An aerosol module is developed and coupled to a regional climate model to investigate the direct and indirect effect of anthropogenic aerosols (sulfate and carbonaceous aerosols) on climate with a focus on precipitation over East Asia. This fully coupled regional climate-chemistry-aerosol model is capable of understanding the interactions between the aerosol perturbation and climate change. The simulated aerosol spatial and seasonal distributions are generally consistent with the observations. The magnitude of the simulated total aerosol concentration and optical depth is about 2/3 of the observed value, suggesting the estimated climatic effects in this work are reasonable and conservative. With the implementation of various aerosol effect, i.e., direct, semi-direct, 1st and 2nd indirect effect, the aerosols?impacts on climate are assessed over the region. The direct, semi-direct and 1st indirect effects generate a negative surface solar forcing, leading to a surface cooling, and the semi-direct effect also heats the atmosphere by BC absorption. This, in turn, increases the atmospheric stability and tends to inhibit the precipitation. The precipitation reduction is largest in the fall and winter, up to -10% with the inclusion of both direct and 1st indirect effects. The 2nd indirect effect using BH94 scheme produces a comparable magnitude in long-wave heating as the solar cooling, leading to the nighttime temperature warming of 0.5K, and a reduction in the diurnal temperature range. The precipitation reduction from the 2nd indirect effect strongly depends on the auto-conversion scheme, with about -30% in the fall and winter, and -15% in the spring and summer using BH94 scheme, while less than -5% using TC80 scheme. By allowing the feedbacks between aerosols and climate, the coupled model generally decreases the discrepancies between the model-simulated and observed precipitation and aerosols over the region. The EOF analysis of the climatological precipitation from last century over East Asia shows a decreasing mode in the EOF leading modes in the fall and winter, and is generally geographically consistent with the distribution of the model simulated precipitation reduction from anthropogenic aerosols.

The current dissertation is motivated by the need for an improved understanding of aerosol water interactions both in subsaturated and supersaturated atmospheric conditions with a strong emphasis on air pollution and climate change modeling. A cloud droplet formation parameterization was developed to i) predict droplet formation from a lognormal representation of aerosol size distribution and composition, and, ii) include a size-dependant mass transfer coefficient for the growth of water droplets which explicitly accounts for the impact of organics on droplet growth kinetics. The parameterization unravels most of the physics of droplet formation and is in remarkable agreement with detailed numerical parcel model simulations, even for low values of the accommodation coefficient. The parameterization offers a much needed rigorous and computationally inexpensive framework for directly linking complex chemical effects on aerosol activation in global climate models. The new aerosol activation parameterization was also tested against observations from highly polluted clouds (within the vicinity of power plant plumes). Remarkable closure was achieved (much less than the 20% measurement uncertainty). The error in predicted cloud droplet concentration was mostly sensitive to updraft velocity. Optimal closure is obtained if the water vapor uptake coefficient is equal to 0.06. These findings can serve as much needed constraints in modeling of aerosol-cloud interactions in the North America. Aerosol water interactions in ambient relative humidities less than 100% were studied using a thermodynamic equilibrium model for inorganic aerosol and a three dimensional air quality model. We developed a new thermodynamic equilibrium model, ISORROPIA-II, which predicts the partitioning of semi-volatiles and the phase state of K+/Ca2+/Mg2+/NH4+/Na+/SO42-/NO3-/Cl-/H2O aerosols. A comprehensive evaluation of its performance was conducted against the thermodynamic module SCAPE2 over a wide range of atmospherically relevant conditions. Based on its computational rigor and performance, ISORROPIA-II appears to be a highly attractive alternative for use in large scale air quality and atmospheric transport models. The new equilibrium model was also used to thermodynamically characterize aerosols measured at a highly polluted area. In the ammonia-rich environment of Mexico City, nitrate and chloride primarily partition in the aerosol phase with a 20-min equilibrium timescale; PM2.5 is insensitive to changes in ammonia but is to acidic semivolatile species. When RH is below 50%, predictions improve substantially if the aerosol follows a deliquescent behavior. The impact of including crustal species (Ca2+, K+, M2+) in equilibrium calculations within a three dimensional air quality model was also studied. A significant change in aerosol water (-19.8%) and ammonium (-27.5%) concentrations was predicted when crustals are explicitly included in the calculations even though they contributed, on average, only a few percent of the total PM2.5 mass, highlighting the need for comprehensive thermodynamic calculations in the presence of dust.

