An optical microscope coupled to a flow cell was used to investigate ice nucleation on five atmospherically relevant mineral dusts at temperatures ranging from 233 to 247 K. Kaolinite and muscovite particles were found to be efficient ice nuclei in the deposition mode, requiring relative humidities with respect to ice (RHi) below 112% in order to initiate ice crystal formation. Quartz and calcite particles, by contrast, were poor ice nuclei, requiring relative humidities close to water saturation before ice crystals would form. Montmorillonite particles were efficient ice nuclei at temperatures below 241 K, but poor ice nuclei at higher temperatures. In several cases, there was a lack of quantitative agreement between these data and previously published work. This can be explained by several factors including mineral source, particle size, observation time and surface area available for nucleation. Heterogeneous nucleation rates (Jhet) were calculated from the onset data. Jhet values ranged from 60 to 1100 cm-²s-¹ for the five minerals studied. These values were then used to calculate contact angles (θ) for each mineral according to classical nucleation theory. The contact angles measured for kaolinite and muscovite ranged from 6 to 12º; for quartz and calcite the contact angles were much higher, ranging from 25 to 27º. The contact angles measured for montmorillonite were less than 15º at temperatures below 241 K, and above 20º at higher temperatures. The reported Jhet and θ values may allow for a more direct comparison between laboratory studies and can be used when modeling ice cloud formation in the atmosphere. The roles of H₂SO₄ and (NH4)₂SO₄ coatings on the ice nucleating properties of kaolinite were also investigated. Onset data was collected for H₂SO₄ coated and (NH4)₂SO₄ coated kaolinite particles at temperatures ranging from 233 to 247 K. In contrast to uncoated kaolinite particles, which were effective ice nuclei, H₂SO₄ coated particles were found to be poor ice nuclei, requiring relative humidities close to water saturation before nucleating ice at all temperatures studied. (NH4)₂SO₄ coated particles were poor ice nuclei at 245 K, but effective ice nuclei at 236 K.

An optical microscope coupled to a flow cell was used to investigate ice nucleation on five atmospherically relevant mineral dusts at temperatures ranging from 233 to 247 K. Kaolinite and muscovite particles were found to be efficient ice nuclei in the deposition mode, requiring relative humidities with respect to ice (RHi) below 112% in order to initiate ice crystal formation. Quartz and calcite particles, by contrast, were poor ice nuclei, requiring relative humidities close to water saturation before ice crystals would form. Montmorillonite particles were efficient ice nuclei at temperatures below 241 K, but poor ice nuclei at higher temperatures. In several cases, there was a lack of quantitative agreement between these data and previously published work. This can be explained by several factors including mineral source, particle size, observation time and surface area available for nucleation. Heterogeneous nucleation rates (Jhet) were calculated from the onset data. Jhet values ranged from 60 to 1100 cm-²s-¹ for the five minerals studied. These values were then used to calculate contact angles (θ) for each mineral according to classical nucleation theory. The contact angles measured for kaolinite and muscovite ranged from 6 to 12º; for quartz and calcite the contact angles were much higher, ranging from 25 to 27º. The contact angles measured for montmorillonite were less than 15º at temperatures below 241 K, and above 20º at higher temperatures. The reported Jhet and θ values may allow for a more direct comparison between laboratory studies and can be used when modeling ice cloud formation in the atmosphere. The roles of H₂SO₄ and (NH4)₂SO₄ coatings on the ice nucleating properties of kaolinite were also investigated. Onset data was collected for H₂SO₄ coated and (NH4)₂SO₄ coated kaolinite particles at temperatures ranging from 233 to 247 K. In contrast to uncoated kaolinite particles, which were effective ice nuclei, H₂SO₄ coated particles were found to be poor ice nuclei, requiring relative humidities close to water saturation before nucleating ice at all temperatures studied. (NH4)₂SO₄ coated particles were poor ice nuclei at 245 K, but effective ice nuclei at 236 K.

