<p>Spatial variability of the Earth's surface has a considerable impact on the atmosphere at all scales and understanding the mechanisms involved in land-atmosphere interactions is hindered by the scarcity of appropriate observations. A measurement gap exists between traditional point sensors and large aircraft and satellite-based sensors in collecting measurements of atmospheric quantities. Point sensors are capable of making long time series of measurements, but cannot make measurements of spatial variability. Large aircraft and satellites make measurements over large spatial areas, but with poor spatial and temporal resolution. A helicopter-based platform can make measurements on scales relevant for towers, especially close to the Earth's surface, and can extend these measurements to account for spatial variability. Thus, the Duke University Helicopter Observation Platform (HOP) is designed to fill the existing measurement gap. </p><p>Because measurements must be made in such a way that they are as uncontaminated by the platform itself as much as is possible, it is necessary to quantify the aerodynamic envelope of the HOP. The results of an analytical analysis of the location of the main rotor wake at various airspeeds are shown. Similarly, the results of a numerical analysis using the commercial Computational Fluid Dynamics software Fluent are shown. The optimal flight speed for the sampling of turbulent fluxes is found to be around 30 m/s. At this airspeed, the sensors located in front of the nose of the HOP are in advance of the wake generated by the main rotor. This airspeed is also low enough that the region of high pressure due to the stagnation point on the nose of the HOP does not protrude far enough forward to affect the sensors. Measurements of differential pressures, variables and turbulent fluxes made while flying the HOP at different airspeeds support these results. No systematic effects of the platform are seen at airspeeds above about 10 m/s.</p><p>Processing of HOP data collected using the current set of sensors is discussed, including the novel use of the Empirical Mode Decomposition (EMD) to detrend and filter the data. The EMD separates the data into a finite number of Impirical Mode Functions (IMFs), each of which is unique and orthogonal. The basis is determined by the data itself, so that it need not be known a priori, and it is adaptive. The EMD is shown to be an ideal tool for the filtering and detrending of HOP data using data gathered during the Cloud and Land Surface Interaction Campaign (CLASIC). </p><p>The ability of the HOP to accurately measure atmospheric profiles of potential temperature is demonstrated. During experiments conducted in the marine boundary layer (MBL) and the convective boundary layer (CBL), HOP profiles are evaluated using profiles from an elastic backscatter lidar. The HOP and the lidar agree on the height of the boundary layer in both cases, and the HOP effectively locates other atmospheric structures.</p><p>Atmospheric sensible and latent heat fluxes, turbulence kinetic energy (TKE) and horizontal momentum fluxes are also measured, and the resulting information is used to provide context to tower-based data collected concurrently. A brief comparison made over homogeneous ocean conditions yields good results. A more exhaustive evaluation is made using short HOP flights made over an orchard during the Canopy Horizontal Turbulence Study (CHATS).</p> / Dissertation

In this work spectral airborne measurements of upward irradiance and a novel remote sensing technique for the cloud droplet number concentration are used to evaluate the representation of clouds in current operational weather prediction models.

We present here the first cloud condensation nuclei (CCN) concentration profiles derived from measurements with the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) aboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO), for different aerosol types at a supersaturation of 0.15%. CCN concentrations, along with the corresponding uncertainties, were inferred for a nighttime CALIPSO overpass on 9 September 2011, with coincident observations with the Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 research aircraft, within the framework of the Evaluation of CALIPSO’s Aerosol Classification scheme over Eastern Mediterranean (ACEMED) research campaign over Thessaloniki, Greece. The CALIPSO aerosol typing is evaluated, based on data from the Copernicus Atmosphere Monitoring Service (CAMS) reanalysis. Backward trajectories and satellite-based fire counts are used to examine the origin of air masses on that day. Our CCN retrievals are evaluated against particle number concentration retrievals at different height levels, based on the ACEMED airborne measurements and compared against CCN-related retrievals from the Moderate Resolution Imaging Spectroradiometer (MODIS) sensors aboard Terra and Aqua product over Thessaloniki showing that it is feasible to obtain CCN concentrations from CALIPSO, with an uncertainty of a factor of two to three.