Secondary organic aerosols (SOA) comprise a substantial fraction of the total global aerosol budget. While laboratory studies involving smog chambers have advanced our understanding of the formation mechanisms responsible for SOA, our knowledge of the processes leading to SOA production under ambient gaseous and particulate concentrations as well as the impact these aerosol types have on climate is poorly understood. Although the majority of atmospheric aerosols scatter radiation either directly or indirectly by serving as cloud condensation nuclei, soot is thought to have a significant warming effect through absorption. Like inorganic salts, soot may undergo atmospheric transformation through the vapor condensation of non-volatile gaseous species which will alter both its chemical and physical properties. Typical smog chamber studies investigating the formation and growth of SOA as well as the soot aging process are temporally limited by the initial gaseous concentrations injected into the chamber environment. Furthermore, data interpretation from such experiments is generally restricted to the singular gaseous species under investigation. This dissertation discusses the use of a new aerosol chamber designed to study the formation and growth of SOA and soot aging under atmospherically relevant conditions. The Ambient Aerosol Chamber for Evolution Studies (AACES) was deployed at three field sites where size and hygroscopic growth factor (HGF) of ammonium sulfate seed particles was monitored over time to examine the formation and growth of SOA. Similar studies investigating the soot aging process were also conducted in Houston, TX. It is shown that during the ambient growth of ammonium sulfate seed particles, as particle size increases, hygroscopic growth factors decrease considerably resulting in a significant organic mass fraction in the particle phase concluding an experiment. Observations of soot aging show an increase in measured size, HGF, mass and single scattering albedo. Ambient growth rate comparisons with chamber growth yielded similar trends verifying the use of AACES to study aerosol aging. Based on the results from this study, it is recommended that AACES be employed in future studies involving the production and growth of SOA and soot aging under ambient conditions in order to bridge the gaps in our current scientific knowledge.

Atmospheric particles can affect climate directly, by scattering solar radiation, or indirectly, by acting as the seed upon which cloud droplets form. These clouds can then cool the earth's surface by reflecting incoming sunlight. In order to constrain the large uncertainties in predicting the ultimate effect of aerosol on climate, the sources of atmospheric particles and their subsequent ability to turn into cloud droplets needs to be better understood. This thesis addresses two parts of this issue: the sources of Arctic aerosol and the hygroscopicity of continental organic aerosol. Small particles were observed in Baffin Bay during September 2008 that coincided with high atmospheric and ocean surface dimethyl sulphide (DMS) concentrations suggesting that the aerosol formed from oceanic sources. An aerosol microphysics box model confirmed that local DMS could have produced the observed particles. In addition, the particle chemical composition was measured using aerosol mass spectrometry in the central Arctic Ocean in August 2008 and particles were found to be 43% organic and 46% sulphate. Factor analysis further apportioned the aerosol mass to marine biogenic and continental sources 33% and 36% of the time, respectively, with the source of the remaining mass unidentified. The second part of the study parameterises the hygroscopicity of the ambient organic aerosol fraction (κorg) at Egbert, Ontario and Whistler, British Columbia. This was done using two methods: 1) by assuming that the oxygenated organic component was hygroscopic and that the unoxygenated organic component was non-hygroscopic, κ of the oxygenated component was found to be 0.22 ± 0.04, and 2) by assuming that κorg varied linearly with the atomic oxygen to atomic carbon ratio, it could be parameterised as κorg = (0.29 ± 0.05) × (O/C). Calculations predict that knowing κorg is important in urban, semi-urban, and remote locations whenever the inorganic mass fraction is low.

