Allan Bertram

Pure water does not freeze homogeneously at temperatures above -35°C. Heterogeneous ice nucleation induced by ice nucleating particles (INPs) occurs at warmer temperatures than homogeneous nucleation. Atmospherically relevant INPs can significantly affect ice formation in mixed-phase and ice clouds, and therefore influence the Earth’s climate system. Several factors, including inorganic ions, acidic or basic solutes, and pressure variations influence the ice nucleating ability of INPs. At present, little is known about the microscopic mechanisms by which these factors affect heterogeneous ice nucleation and the ice nucleating ability of INPs.We examine the influences of inorganic ions and pH changes on kaolinite’s ice nucleating ability employing direct molecular dynamics (MD) simulations. We demonstrate that ionic solutes decrease the ice nucleating ability of the Al (001) kaolinite surface. The hydroxy groups exposed on the Al (001) surface can become deprotonated in basic solution or dual-protonated in acidic solution. We find that the mono-protonated Al (001) surface, which is expected to be stable at near-neutral pH, is the most effective ice nucleating surface. We perform droplet freezing experiments with kaolinite samples under acidic and basic conditions, covering a pH range of 0.18 - 13.26. Our MD simulations and experimental results indicate that the Al (001) surface may be important for ice nucleation by kaolinite.Employing MD simulations and varying the protonation state of the α-alumina (0001) surface, we find that the ice nucleating efficiency of this surface decreases nearly symmetrically with acidic and basic pH changes away from the neutral point. This is in qualitative agreement with previous droplet freezing experiments performed on a single (0001) surface. We carry out droplet freezing experiments on two α-alumina powder samples, covering a pH range of 0.59 - 13.19. The freezing results for the powder differ significantly from those of the single surface.We use MD simulations to probe the influence of pressure on heterogeneous ice nucleation by a finite-size β-AgI disk. We find that negative pressures enhance ice nucleation at high temperature, and we demonstrate how water diffusion can significantly influence ice nucleation and growth at low temperatures and negative pressures.

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Predictions of atmospheric chemistry, air quality, and climate depend on molecular diffusion and viscosity within organic aerosol (OA) particles. These predictions have uncertainties due, in part, to a lack of understanding of how viscosity and diffusion depend on ambient parameters such as temperature and relative humidity (RH). This thesis aims to improve the understanding of the temperature and RH-dependency of molecular diffusion of OA through direct experimental observation of diffusivity and viscosity for different types of OA.The viscosity of cooking organic aerosol (COA) films collected in a real kitchen environment was measured with the poke-flow technique. COA’s viscosity was found to be 7 × 10³ Pa s for RH values from 0 to 69%. This result was many orders of magnitude lower than predicted with a commonly-used parameterization. The parameterization agreed with the measurements after adjusting with a triglycerides-based correction factor.Secondary organic aerosol (SOA) material from biomass burning was generated from the oxidation of phenolic compounds: catechol, guaiacol, and syringol. The SOA viscosity was measured using the poke-flow technique. The viscosity of all systems followed roughly the same trend, with viscosity 3 × 10³ Pa s at RH > 40% and > 2 × 10⁸ Pa s under dry conditions. A parameterization was developed to extrapolate to relevant tropospheric conditions.Few techniques can measure the temperature dependence of viscosity in OA. A new method based on hot-stage microscopy was developed, validated, and applied to SOA material derived from farnesene photooxidation. The farnesene SOA viscosity ranged from 2.6 × 10⁴ to 3.1 × 10⁶ Pa s when changing the temperature from 67 to 51 °C. The RH and temperature-dependent diffusion of organic molecules were directly measured in sucrose-water, a proxy for SOA, using rectangular fluorescence recovery after photobleaching. Diffusion rates were measured at temperatures ranging from –10 to 40 °C and for RH from 43 to 85%. The corresponding mixing times of organics were often larger than 1 h for conditions found in the free troposphere, meaning that the frequently-made assumption of fast mixing ( 1 h) in chemical transport models may be invalid for these conditions.

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The full abstract for this thesis is available in the body of the thesis, and will be available when the embargo expires.

