoid measuring devices and subsequently analyzing the concentration levels and environmental characteristics. This research measured the concentration of aerodispersoids in buildings equipped with a variety of ventilation systems (phase1) and next it identified the main emission sources in a residential apartment (phase 2). It was observed that the concentration levels measured were above the specifications recommended by RE n° 9 (ANVISA, 2003) and by Morawska et al. (1999) which attribute values of 80 µg/m³ and 7.400 part./cm³, for average concentration in mass and number respectively. Based on the above information it was concluded that the average concentration levels of aerodispersoids in mass and number in home related activities (cooking, restoration, cleaning, etc) were many times higher than the concentration levels found in business environments or in environments with less occupation during the day.