Atmospheric particles can affect climate directly, by scattering solar radiation, or indirectly, by acting as the seed upon which cloud droplets form. These clouds can then cool the earth's surface by reflecting incoming sunlight. In order to constrain the large uncertainties in predicting the ultimate effect of aerosol on climate, the sources of atmospheric particles and their subsequent ability to turn into cloud droplets needs to be better understood. This thesis addresses two parts of this issue: the sources of Arctic aerosol and the hygroscopicity of continental organic aerosol. Small particles were observed in Baffin Bay during September 2008 that coincided with high atmospheric and ocean surface dimethyl sulphide (DMS) concentrations suggesting that the aerosol formed from oceanic sources. An aerosol microphysics box model confirmed that local DMS could have produced the observed particles. In addition, the particle chemical composition was measured using aerosol mass spectrometry in the central Arctic Ocean in August 2008 and particles were found to be 43% organic and 46% sulphate. Factor analysis further apportioned the aerosol mass to marine biogenic and continental sources 33% and 36% of the time, respectively, with the source of the remaining mass unidentified. The second part of the study parameterises the hygroscopicity of the ambient organic aerosol fraction (κorg) at Egbert, Ontario and Whistler, British Columbia. This was done using two methods: 1) by assuming that the oxygenated organic component was hygroscopic and that the unoxygenated organic component was non-hygroscopic, κ of the oxygenated component was found to be 0.22 ± 0.04, and 2) by assuming that κorg varied linearly with the atomic oxygen to atomic carbon ratio, it could be parameterised as κorg = (0.29 ± 0.05) × (O/C). Calculations predict that knowing κorg is important in urban, semi-urban, and remote locations whenever the inorganic mass fraction is low.

Zugl.: Hamburg, Univ., Diss.