The development of new analytical techniques is one of the driving forces in the advancement of scientific understanding. The measurement of the properties of aerosol particles is an active area of research due to the impact aerosol has on atmospheric processes. Single particle size and composition are key properties that govern many atmospheric processes, but the measurement of these properties is challenging due to the large dynamic range of size and composition that exists in the environment. Mineral dust represents a significant fraction of the global aerosol mass loading and has a profound impact on the earth's radiative budget through the direct interaction with solar and terrestrial radiation, and by affecting microphysical properties of clouds. In addition, mineral dust is involved in the geochemical cycling of many compounds that are vital for the health and vitality of ecosystems. The importance of the chemical and crystallographic properties of a material, or mineral phase, has been highlighted recently. Measurements of the elemental composition of single particles is possible with off-line analysis of dust collected on filters , but mineral phase is usually obtained from X-ray diffraction of bulk samples. These techniques are labour intensive and the lack of ambient measurements is a limiting factor in the development of models that attempt to resolve the complexity of atmospheric processes. Time-of-flight mass spectrometry (TOF-MS) is well suited to on-line single particle composition measurements due its sensitivity and high temporal resolution. Single particle mass spectrometry (SPMS) is a class of TOF-MS technique that is able to identify mineral dust particles from their chemical signature in the mass spectrum. Analysis of refractory mineral dust by mass spectrometry requires laser desorption ionisation (LDI) by high energy pulsed lasers, a process that renders the composition measurement non-quantitative due to incomplete ionisation and matrix effects. Consequently, the identification of mineral phase is not possible because the reproducibility of the measurement is lower than the natural variation between common minerals. This thesis reports the development of a commercially available single particle mass spectrometer for the measurement of the physiochemical properties of mineral dust. The optical particle detection system is improved for the more efficient detection of single particles in the size range relevant to the ambient measurement of mineral dust aerosol, and a model is developed that will aid the further development of particle detection in SPMS. A novel method for the on-line differentiation of mineral phase in single particles is presented which exploits differences in ion arrival times at the TOF-MS detector of a silicate molecular ion species, that arise from the influence of mineral phase on the ion formation process during the LDI process. The efficacy of the technique is demonstrated with the differentiation of mineral phase in laboratory generated mineral dust from clay mineral standards. The deployment of the improved instrument to measure Saharan dust outflow resulted in the first ever on-line identification of the clay mineral fraction in ambient mineral dust.

An optical microscope coupled to a flow cell was used to investigate ice nucleation on five atmospherically relevant mineral dusts at temperatures ranging from 233 to 247 K. Kaolinite and muscovite particles were found to be efficient ice nuclei in the deposition mode, requiring relative humidities with respect to ice (RHi) below 112% in order to initiate ice crystal formation. Quartz and calcite particles, by contrast, were poor ice nuclei, requiring relative humidities close to water saturation before ice crystals would form. Montmorillonite particles were efficient ice nuclei at temperatures below 241 K, but poor ice nuclei at higher temperatures. In several cases, there was a lack of quantitative agreement between these data and previously published work. This can be explained by several factors including mineral source, particle size, observation time and surface area available for nucleation. Heterogeneous nucleation rates (Jhet) were calculated from the onset data. Jhet values ranged from 60 to 1100 cm-²s-¹ for the five minerals studied. These values were then used to calculate contact angles (θ) for each mineral according to classical nucleation theory. The contact angles measured for kaolinite and muscovite ranged from 6 to 12º; for quartz and calcite the contact angles were much higher, ranging from 25 to 27º. The contact angles measured for montmorillonite were less than 15º at temperatures below 241 K, and above 20º at higher temperatures. The reported Jhet and θ values may allow for a more direct comparison between laboratory studies and can be used when modeling ice cloud formation in the atmosphere. The roles of H₂SO₄ and (NH4)₂SO₄ coatings on the ice nucleating properties of kaolinite were also investigated. Onset data was collected for H₂SO₄ coated and (NH4)₂SO₄ coated kaolinite particles at temperatures ranging from 233 to 247 K. In contrast to uncoated kaolinite particles, which were effective ice nuclei, H₂SO₄ coated particles were found to be poor ice nuclei, requiring relative humidities close to water saturation before nucleating ice at all temperatures studied. (NH4)₂SO₄ coated particles were poor ice nuclei at 245 K, but effective ice nuclei at 236 K. / Science, Faculty of / Chemistry, Department of / Graduate