To understand the contribution of aerosol particles to radiative forcing and heterogeneous chemical processes in the upper troposphere and lowermost stratosphere (UT/LMS), the knowledge of the particle size distribution is mandatory. Unfortunately, measurements in the UT/LMS are costly. Research aircrafts are expensive and thus their application is limited in time and space. Satellite remote sensing measurements provide a good temporal and spatial (horizontal) coverage, but only a limited vertical resolution and currently cannot resolve the particle size distribution. Therefore, within this thesis an optical particle counter (OPC) unit was modified for the application onboard a passenger long-haul aircraft within the CARIBIC project (www.caribic-atmospheric.com). The CARIBIC OPC unit provides regular and cost-efficient particle size distribution measurements of accumulation mode particles in the UT/LMS. In April 2010, the new OPC unit was installed for the first time onboard the Lufthansa Airbus A340 600 (D-AIHE) for the measurement of the volcanic ash cloud from the Eyjafjallajökull eruption (April to May 2010). Since June 2010 the OPC unit measures on usually four intercontinental flights per month the UT/LMS particle size distribution in the particle size range 125 to 1300 nm particle diameter. As the data acquisition stores the scattering raw signal and all housekeeping data as well, during the post flight data analysis the temporal- and size channel resolution can be flexible set. Within this work the data were analyzed with 32 size channels and 300 seconds. As aircraft-borne measurements are always time-consuming, the development of the OPC unit and the analysis routine, as well as its characterization and certification took more than two thirds of the total working time of this thesis. Therefore, the analysis of the data is limited to the first year of regular measurements until May 2011. Nevertheless, this dataset is sufficient to demonstrate the scientific relevance of these measurements. To validate the OPC data, a comparison to particle size distributions measured from board research aircraft was carried out. The analysis of the volcanic ash flights in April and May 2010 showed strongly enhanced particle mass concentrations inside the plumes and agreed in some regions very well to the particle mass concentration predicted by a dispersion model. A further case study shows the occurrence of a surprising large (1000 km) and high concentrated pollution plume over eastern Asia close to Osaka (Japan). Inside the plume the highest particle number- and mass concentrations measured with the OPC unit in the analysis period were observed (except volcanic ash flights). A detailed analysis of the in parallel measured trace gasses as well as meteorological- and LIDAR data showed, the observed plume originate from biomass burning and industrial emissions in eastern China. A third case study gives a first attempt of a mass closure/validation between the particle masses derived by the CARIBIC OPC unit and the CARIBIC impactor particle samples. First statistical analyses to the vertical, meridional, and seasonal variation of the accumulation mode particle size distribution and therefrom derived parameter indicate a stratospheric vertical increasing gradient for the particle number- and mass concentration. In general in the mid-latitude LMS the concentration of accumulation mode particles was found to be on average 120% higher than in the mid-latitude UT. The mid-latitude LMS particle size distribution shows a seasonal variation with on average 120% higher concentrations during spring compared to fall. This results can be explained with general dynamics in the stratosphere (Brewer-Dobson Circulation) and in the tropopause region (stratosphere-troposphere-exchange, STE). An anti-correlation of gaseous mercury to the stratospheric particle surface area concentration (R²=0.97) indicates that most likely stratospheric aerosol particles do act as a sink for gaseous mercury. Finally, two comparisons of the OPC data to data from satellite remote sensing and a global aerosol model underline the OPC potential and the benefits of creating an in situ measured reference dataset. / Um die Rolle von Aerosolpartikeln beim Strahlungsantrieb und der heterogenen chemischen Prozessen in der oberen Troposphäre und untersten Stratosphäre (OT/US) verstehen zu können, ist es unabdingbar die Partikelgrößenverteilung zu kennen. Messungen der Partikelgrößenverteilung in dieser Region sind allerdings aufwendig. Der Einsatz von Forschungsflugzeugen ist teuer und deshalb zeitlich und räumlich nur begrenzt. Satellitenmessungen bieten zwar eine gute zeitliche und räumliche (horizontal) Abdeckung, aber nur eine begrenzte vertikale Auflösung. Weiterhin können bisherige Satellitenmessungen die Partikelgrößenverteilung nicht auflösen. Im Rahmen dieser Arbeit wurde deshalb ein optischer Partikelzähler (OPC) Messeinschub für den Einsatz an Bord eines Langstrecken-Passagierflugzeugs aufgebaut (CARIBIC Projekt, www.caribic-atmospheric.com). Mit diesem Messeinschub kann regelmäßig und kosteneffizient die Partikelgrößenverteilung des Akkumulationsmodes in der OT/US gemessen werden. Im April 2010 wurde der neue OPC Einschub erstmals an Bord des Lufthansa Airbus A340-600 (D-AIHE) installiert um die Vulkanasche der Eyjafjallajökull Eruption (April bis Mai 2010) zu messen. Seit Juni 2010 misst der OPC Einschub auf durchschnittlich vier Interkontinentalflügen pro Monat die Partikelgrößenverteilung der OT/US im Größenbereich zwischen 125 und 1300 nm Partikeldurchmesser. Während des Fluges speichert die Datenerfassung alle Rohsignale ab und ermöglicht dadurch eine nutzerspezifische Datenauswertung nach dem Flug (z. B. Anzahl der Größenkanäle oder Zeitauflösung). Im Rahmen dieser Arbeit wurden die Daten mit 32 Größenkanälen und 300 Sekunden analysiert. Da fluggetragene Messungen immer sehr aufwendig sind, beanspruchte die Entwicklung des OPC Einschubs und des Analysealgorithmus, sowie die Charakterisierung und Zertifizierung mehr als zwei Drittel der Gesamtarbeitszeit dieser Arbeit. Daher ist die Analyse der Messdaten auf das erste Jahr der regulären Messungen bis Mai 2011 beschränkt. Dennoch ist dieser Datensatz geeignet um die wissenschaftliche Relevanz dieser Messungen zu demonstrieren. Um die OPC-Daten zu validieren, wurde ein Vergleich