Die Wechselwirkung von Aerosol und Strahlung in der Atmosphäre beeinflusst stark die Energiebilanz der Erde. Durch die großräumige Erfassung der horizontalen und vertikalen Verteilung von Aerosoleigenschaften in der Atmosphäre liefern Fernerkundungstechniken einen wichtigen Beitrag zu unserem Verständnis des Klimasystems. Genaue Beobachtungen durch langfristige operationelle Satellitenmissionen und zuverlässige Referenzmessungen vom Boden aus sind auch für die Ableitung und Verbesserung satelliten- und modellgestützter Aerosoldatensätze unerlässlich. Dies gilt insbesondere über dem Ozean. Mittels Fernerkundungsmethoden werden in dieser Dissertation bestimmte optische Eigenschaften von Aerosol und dessen Strahlungseffekt untersucht. Ein Teil der Datengrundlage hierfür wurde auf fünf Fahrten mit dem Forschungsschiff Polarstern mittels eines multispektralen Schattenbandradiometers erhoben. Anhand dieser Daten werden die aus theoretischen Betrachtungen abgeleitete Unsicherheit der Irradianzmessung von etwa 2 % anhand eines Vergleichs mit Sonnenphotometerbeobachtungen an Land und auf dem Schiff bestätigt. Unter Verwendung Schiffs-gestützter Referenzdaten werden im Rahmen dieser Dissertation mehrere weitere Aerosoldatensätze evaluiert. Für zwei satellitengestützte Datensätze können die erwarteten Fehlergrenzen bestätigt und die vom Aerosoltyp abhängigen Einschränkungen aufgrund von Modellannahmen diskutiert werden. Darüber hinaus werden die optischen Eigenschaften von Aerosol in der CAMS-Reanalyse betrachtet. Dabei findet sich die größte Diskrepanz in der Aerosolabsorption, die von der CAMS-Reanalyse um etwa 30 % überschätzt wird. Schließlich wird der Strahlungseffekt von Aerosol für die Region Deutschland und das Jahr 2015 unter unbewölkten Bedingungen mit zwei komplementären Ansätzen untersucht. Hierbei werden Messungen der solaren Einstrahlung an 25 Stationen des Beobachtungsnetzes des Deutschen Wetterdienstes als Datengrundlage verwendet. Einerseits wird ein Ensemble von empirischen Modellen verwendet, um die direkte Strahlungswirkung von Aerosol am Boden mithilfe einer Fehlerminimierung zu bestimmen. Die zugrundeliegenden Annahmen über Aerosol- und atmosphärische Eigenschaften in diesen Modellen werden kritisch analysiert und diskutiert. Im zweiten Ansatz werden explizite Strahlungstransfersimulationen des Strahlungseffekts unter Verwendung der CAMS-Reanalyse genutzt. Weiterhin wird die Sensitivität der Simulationen auf Unsicherheiten in den Eingangsgrößen untersucht, und damit die resultierende Unsicherheit im Strahlungseffekt abgeschätzt. Nach Korrektur von systematischen Abweichungen in der CAMS-Reanalyse hat Aerosol im Jahre 2015 einen mittleren abkühlenden Strahlungseffekt von -10.6 Wm-2 am Boden in Deutschland. / The interaction of aerosol and radiation in the atmosphere exerts a strong influence on the Earth's energy balance. Remote sensing techniques provide an important contribution to our understanding of the climate system, by observing the horizontal and vertical distribution of aerosol properties in the atmosphere on a large scale. Accurate observations from long-term operational satellite missions and reliable ground-based reference measurements are essential for deriving and improving satellite- and model-based aerosol data sets. This is especially true over the ocean. In this dissertation, certain optical properties of aerosol particles and their radiation effect are investigated using remote sensing methods. Parts of the considered data basis were collected on five cruises with the research vessel Polarstern using a multispectral shadow-band radiometer. This unique data set contributes to the global available reference observations over the ocean by partially filling known gaps. On this database, an algorithm to evaluate shadow-band radiometer observations for the determination of spectral irradiance and optical properties of aerosol has been advanced. The basis algorithm was developed by the author as part of his master's thesis. The uncertainty of the irradiance measurement of about 2 % derived from theoretical considerations is validated by comparison with sun photometer observations on land and on ship. Using ship-borne reference data, several aerosol products are evaluated as part of this dissertation. For two satellite-based datasets, the expected error bounds has been confirmed and the aerosol-type dependent limitations due to model assumptions in the satellite retrievals are discussed. Furthermore, the optical properties of aerosol considered in the CAMS reanalysis are evaluated. The largest discrepancy is found in the aerosol absorption, which is overestimated by the CAMS reanalysis by about 30 %. Finally, the radiative effect of aerosol is investigated for the region of Germany and the year 2015 under cloud-free conditions using two complementary approaches. Here, measurements of solar irradiance at 25 stations of the observation network of the German Weather Service are used as a data basis. In the first approach, an ensemble of empirical models is used to determine the direct radiative effect of aerosols on the ground using error minimization. The underlying assumptions about aerosol and atmospheric properties in these models are critically analysed and discussed. The second approach quantifies the radiative effect by applying explicit radiative transfer simulations using CAMS reanalysis. The uncertainty in the radiative effect is estimated by studying the sensitivity of the simulations to uncertainties in the input variables. After correcting for systematic deviations in the CAMS reanalysis, aerosol has a cooling radiative effect of -10.6 Wm-2 on the ground in Germany in the annual mean of 2015.