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Ice nucleating substances (INSs) are substances capable of initiating ice formation. Atmospheric INSs can affect the formations and properties of mixed-phase clouds and ice clouds and thus influence the Earth’s climate system. Despite the importance of INSs, our understanding of the sources, concentrations, and properties of INSs is still limited. This dissertation focuses on INSs from high latitude regions.Sea-ice diatom exudates collected from two locations in the Antarctic caused freezing at temperatures from -17 to -22 °C. The results suggested that sea-ice diatom exudates can act as INSs once emitted to the atmosphere. According to a heat assay and a filter assay, possible candidates for the INSs in the exudate samples from the Ross Sea and the McMurdo Sound are polysaccharide-containing nanogels and protein-containing nanogels, respectively. Cyanobacteria mat exudates from the Antarctic caused freezing at temperatures from -5 to -13 °C, with possible INS candidates being aggregates containing heat-sensitive proteins. These results indicate that cyanobacteria mat exudates can also cause ice nucleation in the atmosphere.Airborne dust samples collected near the Kaskawulsh Glacier contained INSs, which nucleated ice at temperatures from -6 to -23 °C. The ice nucleating ability of the INSs was similar to that of K-feldspar and Icelandic dust at freezing temperatures less than -15 °C. According to a heat assay and an ammonium sulfate assay, the INSs that caused freezing at temperatures warmer than -15 °C were possibly biological materials. The INS concentrations at the site in May 2018 are significantly higher than those predicted with dust concentrations simulated by a global chemical transport model (GEOS-Chem) without the inclusion of highlatitude dust sources. The under-prediction of the GEOS-Chem model suggests that high latitude dust sources should be included in modeling studies of INS.Furthermore, ice recrystallization inhibition substances (IRISs) in cyanobacteria mat exudates were studied to investigate the cold tolerance mechanism of cyanobacteria and the relationship between INSs and IRISs. IRISs were observed in the cyanobacteria mat exudates and the properties of IRISs were different from the INSs in the cyanobacteria mat exudates, with possible IRISs being polysaccharides or heat-stable proteins.

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Aerosol particles can indirectly affect climate by acting as ice nucleating particles (INPs). Although INPs are only a small subset of atmospheric particles, they can have a significant impact on the hydrological cycle and climate by initiating ice formation in clouds and by modifying the lifetime and optical properties of clouds. Nevertheless, the properties of atmospheric INPs are not yet fully understood. Two important types of atmospheric INPs are mineral dust and biological particles. This dissertation focuses on these two types of INPs. During atmospheric transport, mineral dust particles can acquire water-soluble coatings, such as coatings containing alkali metal nitrates, inorganic acids, and organic solutes. As a result, the effects of alkali metal nitrates, inorganic acids, polyols, and carboxylic acids on the ice nucleation properties of potassium-rich feldspar (K-feldspar), a type of mineral dust INP in the atmosphere, were examined. In addition, daily INP concentrations at Alert, Nunavut, a ground site in the Canadian High Arctic, were determined for October and November of 2018, and the contribution of mineral dust and biological particles to the total INP population was evaluated for this location and time period. The results in this dissertation improve our understanding of the properties of mineral dust INPs under atmospheric conditions, as well as the concentration, composition, and source of INPs in the Arctic. This information should be useful for global and regional climate models.

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Physical properties such as phase state and the mixing times of water and organic molecules within secondary organic aerosol (SOA) are critical for predicting the formation, growth, and impact of SOA in the atmosphere. In the past, it has been assumed that SOA is liquid with rapid mixing times of water and organic molecules. However, recent laboratory measurements and field studies have shown that SOA may be semi-solid or solid in the atmosphere with long mixing times for certain conditions (i.e. low temperature and low relative humidity (RH)). Despite these recent measurements, the global distributions of phase state and mixing times within SOA are not well constrained. To address this knowledge gap, this thesis presents predictions of the global distribution of phase state and mixing times within SOA for the troposphere.Global distributions of mixing times of organic molecules in SOA were predicted for the planetary boundary layer (PBL) for α-pinene SOA and sucrose-water particles based on literature viscosity data. The predicted mixing times in the PBL were fast, indicating the assumption of rapid mixing may be valid for this region of the atmosphere. The viscosities of β-caryophyllene SOA were measured as a function of RH. These viscosities were used to calculate the mixing times of organic molecules in the SOA. Mixing times increased by 3-4 orders of magnitude as the RH decreased from 50 to 0%. However, the mixing times were rapid at RH values ≥ 15%, which indicated that β-caryophyllene SOA likely mixes rapidly in the PBL. Finally, global distributions of phase states and mixing times of water and organic molecules were predicted based on room temperature viscosities for tree emission SOA and toluene SOA. Both of the SOA were predicted to be in a solid, glassy state in the upper troposphere with slow mixing times of water. Mixing times of organic molecules in SOA were predicted to be long in the middle and upper troposphere, with implications for the growth, formation. and impact of SOA in the atmosphere. The results presented here increase our knowledge of the phase state and mixing times in SOA for the troposphere.