mit bisherigen OPC Messungen von Bord Forschungsflugzeugen durchgeführt. Die Analyse der Vulkanascheflüge im April und Mai 2010 zeigte in der Abluftfahne stark erhöhte Partikelmassekonzentrationen, welche in einigen Vergleichsregionen sehr gut mit der Vorhersage eines Disperionsmodells übereinstimmten. Eine weitere Fallstudie zeigt das Auftreten einer überraschend großen (1000 km) und hoch konzentrierten Abluftfahne über Ostasien nahe Osaka (Japan). In der Abluftfahne wurde die im Analysezeitraum höchste mit dem CARIBIC OPC gemessene Partikelanzahl- und Massenkonzentration beobachtet (ausgenommen Vulkanascheflüge). Eine detaillierte Analyse der parallel gemessenen Spurengase, sowie meteorologischer Daten und LIDAR Profile zeigte, dass die beobachtete Abluftfahne eine Mischung aus Biomasseverbrennungs- und Industrieabgasen aus Ost-China war. Eine dritte Fallstudie stellt einen ersten Versuch einer Massenschließung/Validierung zwischen der aus den CARIBIC OPC-Daten abgeleiteten Partikelmasse und der Partikelmasse aus CARIBIC Impaktorproben dar. Erste statistische Analysen zur vertikalen, meridionalen und saisonalen Variabilität der Partikelgrößenverteilung im Akkumulationsmode und daraus abgeleiteten Parametern zeigen einen vertikal ansteigenden Gradienten für die Partikelanzahl- und Massenkonzentration. Generell war in der US der mittleren Breiten die Konzentration von Akkumulationsmode Partikeln im Mittel um 120% höher als in der OT der mittleren Breiten. Weiterhin wurde in der US der mittleren Breiten eine jahreszeitliche Schwankung gefunden. Im Frühling war die mit dem OPC gemessene Partikelkonzentrationen im Mittel um 120% höher als im Herbst. Diese Befunde lassen sich mit der atmosphärischen Dynamik in der Stratosphäre (Brewer-Dobson Zirkulation) und in der Tropopausenregion (Stratosphäre-Troposphäre-Austauschprozesse) erklären. Eine gefundene negative Korrelation von gasförmigen Quecksilber mit der stratosphärischen Partikeloberflächenkonzentration (R²=0.97) ist ein starker Indikator dafür, dass in der US Aerosolpartikel eine Senke für gasförmiges Quecksilber darstellen. Zum Abschluss unterstreichen zwei Vergleiche der OPC-Daten mit Satellitenmessungen und Ergebnissen eines globalen Aerosolmodels das Potential und den Nutzen der CARIBIC OPC Daten als in-situ gemessenen Referenzdatensatz.

Le changement climatique est relié à l’évolution de la composition chimique de l’atmosphère et de sa capacité oxydante, impliquant le système COV-NOy-HOx-O3. La troposphère tropicale, de l’Afrique de l’Ouest en particulier, joue un rôle critique sur la composition atmosphérique globale pour trois raisons majeures : (1) l’existence d’importantes sources de précurseurs d’espèces photooxydantes, (2) une photochimie active, (3) une activité convective intense en période de mousson. Pour évaluer son rôle, il est nécessaire de bien caractériser ces différents processus et leur interaction. Cette question est au coeur du programme international AMMA (Analyse Multidisciplinaire de la Mousson Africaine) dans lequel s’inscrit cette thèse. Ce travail a pour objectif de caractériser et d’évaluer l’impact de la convection nuageuse profonde sur la chimie photooxydante de la troposphère libre en Afrique de l’Ouest, en particulier pour les composés organiques volatils (COV), qui sont d’importants précurseurs d’ozone. Ce travail s’appuie sur les données physico-chimiques recueillies sur les deux avions de recherche français au cours de la campagne d’observation intensive de l’été 2006 de AMMA. Afin de compléter le dispositif instrumental embarqué, une nouvelle instrumentation de mesure indirecte des COV a été d’abord développée. Puis, l’utilisation de traceurs physico-chimiques et la mise en place d’outils diagnostiques appliqués aux COV (profils verticaux de concentrations, rapport de concentration de COV ad hoc, horloge photochimique, réactivité totale vis-à-vis de OH) ont montré que la convection profonde assure un transport vertical rapide et efficace des espèces gazeuses réactives émises près de la surface vers la haute troposphère. Enfin, un modèle photochimique de boîte 0D a permis de renseigner l’évolution de la composition chimique des masses d’air post-convectives. Les simulations montrent que les espèces transportées par la convection participent activement à la chimie et conduisent à une production nette et significative d’ozone dans la haute troposphère. La sensibilité de la production d’ozone aux précurseurs gazeux (COV et NOx) a été également évaluée. / Recent climatic change is tightly linked to the evolution of the chemical composition of the atmosphere and its oxidizing capacity through VOC-NOy-HOx-O3 system. The tropical troposphere, in particular of West Africa, plays a major role in the global atmospheric composition for three major reasons: (1) the existence of important ozone precursor sources, (2) an active photochemistry, (3) an intense convective activity during the monsoon period. To evaluate its role, it is necessary to characterize these processes and their interactions. This is one of the main objectives of the AMMA (African Monsoon Multidisciplinary Analyzes) international program. The present work goes through the frame of AMMA. Its main objective is to characterize and evaluate deep convection impact on the upper troposphere chemistry of West Africa, in particular for volatile organic compounds (VOC). This work is based on the data collected on the two French research aircrafts during the special observation period of AMMA in summer 2006. In order to enhance the instrumental device deployed onboard, a new offline instrumentation for non-methane hydrocarbons (NMHC) measurement was developed. Then, various physical and chemical tracers and several diagnostic tools applied to VOC data (vertical profiles, concentration ratios, photochemical clock, OH reactivity) showed that deep convection provides a fast and effective vertical transfer of reactive species emitted near the surface to the upper troposphere. At last, a photochemical box model 0D was used to simulate the chemical evolution of the composition of postconvective air masses. Simulations showed that reactive species transported by deep convection participate actively to the upper troposphere chemistry and lead to a significant and net ozone production. Ozone production sensitivity to VOC and NOx was also evaluated in the model.