A special challenge posed by mineral dust aerosols is associated with their predominantly nonspherical particle shapes. In the present study, the scattering and radiative properties for nonspherical mineral dust aerosols at violet-to-blue (0.412, 0.441, and 0.470 μm) and red (0.650 μm) wavelengths are investigated. To account for the effect of particle nonsphericity on the optical properties of dust aerosols, the particle shapes for these particles are assumed to be spheroids. A combination of the T-matrix method and an improved geometric optics method is applied to the computation of the single-scattering properties of spheroidal particles with size parameters ranging from the Rayleigh to geometric optics regimes. For comparison, the Mie theory is employed to compute the optical properties of spherical dust particles that have the same volumes as their nonspherical counterparts. The differences between the phase functions of spheroidal and spherical particles lead to quite different lookup tables (LUTs) involved in retrieving dust aerosol properties. Moreover, the applicability of a hybrid approach based on the spheroid model for the phase function and the sphere model for the other phase matrix elements is demonstrated. The present sensitivity study, employing the Moderate Resolution Imaging Spectroradiometer (MODIS) observations and the fundamental principle of the Deep Blue algorithm, illustrates that neglecting the nonsphericity of dust particles leads to an underestimate of retrieved aerosol optical depth at most scattering angles, and an overestimate is noted in some cases. The sensitivity study of the effect of thin cirrus clouds on dust optical depth retrievals is also investigated and quantified from MODIS observations. The importance of identifying thin cirrus clouds in dust optical depth retrievals is demonstrated. This has been undertaken through the comparison of retrieved dust optical depths by using two different LUTs. One is for the dust only atmosphere, and the other is for the atmosphere with overlapping mineral dust and thin cirrus clouds. For simplicity, the optical depth and bulk scattering properties of thin cirrus clouds are prescribed a priori. Under heavy dusty conditions, the errors in the retrieved dust optical depths due to the effect of thin cirrus are comparable to the assumed optical depth of thin cirrus clouds. With the spheroidal and spherical particle shape assumptions for mineral dust aerosols, the effect of particle shapes on dust radiative forcing calculations is estimated based on Fu-Liou radiative transfer model. The effect of particle shapes on dust radiative forcing is illustrated in the following two aspects. First, the effect of particle shapes on the single-scattering properties of dust aerosols and associated dust direct radiative forcing is assessed, without considering the effect on dust optical depth retrievals. Second, the effect of particle shapes on dust direct radiative forcing is further discussed by including the effect of particle nonsphericity on dust optical depth retrievals.

Die vorliegende Arbeit beschäftigt sich mit der Auswertung und den Ergebnissen von Mehrwellenlängen–Polarisations–Ramanlidarmessungen, die im Rahmen des Saharastaubschließungsexperiments Saharan Mineral Dust Experiment (SAMUM) durchgeführt wurden. Das SAMUM–Projekt erstreckte sich über zwei Intensivmesszeiträume im Mai und Juni 2006 in Marokko (SAMUM–1) und im Januar und Februar 2008 auf den Kapverdischen Inseln (SAMUM–2). Desweiteren werden zusätzliche Lidarmessungen besprochen, die im Mai und Juni 2008 auf den Kapverdischen Inseln durchgeführt wurden. Die geometrischen und optischen Eigenschaften der während dieser Experimente mit mehreren hochmodernen Lidargeräten beobachteten Mineralstaub- und Biomassenverbrennungsaerosolschichten werden anhand von Fallstudien und mehrwöchigen, höhenaufgelösten Mittelwerten beschrieben. Zudem werden Kalibrierungen und Korrekturen vorgestellt, die zur Qualitätssicherung der gewonnenen Messdaten durchgeführt wurden. Ein im Rahmen der Arbeit entwickeltes, auf quantitativen Messungen des linearen Partikeldepolarisationsverhältnisses basierendes Verfahren zur höhenaufgelösten Trennung der Anteile von Mineralstaub und Biomassenverbrennungsaerosol an den während SAMUM–2 gemessenen Rücktreu- und Extinktionsprofilen wird vorgestellt und angewandt. Die Auswertung der Mehrwellenlängenlidarmessungen der SAMUM–Kampagnen ermöglichte eine spektral aufgelöste Charakterisierung der optischen Eigenschaften von Saharastaubpartikeln. Besondere Aufmerksamkeit wurde auf die Bestimmung der intensiven Parameter Extinktions–zu–Rückstreuverhältnis (Lidarverhältnis), lineares Partikeldepolarisationsverhältnis sowie Ångströmexponent der Rückstreu- und Extinktionskoeffizienten gelegt. Die im Rahmen von SAMUM bei den Wellenlängen 355, 532 und 1064 nm durchgeführten Lidarmessungen ergaben mittlere Lidarverhältnisse von 55±5 sr für reinen Saharastaub. Während SAMUM wurden außerdem erstmals quantitative Messergebnisse des linearen Partikeldepolarisationsverhältnisses von reinem Saharastaub bei mehreren Wellenlängen gewonnen. Die mittleren Werte dieser Größe lagen bei 0.26±0.06 (355 und 1064 nm), 0.31±0.03 (532 nm) und 0.37±0.07 (710 nm). Diese Erkenntnisse liefern wichtige Informationen für die Auswertung von Messungen mit weniger fortschrittlichen Lidargeräten. Die durch SAMUM gewonnenen Erkenntnisse der optischen Eigenschaften von Mineralstaub erlauben eine eindeutige Identifikation des Staubanteils in Aerosolschichten im Abluftbereich der Wüsten. Zudem wurden Richtgrößen ermittelt, die zur Validierung von Modellen zur Beschreibung von Lichtstreuung an großen, nicht–kugelförmigen Teilchen verwendet werden können. Derartige Streumodelle werden für die Auswertung von Messungen der optischen Eigenschaften von Mineralstaubpartikeln mit passiven Sensoren benötigt und befinden sich zur Zeit eher in einer frühen Entwicklungsphase.