Phase transitions and other intrinsic properties (shape, size, architecture) of molecularly structured aerosol particles are important for understanding their role in planetary atmospheres and for technical applications. By combining bath gas cooling with time resolved mid-infrared spectroscopy and modeling, information is obtained on dynamic processes and intrinsic properties of fluoroform and ethane aerosol particles. The distinct infrared spectral features of fluoroform aerosol particles make it a particularly suitable model system. Homogeneous crystallization rates of the sub-micron sized aerosol particles are determined (JV = 10⁸ - 10¹⁰ cm-³s-¹ or JS = 10³ – 10⁵ cm-²s-¹ at a temperature of T = 78 K), and the controversial question regarding volume versus surface nucleation in freezing aerosols is addressed. It is demonstrated that current state of the art measurements of droplet ensembles cannot distinguish between the two mechanisms due to inherent experimental uncertainties. The evolution of particle shape from spherical supercooled droplets to cube-like crystalline particles and eventually to elongated crystalline particles is recorded and analyzed in detail with the help of vibrational exciton model calculations. Phase behaviour of pure ethane aerosols and ethane aerosols formed in the presence of other ice nuclei under conditions mimicking Titan’s atmosphere provide evidence for the formation of supercooled liquid ethane aerosol droplets, which subsequently crystallize. The observed homogeneous freezing rates (JV = 10⁷ – 10⁹ cm-³s-¹) imply that supercooled ethane could play a similar role in ethane rich regions of Titan’s atmosphere as supercooled water does in the Earth’s atmosphere.

Phase transitions and other intrinsic properties (shape, size, architecture) of molecularly structured aerosol particles are important for understanding their role in planetary atmospheres and for technical applications. By combining bath gas cooling with time resolved mid-infrared spectroscopy and modeling, information is obtained on dynamic processes and intrinsic properties of fluoroform and ethane aerosol particles. The distinct infrared spectral features of fluoroform aerosol particles make it a particularly suitable model system. Homogeneous crystallization rates of the sub-micron sized aerosol particles are determined (JV = 10⁸ - 10¹⁰ cm-³s-¹ or JS = 10³ – 10⁵ cm-²s-¹ at a temperature of T = 78 K), and the controversial question regarding volume versus surface nucleation in freezing aerosols is addressed. It is demonstrated that current state of the art measurements of droplet ensembles cannot distinguish between the two mechanisms due to inherent experimental uncertainties. The evolution of particle shape from spherical supercooled droplets to cube-like crystalline particles and eventually to elongated crystalline particles is recorded and analyzed in detail with the help of vibrational exciton model calculations. Phase behaviour of pure ethane aerosols and ethane aerosols formed in the presence of other ice nuclei under conditions mimicking Titan’s atmosphere provide evidence for the formation of supercooled liquid ethane aerosol droplets, which subsequently crystallize. The observed homogeneous freezing rates (JV = 10⁷ – 10⁹ cm-³s-¹) imply that supercooled ethane could play a similar role in ethane rich regions of Titan’s atmosphere as supercooled water does in the Earth’s atmosphere.

Phase transitions and other intrinsic properties (shape, size, architecture) of molecularly structured aerosol particles are important for understanding their role in planetary atmospheres and for technical applications. By combining bath gas cooling with time resolved mid-infrared spectroscopy and modeling, information is obtained on dynamic processes and intrinsic properties of fluoroform and ethane aerosol particles. The distinct infrared spectral features of fluoroform aerosol particles make it a particularly suitable model system. Homogeneous crystallization rates of the sub-micron sized aerosol particles are determined (JV = 10⁸ - 10¹⁰ cm-³s-¹ or JS = 10³ – 10⁵ cm-²s-¹ at a temperature of T = 78 K), and the controversial question regarding volume versus surface nucleation in freezing aerosols is addressed. It is demonstrated that current state of the art measurements of droplet ensembles cannot distinguish between the two mechanisms due to inherent experimental uncertainties. The evolution of particle shape from spherical supercooled droplets to cube-like crystalline particles and eventually to elongated crystalline particles is recorded and analyzed in detail with the help of vibrational exciton model calculations. Phase behaviour of pure ethane aerosols and ethane aerosols formed in the presence of other ice nuclei under conditions mimicking Titan’s atmosphere provide evidence for the formation of supercooled liquid ethane aerosol droplets, which subsequently crystallize. The observed homogeneous freezing rates (JV = 10⁷ – 10⁹ cm-³s-¹) imply that supercooled ethane could play a similar role in ethane rich regions of Titan’s atmosphere as supercooled water does in the Earth’s atmosphere. / Science, Faculty of / Chemistry, Department of / Graduate