En période hivernale, le golfe du Lion est sujet à des conditions de vents régionaux forts (Mistral et/ou Tramontane) qui transportent des masses d'air continentales froides et sèches au dessus de la mer. Ces événements, les Cold Air Outbreaks (CAO) , conduisent à d'intenses échanges air-mer et donc à un pompage de chaleur qui favorise la formation d'eaux denses et le déclenchement de la convection océanique profonde. La bonne représentation de ces échanges air-mer intenses dans les modèles de climat et de prévision numérique du temps reste à l'heure actuelle une problématique majeure. Elle est au cœur du projet ASICS-MED centré sur compréhension des mécanismes de formation d'eaux denses en Méditerranée et qui s'inscrit dans le cadre de la thématique " Échanges air-mer intenses " du programme HyMeX dédié à l'étude du cycle de l'eau en Méditerranée. Les processus qui s'opèrent au sein de la couche limite atmosphérique marine (CLAM) et de la couche de mélange océanique (CMO) interagissent entre eux à différentes échelles spatiales et temporelles. La compréhension de l'évolution globale de la CLAM mais également des mécanismes locaux nécessitent la prise en compte de l'ensemble des processus. L'étude présentée ici est consacrée à la structure moyenne et turbulente de la CLAM en conditions de vents forts. L'objectif est de déterminer comment l'organisation du champ turbulent est impactée lors d'épisodes de CAO et d'estimer les flux de surface associés à ces conditions de vents forts. La méthodologie adoptée est basée sur l'utilisation conjointe d'observations aéroportées collectées lors de la campagne de mesure SOP2 d'HyMeX et de simulations numériques. La campagne de mesure SOP2 d'HyMeX qui a eu lieu au cours de l'hiver 2013 dans le golfe du Lion a permis de documenter grâce à l'avion de recherche ATR42 la structure moyenne et turbulente de la CLAM lors de 11 épisodes de CAO. Une analyse spectrale s'appuyant sur un modèle analytique a été réalisé sur 181 paliers (i.e. segments de vol rectilignes et stabilisés en altitude). Les profils verticaux des échelles turbulentes caractéristiques ainsi que la forme du spectre de la vitesse verticale ont permis de mettre en évidence un allongement des structures énergétiques dans l'axe du vent moyen associé à l'organisation du champ turbulent sous la forme de rouleaux longitudinaux. Une description unidirectionnelle du champ turbulent tridimensionnel peut conduire à une représentativité limitée des structures cohérentes au sein des échantillons. Cependant, la connaissance des profils de flux sur toute l'épaisseur de la CLAM est nécessaire pour l'estimation des échanges air-mer. Une méthode de correction des flux turbulents calculés par eddy correlation a été appliqué afin de prendre en compte les erreurs systématique et aléatoire relatives à la mesure et au traitement de données. Cette correction a permis de déterminer les meilleures estimations possibles des flux extrapolés à la surface avec une marge d'incertitude pour les 11 épisodes de CAO documentés lors de la campagne SOP2 d'HyMeX. La comparaison de ces estimations aéroportées aux autres sources d'information dérivées de paramétrisations des flux a permis de mettre en évidence une sous-estimation systématique du flux de chaleur latente en conditions de vents forts. Une approche numérique a permis de compléter l'analyse de la structure moyenne et turbulente de la CLAM lors d'épisodes de CAO. / During winter, local strong winds (Mistral or Tramontana) occurred in the Gulf of Lion which bring cold and dry continental air over a warmer sea. Those events, the cold air outbreaks, can lead to intense air-sea interactions which favour dense water formation and deep oceanic convection. The representation of air-sea exchanges is a fundamental aspect of of climate modelling and numerical weather forecasting. The ASICS-MED project aims to identify fine-scale processes leading to dense water formation and is a part of the "Intense air-sea exchanges" topic of the HyMeX program devoted to hydrological cycle in the Mediterranean. The processes occurring within the marine atmospheric boundary layer (MABL) and the oceanic mixing layer (ML) interact with one another at different spatial and temporal scales. Understanding the overall evolution of the MABL but also the local mechanisms requires taking into account all the processes. The study presented here is devoted to the mean and turbulent structure of the MABL under strong wind conditions. The objective is to determine how the organization of the turbulent field is impacted during CAO events and to estimate the surface fluxes associated with these strong wind conditions. The methodology adopted is based on the joint use of airborne observations collected during the HyMeX-SOP2 field campaign and numerical simulations. The HyMeX-SOP2 field campaign took place during the winter of 2013 in the Gulf of Lion. The research aircraft ATR42 was operated to document the mean and turbulent structure of the MABL during 11 CAO events. A spectral analysis based on an analytic model was carried out on 181 legs (i.e. stacked straight and level runs stabilized in altitude). The vertical profiles of the turbulent characteristic scales as well as the shape of the vertical velocity spectrum revealed an elongation of the energy structures in the mean wind direction associated with the organization of the turbulent field into longitudinal rolls. A unidirectional sampling of the three-dimensional turbulent field may lead to a limited representativeness of the coherent structures within the samples. However, knowledge of kinematic fluxes profiles over the entire thickness of the CLAM is necessary to estimate air-sea exchanges. A correction method was applied to turbulent fluxes calculated by eddy correlation in order to take into account systematic and random errors related to measurement and data processing. This correction made it possible to determine the best possible estimates of the extrapolated surface fluxes with a margin of uncertainty for the 11 CAO events documented during the HyMeX-SOP2 field campaign. The comparison of these airborne estimates with the other sources of information derived from bulk parameterizations show a systematic underestimation of the latent heat flux under strong wind conditions. A numerical approach allowed to complete the analysis of the mean and turbulent structure of the MABL during CAO events. The numerical study, based on the non-hydrostatic Meso-NH model, focuses on an episode of strong Tramontana with winds greater than 25m/s documented during the HyMeX-SOP2 field campaign. In a first step, a one-dimensional framework made it possible to understand the forcing terms necessary to reproduce in a realistic way the development of the observed MABL. This reference configuration allowed, in a second time, a Large-Eddy Simulation of the CAO event. This simulation has been validated using airborne data and has allowed to deepen the description of the turbulent field as well as the evolution of the coherent structures oriented in the axis of the mean wind.