The indirect aerosol effect contributes to major uncertainties in determining the radiation budget of the earth. A large uncertainty is due to the formation of ice clouds onto natural or anthropogenic aerosols. Field studies have shown that mineral type particles are often associated with ice crystals in the mid-upper troposphere and given the long residence time in the atmosphere of dust particles (~2 weeks in the absence of precipitation), their contribution to ice formation processes is not fully defined. In order to probe ice formation onto natural mineral dust in a setting where it could be suspended as aerosol, a new continuous flow diffusion chamber (CFDC) was built. This allowed investigations of the effects of total aerosol surface area and particle size. The CFDC was also used in an international inter-comparison of ice nucleation instrumentation to compare efficiencies of soot, biological aerosol (bacteria) and samples of natural desert dusts from different regions of the world. The laboratory observations were parameterized using nucleation rates (Jhet) and contact angles () as described by classical nucleation theory. For both this experimental technique and a static one developed during the candidate’s Masters degree, mineral dust particulate proved to be the most efficient ice nuclei (IN) activating at RH with respect to ice (RHi) as low as 105% at T = 233 K. The efficiency varied with particle size and aerosol surface area (SA). Large particles or higher SA activated at lower RHi than small particles or lower SA. The static chamber was sensitive to the first ice event out of a large SA and therefore gave true onset RHi, which was lower than the onset defined by the CFDC studies, which was not sensitive to a single ice event. In addition the static chamber used a broader size range of particulate matter, including super micron particles while the CFDC particles sizes were restricted to below 0.5 µm. Soot and organic coated dust particles were inefficient IN compared to pure dust. Soot aerosols showed some efficiency at T < 233K where deposition ice formation was apparent. The hygroscopic organics had intermediate ice activity between dusts and alkyl-organics and soot. Bacteria aerosols were active in the deposition mode for T as high as 247 K. Contact angles () computed for ice germs forming onto natural mineral dust were small, 7<  < 29, at 223 K for RH ranging from ice to water saturation. It was concluded that there is no single value for the onset of ice formation in the atmosphere via deposition freezing. The associated contact angles show that there is a distribution of active sites on IN and that not all active sites have the same affinity for initiation of ice formation even within the same aerosol type. This work provides evidence that deposition mode nucleation can be an alternate pathway to homogeneous nucleation when mineral aerosols are present in the troposphere since the high T - low RH conditions required for deposition mode nucleation are more easily encountered in the atmosphere than the low T - high RH required for homogeneous nucleation.

The potential of atmospheric dust aerosols to modify the Earth's environment and climate has been recognized for some time. However, predicting the diverse impact of dust has several significant challenges. One is to quantify the complex spatial and temporal variability of dust burden in the atmosphere. Another is to quantify the fraction of dust originating from human-made sources. This thesis focuses on the spatiotemporal characterization of sources and dust outbreaks in Central and East Asia by integrating ground-based data, satellite multi-sensor observations, and modeling. A new regional dust modeling system capable of operating over a span of scales was developed. The modeling system consists of a dust module DuMo, which incorporates several dust emission schemes of different complexity, and the PSU/NCAR mesoscale model MM5, which offers a variety of physical parameterizations and flexible nesting capability. The modeling system was used to perform for the first time a comprehensive study of the timing, duration, and intensity of individual dust events in Central and East Asia. Determining the uncertainties caused by the choice of model physics, especially the boundary layer parameterization, and the dust production scheme was the focus of our study. Implications to assessments of the anthropogenic dust fraction in these regions were also addressed. Focusing on Spring 2001, an analysis of routine surface meteorological observations and satellite multi-sensor data was carried out in conjunction with modeling to determine the extent to which to this integrated data set can be used to characterize the spatiotemporal distribution of dust plumes at a range of temporal scales, addressing the active dust sources in China and Mongolia, mid-range transport and trans-Pacific, long-range transport of dust outbreaks on a case-by-case basis. This work demonstrates that adequate and consistent characterization of individual dust events is central to establishing a reliable climatology, ultimately leading to improved assessments of dust impacts on the environment and climate. This will also help to identify the appropriate temporal and spatial scales for adequate intercomparison between model results and observational data as well as for developing an integrated analysis methodology for dust studies.