Biomass burning started to attract attention since the last decade because of its impacts on the atmosphere and the environmental air quality, as well as significant potential effects on human health and global climate change. Knowledge of particle emission characteristics from biomass burning is crucially important for the quantitative assessment of the potential impacts. This thesis presents the results of study aimed towards comprehensive characterization of particle emissions from biomass burning. The study was conducted both under controlled laboratory conditions, to quantify the particle size distribution and emission factors by taking into account various factors which may affect the particle characteristics, and in the field, to investigate biomass burning processes in the real life situations and to examine vertical profile of particles in the atmosphere. To simulate different environmental conditions, a new technique has been developed for investigating particle emissions from biomass burning in the laboratory. As biomass burning may occur in a field at various wind speeds and burning rates, the technique was designed to allow adjustment of the flow rates of the air introduced into the chamber, in order to control burning under different conditions. In addition, the technique design has enabled alteration of the high particle concentrations, allowing conducting measurements with the instrumentations that had the upper concentration limits exciding the concentrations characteristic to the biomass burning. The technique was applied to characterize particle emissions from burning of several tree species common to Australian forests. The aerosol particles were characterized in terms of size distribution and emission factors, such as PM2.5 particle mass emission factor and particle number emission factor, under various burning conditions. The characteristics of particles over a range of burning phases (e.g., ignition, flaming, and smoldering) were also investigated. The results showed that particle characteristics depend on the type of tree, part of tree, and the burning rate. In particular, fast burning of the wood samples produced particles with the CMD of 60 nm during the ignition phase and 30 nm for the rest of the burning process. Slow burning of the wood samples produced large particles with the CMD of 120 nm, 60 nm and 40 nm for the ignition, flaming and smoldering phases, respectively. The CMD of particles emitted by burning the leaves and branches was found to be 50 nm for the flaming phase and 30 nm for the smoldering phase, under fast burning conditions. Under slow burning conditions, the CMD of particles was found to be between 100 to 200 nm for the ignition and flaming phase, and 50 nm for the smoldering phase. For fast burning, the average particle number emission factors were between 3.3 to 5.7 x 1015 particles/kg for wood and 0.5 to 6.9 x 1015 particles/kg for leaves and branches. The PM2.5 emission factors were between 140 to 210 mg/kg for wood and 450 to 4700 mg/kg for leaves and branches. For slow burning conditions, the average particle number emission factors were between 2.8 to 44.8 x 1013 particles/kg for wood and 0.5 to 9.3 x 1013 particles/kg for leaves and branches, and the PM2.5 emissions factors were between 120 to 480 mg/kg for wood and 3300 to 4900 mg/kg for leaves and branches. The field measurements were conducted to investigate particle emissions from biomass burning in the Northern Territory of Australia over dry seasons. The results of field studies revealed that diameters of particles in ambient air emissions were within the size range observed during laboratory investigations. The laboratory measurements found that the particles released during the controlled burning were of a diameter between 30 and 210 nm, depending on the burning conditions. Under fast burning conditions, smaller particles were produced with a diameter in the range of 30 to 60 nm, whilst larger particles, with a diameter between 60 nm and 210 nm, were produced during slow burning. The airborne field measurements of biomass particles found that most of the particles measured under the boundary layer had a CMD of (83 ± 13) nm during the early dry season (EDS), and (127 ± 6) nm during the late dry season (LDS). The characteristics of ambient particles were found to be significantly different at the EDS and the LDS due to several factors including moisture content of vegetation, location of fires related to the flight paths, intensity of fires, and burned areas. Specifically, the investigations of the vertical profiles of particles in the atmosphere have revealed significant differences in the particle properties during early dry season and late dry season. The characteristics of particle size distribution played a significant role in these differences.

To understand the contribution of aerosol particles to radiative forcing and heterogeneous chemical processes in the upper troposphere and lowermost stratosphere (UT/LMS), the knowledge of the particle size distribution is mandatory. Unfortunately, measurements in the UT/LMS are costly. Research aircrafts are expensive and thus their application is limited in time and space. Satellite remote sensing measurements provide a good temporal and spatial (horizontal) coverage, but only a limited vertical resolution and currently cannot resolve the particle size distribution. Therefore, within this thesis an optical particle counter (OPC) unit was modified for the application onboard a passenger long-haul aircraft within the CARIBIC project (www.caribic-atmospheric.com). The CARIBIC OPC unit provides regular and cost-efficient particle size distribution measurements of accumulation mode particles in the UT/LMS. In April 2010, the new OPC unit was installed for the first time onboard the Lufthansa Airbus A340 600 (D-AIHE) for the measurement of the volcanic ash cloud from the Eyjafjallajökull eruption (April to May 2010). Since June 2010 the OPC unit measures on usually four intercontinental flights per month the UT/LMS particle size distribution in the particle size range 125 to 1300 nm particle diameter. As the data acquisition stores the scattering raw signal and all housekeeping data as well, during the post flight data analysis the temporal- and size channel resolution can be flexible set. Within this work the data were analyzed with 32 size channels and 300 seconds. As aircraft-borne measurements are always time-consuming, the development of the OPC unit and the analysis routine, as well as its characterization and certification took more than two thirds of the total working time of this thesis. Therefore, the analysis of the data is limited to the first year of regular measurements until May 2011. Nevertheless, this dataset is sufficient to demonstrate the scientific relevance of these measurements. To validate the OPC data, a comparison to particle size distributions measured from board research aircraft was carried out. The analysis of the volcanic ash flights in April and May 2010 showed strongly enhanced particle mass concentrations inside the plumes and agreed in some regions very well to the particle mass concentration predicted by a dispersion model. A further case study shows the occurrence of a surprising large (1000 km) and high concentrated pollution plume over eastern Asia close to Osaka (Japan). Inside the plume the highest particle number- and mass concentrations measured with the OPC unit in the analysis period were observed (except volcanic ash flights). A detailed analysis of the in parallel measured trace gasses as well as meteorological- and LIDAR data showed, the observed plume originate from biomass burning and industrial emissions in eastern China. A third case study gives a first attempt of a mass closure/validation between the particle masses derived by the CARIBIC OPC unit and the CARIBIC impactor particle samples. First statistical analyses to the vertical, meridional, and seasonal variation of the accumulation mode particle size distribution and therefrom derived parameter indicate a stratospheric vertical increasing gradient for the particle number- and mass concentration. In general in the mid-latitude LMS the concentration of accumulation mode particles was found to be on average 120% higher than in the mid-latitude UT. The mid-latitude LMS particle size distribution shows a seasonal variation with on average 120% higher concentrations during spring compared to fall. This results can be explained with general dynamics in the stratosphere (Brewer-Dobson Circulation) and in the tropopause region (stratosphere-troposphere-exchange, STE). An anti-correlation of gaseous mercury to the stratospheric particle surface area concentration (R²=0.97) indicates that most likely stratospheric aerosol particles do act as a sink for gaseous mercury. Finally, two comparisons of the OPC data to data from satellite remote sensing and a global aerosol model underline the OPC potential and the benefits of creating an in situ measured reference dataset. / Um die Rolle von Aerosolpartikeln beim Strahlungsantrieb und der heterogenen chemischen Prozessen in der oberen Troposphäre und untersten Stratosphäre (OT/US) verstehen zu können, ist es unabdingbar die Partikelgrößenverteilung zu kennen. Messungen der Partikelgrößenverteilung in dieser Region sind allerdings aufwendig. Der Einsatz von Forschungsflugzeugen ist teuer und deshalb zeitlich und räumlich nur begrenzt. Satellitenmessungen bieten zwar eine gute zeitliche und räumliche (horizontal) Abdeckung, aber nur eine begrenzte vertikale Auflösung. Weiterhin können bisherige Satellitenmessungen die Partikelgrößenverteilung nicht auflösen. Im Rahmen dieser Arbeit wurde deshalb ein optischer Partikelzähler (OPC) Messeinschub für den Einsatz an Bord eines Langstrecken-Passagierflugzeugs aufgebaut (CARIBIC Projekt, www.caribic-atmospheric.com). Mit diesem Messeinschub kann regelmäßig und kosteneffizient die Partikelgrößenverteilung des Akkumulationsmodes in der OT/US gemessen werden. Im April 2010 wurde der neue OPC Einschub erstmals an Bord des Lufthansa Airbus A340-600 (D-AIHE) installiert um die Vulkanasche der Eyjafjallajökull Eruption (April bis Mai 2010) zu messen. Seit Juni 2010 misst der OPC Einschub auf durchschnittlich vier Interkontinentalflügen pro Monat die Partikelgrößenverteilung der OT/US im Größenbereich zwischen 125 und 1300 nm Partikeldurchmesser. Während des Fluges speichert die Datenerfassung alle Rohsignale ab und ermöglicht dadurch eine nutzerspezifische Datenauswertung nach dem Flug (z. B. Anzahl der Größenkanäle oder Zeitauflösung). Im Rahmen dieser Arbeit wurden die Daten mit 32 Größenkanälen und 300 Sekunden analysiert. Da fluggetragene Messungen immer sehr aufwendig sind, beanspruchte die Entwicklung des OPC Einschubs und des Analysealgorithmus, sowie die