Little is currently known regarding the nature and consequences of interactions between photoactive surfaces, including mineral dust and ‘urban film’, and gas-phase pollutants in urban environments. In order to address this knowledge gap, this thesis explores the photochemical reactivity of these environmental surfaces in controlled laboratory settings. The photoenhanced ozonation of pyrene, a toxic product of incomplete combustion, proceeds at different rates and via different mechanisms at three model ‘urban film’ surfaces. These results are important because they suggest that the reactivity of a molecule on simplified surfaces may not accurately reflect its reactivity in the real environment. The photooxidation of isopropanol at the surface of TiO2, here used as a proxy for the photoactive component of mineral dust, yields gas-phase acetone. This chemistry is amplified by nitrate, a major surficial component of atmospherically processed dust. These results suggest that dust has the potential to convert non-absorbing species to photochemically active species, and thereby serve as a source of reactive organic radicals for further gas- or surface-phase chemistry. Oxalic acid, the most atmospherically abundant dicarboxylic acid, is efficiently oxidized to gas-phase CO2 at the surface of Mauritanian sand and Icelandic volcanic ash. These experiments indicate that the lifetime of oxalic acid may be limited in arid regions by Fe and Ti-catalyzed aerosol-phase photochemistry. Fluorotelomer alcohols (FTOHs), a class of industrial chemicals used in the production of surface coatings, undergo photooxidation at the surface of sand and ash to yield toxic and persistent perfluorinated carboxylic acids (PFCAs). These results provide the first evidence that the metal-catalyzed heterogeneous oxidation of FTOHs may act as a local source of aerosol-phase PFCAs. Illumination of Nigerien sand in the presence of gas-phase SO2 leads to the formation of surface-sorbed sulfate. This chemistry proceeds more efficiently on fine sand than on coarse sand. In chamber experiments, the illumination of SO2 in the presence of realistically produced dust aerosol results in new particle formation. Together, these results suggest that SO2 photochemistry at the dust surface has the potential to change not only dust hygroscopicity but also the net scattering potential of dust-containing air masses.

The indirect aerosol effect contributes to major uncertainties in determining the radiation budget of the earth. A large uncertainty is due to the formation of ice clouds onto natural or anthropogenic aerosols. Field studies have shown that mineral type particles are often associated with ice crystals in the mid-upper troposphere and given the long residence time in the atmosphere of dust particles (~2 weeks in the absence of precipitation), their contribution to ice formation processes is not fully defined. In order to probe ice formation onto natural mineral dust in a setting where it could be suspended as aerosol, a new continuous flow diffusion chamber (CFDC) was built. This allowed investigations of the effects of total aerosol surface area and particle size. The CFDC was also used in an international inter-comparison of ice nucleation instrumentation to compare efficiencies of soot, biological aerosol (bacteria) and samples of natural desert dusts from different regions of the world. The laboratory observations were parameterized using nucleation rates (Jhet) and contact angles () as described by classical nucleation theory. For both this experimental technique and a static one developed during the candidate’s Masters degree, mineral dust particulate proved to be the most efficient ice nuclei (IN) activating at RH with respect to ice (RHi) as low as 105% at T = 233 K. The efficiency varied with particle size and aerosol surface area (SA). Large particles or higher SA activated at lower RHi than small particles or lower SA. The static chamber was sensitive to the first ice event out of a large SA and therefore gave true onset RHi, which was lower than the onset defined by the CFDC studies, which was not sensitive to a single ice event. In addition the static chamber used a broader size range of particulate matter, including super micron particles while the CFDC particles sizes were restricted to below 0.5 µm. Soot and organic coated dust particles were inefficient IN compared to pure dust. Soot aerosols showed some efficiency at T < 233K where deposition ice formation was apparent. The hygroscopic organics had intermediate ice activity between dusts and alkyl-organics and soot. Bacteria aerosols were active in the deposition mode for T as high as 247 K. Contact angles () computed for ice germs forming onto natural mineral dust were small, 7<  < 29, at 223 K for RH ranging from ice to water saturation. It was concluded that there is no single value for the onset of ice formation in the atmosphere via deposition freezing. The associated contact angles show that there is a distribution of active sites on IN and that not all active sites have the same affinity for initiation of ice formation even within the same aerosol type. This work provides evidence that deposition mode nucleation can be an alternate pathway to homogeneous nucleation when mineral aerosols are present in the troposphere since the high T - low RH conditions required for deposition mode nucleation are more easily encountered in the atmosphere than the low T - high RH required for homogeneous nucleation.