Charakterisierung und Zertifizierung mehr als zwei Drittel der Gesamtarbeitszeit dieser Arbeit. Daher ist die Analyse der Messdaten auf das erste Jahr der regulären Messungen bis Mai 2011 beschränkt. Dennoch ist dieser Datensatz geeignet um die wissenschaftliche Relevanz dieser Messungen zu demonstrieren. Um die OPC-Daten zu validieren, wurde ein Vergleich mit bisherigen OPC Messungen von Bord Forschungsflugzeugen durchgeführt. Die Analyse der Vulkanascheflüge im April und Mai 2010 zeigte in der Abluftfahne stark erhöhte Partikelmassekonzentrationen, welche in einigen Vergleichsregionen sehr gut mit der Vorhersage eines Disperionsmodells übereinstimmten. Eine weitere Fallstudie zeigt das Auftreten einer überraschend großen (1000 km) und hoch konzentrierten Abluftfahne über Ostasien nahe Osaka (Japan). In der Abluftfahne wurde die im Analysezeitraum höchste mit dem CARIBIC OPC gemessene Partikelanzahl- und Massenkonzentration beobachtet (ausgenommen Vulkanascheflüge). Eine detaillierte Analyse der parallel gemessenen Spurengase, sowie meteorologischer Daten und LIDAR Profile zeigte, dass die beobachtete Abluftfahne eine Mischung aus Biomasseverbrennungs- und Industrieabgasen aus Ost-China war. Eine dritte Fallstudie stellt einen ersten Versuch einer Massenschließung/Validierung zwischen der aus den CARIBIC OPC-Daten abgeleiteten Partikelmasse und der Partikelmasse aus CARIBIC Impaktorproben dar. Erste statistische Analysen zur vertikalen, meridionalen und saisonalen Variabilität der Partikelgrößenverteilung im Akkumulationsmode und daraus abgeleiteten Parametern zeigen einen vertikal ansteigenden Gradienten für die Partikelanzahl- und Massenkonzentration. Generell war in der US der mittleren Breiten die Konzentration von Akkumulationsmode Partikeln im Mittel um 120% höher als in der OT der mittleren Breiten. Weiterhin wurde in der US der mittleren Breiten eine jahreszeitliche Schwankung gefunden. Im Frühling war die mit dem OPC gemessene Partikelkonzentrationen im Mittel um 120% höher als im Herbst. Diese Befunde lassen sich mit der atmosphärischen Dynamik in der Stratosphäre (Brewer-Dobson Zirkulation) und in der Tropopausenregion (Stratosphäre-Troposphäre-Austauschprozesse) erklären. Eine gefundene negative Korrelation von gasförmigen Quecksilber mit der stratosphärischen Partikeloberflächenkonzentration (R²=0.97) ist ein starker Indikator dafür, dass in der US Aerosolpartikel eine Senke für gasförmiges Quecksilber darstellen. Zum Abschluss unterstreichen zwei Vergleiche der OPC-Daten mit Satellitenmessungen und Ergebnissen eines globalen Aerosolmodels das Potential und den Nutzen der CARIBIC OPC Daten als in-situ gemessenen Referenzdatensatz.

<p>The Earth–atmosphere energy balance is dictated by incoming solar radiation and outgoing thermal radiation with greenhouse gases (GHG) and aerosols playing a major role in this effect. The atmospheric abundance and properties of airborne particles and gases lead to the redistribution of radiative energy, resulting in a warming or cooling effect. However, the extent of this effect remains to be insufficiently constrained. Improved quantification and characterization of GHG and aerosols are important requirements to inform current climate models. High-precision instrumentation and thoughtful experimental strategies are necessary to yield various analytical measurement datasets, despite complex meteorological and environmental conditions. This dissertation focuses on the assessment of CO₂and atmospheric particles from aircraft-based measurements enabling representative and spatially sampling of local regions of interest.</p> <p>Chapter 1 provides introductory discussion on the atmospheric implication of GHG and aerosols on the climate and related uncertainties. Chapter 2 summarizes the employed experimental techniques for quantification of GHG and characterization of atmospheric particles. We relied on an aircraft platform equipped with an air turbulence probe for 3D wind vector calculation and a high-precision cavity ring-down spectrometer for the quantification of ambient CO₂, CH₄, and H2O_<em>v</em>. Furthermore, the simultaneous composition and morphological information of aerosol samples were assessed using complementary chemical imaging techniques. Chemical composition of elements with Z > 23 was determined using computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM/EDX). Scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) was used to determined spatially resolved elemental specific molecular information present in atmospheric particles.</p> <p>Chapter 3 presents our study focused on the characterization of mixed mineral dust and biomass burning (BB) aerosols during an intensive burning event. We identified distinct particle types based on individual elemental contribution pre-, syn-, and post-burning event including highly carbonaceous (54–83%) particles, aged mineral dust (1–6%), and sulfur-containing particles (17–41%). X-ray spectromicroscopy techniques were used to characterize the internal chemical heterogeneity of individual BB particles and the morphology of soot inclusions, as well as changes in the particle organic volume fraction (OVF). An estimation method for particle component masses (i.e., organics, elemental carbon, and inorganics) inferred from STXM measurements was used to determine quantitative mixing state metrics based on entropy-derived diversity measures for particles acquired at different periods of the BB event. In general, there was a small difference in the particle-specific diversity among the samples (<em>D</em>_<em>α</em> = 1.3–1.8). However, the disparity from the bulk population diversity observed during the intense periods was found to have high values of <em>D</em>_<em>γ</em> = 2.5–2.9, while particles collected outside of the burning event displayed lower bulk diversity of <em>D</em>_<em>γ</em> = 1.5–2.0. Quantitative methods obtained from chemical imaging measurements presented here will serve to accurately characterize the evolution of mixed BB aerosols within urban environments.</p> <p>Chapter 4 follows the investigation of the physicochemical properties of atmospheric particles collected onboard a research aircraft flown over the Azores using offline spectromicroscopy techniques. Particles were collected within the marine boundary layer (MBL) and free troposphere (FT) comparing samples after long-range atmospheric transport episodes facilitated by dry intrusion (DI) events. The quantification of the OVF of individual particles derived from X-ray spectromicroscopy, which relates to the multi-component internal composition of individual particles, showed a factor of 2.06±0.16 and 1.11±0.04 increase in the MBL and FT, respectively, among DI samples. We show that supplying particle OVF into the <em>κ</em>-Köhler equation can be used as a good approximation of field-measured <em>in situ</em> CCN concentrations. We also report changes in the <em>κ</em> values in the MBL from <em>κ</em>_{MBL, non-DI} = 0.48 to <em>κ</em>_{MBL, DI} = 0.41, while changes in the FT result in <em>κ</em>_{FT, non-D}_I = 0.36 to <em>κ</em>_{FT, DI} = 0.33, which is consistent with enhancements in OVF followed by the DI episodes. Our observations suggest that the entrainment of particles from long-range continental sources alters the mixing state population and CCN properties of aerosol in the region.</p> <p>Chapter 5 discusses the identification and characterization of fine-mode primary biogenic atmospheric particles (PBAP) from the harvesting of crops. Particle samples were analyzed using complementary chemical imaging techniques to apportion the particle-type population based on their size, morphology, and composition. The contribution of PBAP in the size range of 0.15−1.25 μm is estimated to be 10−12% of ∼39,000 analyzed particles. In addition, particle viscosity and phase state were inferred with X-ray spectromicroscopic analysis has shown that the fine-mode organic particles collected are viscous/semisolid (10²−10¹² Pa s) while the majority of PBAP fragments are solid (>10¹²Pa s). The observation of submicrometer, solid carbonaceous fragments of biogenic origin have implications for the regional CCN and ice nuclei budget. Therefore, the seasonal harvesting of crops may play an important, yet unrecognized, role in regional cloud formation and climate.</p> <p>Chapter 6  explores the measurements and quantification of latent heat, sensible heat, and CO₂ fluxes among different land covers in the surrounding area of urban regions using airborne flux techniques. Cities account for the majority of the global CO₂ emissions due to the consumption of energy, resources, infrastructure, and transportation demands. Accordingly, the accurate quantification of these emissions, with exceptional precision, is necessary so that progress towards emission reduction can be monitored. However, a major challenge in quantifying urban emission estimates arises from accurate background emission definitions and apportionment of emission sources in complex urban environments. Airborne eddy covariance measurements were performed to quantify the bidirectional exchange of latent heat, sensible heat, and CO₂ fluxes in the upwind region of Indianapolis within an active biosphere. Here, we observed differences in fluxes across different days and land covers (e.g., corn, soybean, and forests) allowing us to understand the impact of seasonal variability in urban emissions during the full growing season. These experiments illustrate the capability of a research aircraft to perform technically challenging near-direct measurements of atmosphere–surface exchange over local and regional scales.</p> <p>Chapter 7 presents a new method to spatially allocate airborne mass balance CO₂ emissions. We performed seven aircraft measurements downwind of New York City (NYC) quantifying CO₂ emissions during the non-growing seasons of 2018–2020. A series of prior inventories and footprint transport models were used to account for flux contribution outside the area of interest and attribute emission sources within policy-relevant boundaries of the five boroughs encompassing NYC and then employ the modeled enhancement fraction (Φ) to the bulk emission observations from the mass balance approach. Here, we calculated a campaign-averaged source apportioned mass balance CO₂ emission rate of 56±24 kmol/s. The performance and accuracy of this approach were evaluated against other published works including inventory scaling and inverse modeling, yielding a difference of 5.1% with respect to the average emission rate reported by the two complementary approaches. Utilizing the ensemble of emissions inventories and transport models, we also evaluated the overall sources of variability induced by the prior (1.7%), the transport (4.2%), and the daily variability (42.0%). This approach provides a solution to interpreting aircraft-based mass balance results in complex emission environments.</p> <p>Chapter 8 concludes with a brief discussion of technological advances and research outlooks for X-ray spectromicroscopy analysis on atmospheric particles and the quantification of GHG. Opportunities for future applications and novel development of CCSEM/EDX and STXM/NEXAFS to substantially extend the instrument capabilities and improve our understanding of the physicochemical properties of individual atmospheric particles. Chapter 8 also discusses recent developments in satellite-based CO₂ monitoring to complement direct airborne observations. In recent years, significant progress has been made in satellite-based measurements of CO₂ to reveal the spatio-temporal variation in atmospheric CO₂ concentration. The column-averaged dry air CO₂ mole have reached an accuracy of ~1 ppm with a spatial resolution of less than 4 km. Furthermore, column-averaged retrievals can be used to detect and estimate the surface CO₂ fluxes in an active biosphere, quantify anthropogenic emissions over megacities, and monitor the transport of fossil fuel plumes across different continents and seasons.</p>