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The diffusion coefficients of large and small molecules in organic-water mixtures are important to atmospheric chemistry, as organic-water mixtures are useful proxies for atmospheric organic aerosol. Diffusion coefficients of large molecules (molecules with radius Rdiff ≥ the radius of the organic matrix molecule, Rmatrix) and small molecules (Rdiff Rmatrix) in organic-water mixtures have been presented in the literature. However, these data are limited.Frequently, the Stokes-Einstein relation, which relates diffusion and viscosity (D ∝ 1/η), where D is the diffusion coefficient and η is the viscosity, is used to calculate diffusion coefficients. An alternative relation is the fractional Stokes-Einstein relation (D ∝ 1/η^ξ), where ξ is a fractional exponent. However, the accuracy of neither of these relations has been thoroughly assessed for predicting diffusion coefficients in organic-water mixtures. This thesis combines new diffusion measurements with literature data to test the Stokes-Einstein and fractional Stokes-Einstein relations. When Rdiff/Rmatrix ≥ 1, the Stokes-Einstein relation is able to describe most diffusion coefficients within a factor of 10, up to a viscosity of 10^6 Pa s. However, a fractional Stokes-Einstein relation with a single ξ value does a better job of describing the data. When a data set includes both Rdiff/Rmatrix ≥ 1 and Rdiff/Rmatrix 1, the Stokes-Einstein relation describes only 75% of the data. A fractional Stokes-Einstein relation, where ξ is a function of Rdiff/Rmatrix, is able to describe 98% of the data. These equations are tested in more realistic and chemically complex aerosol samples. The Stokes-Einstein relation is able to accurately describe diffusion coefficients of organic molecules in one lab-generated organic aerosol sample, while the fractional Stokes-Einstein relation is required to describe the diffusion coefficients in the second sample.Finally, diffusion measurements of a very large organic molecule (Rdiff >> Rmatrix) are combined with the Stokes-Einstein relation to calculate the viscosity of an organic-water mixture, resolving a discrepancy in the literature between two previously published viscosity data sets.The results presented here increase our ability to quantify the relationship between diffusion of large and small molecules and the viscosity of organic-water mixtures, which are useful proxies for atmospheric organic aerosol.

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Ice nucleating particles (INPs) are particles that cause heterogeneous ice nucleation in the atmosphere. INPs affect the formation and properties of ice and mixed-phase clouds and therefore influence the radiative forcing of the Earth-atmosphere system. However, the climatic effect of INPs is poorly understood, in part, because the concentrations, properties, and sources of INPs are not well understood, especially at remote locations.In the following dissertation, the concentrations, properties, and sources of INPs in remote Canadian environments are investigated. The environments studied included three coastal marine sites (two at mid-latitude and one in the Arctic), one ground site in the Arctic boundary layer, and the Arctic free troposphere. The concentrations of INPs at -25 oC were found to range from 0.01 to 3 L-1, and the INP concentrations measured in the Arctic were lower than that at mid-latitude.At the three coastal marine sites, the ice nucleating ability of aerosol particles was found to be dependent on the particle size with larger particles being more efficient at nucleating ice. Mineral dust was likely a major component of the supermicron INPs, and sea spray aerosol was not likely the major source of INPs at these sites. At the ground site in the Arctic boundary layer, INP concentrations at -25 oC were correlated with tracers of mineral dust, anti-correlated with tracers of sea spray aerosols, and not correlated with tracers of anthropogenic aerosols, which suggest that mineral dust was a major contributor to the INP population at this site. The majority of the particles collected in the Arctic free troposphere were mineral dust, and aluminosilicates and silicates were the major mineral types. A large fraction of the mineral dust was internallymixed with inorganic species (e.g., sea salt and sulfates). Particle dispersion modelling suggested iiithat mineral dust particles collected at both ground level and in the free troposphere were transported over long distances from East Asia.The results presented in this dissertation increase our understanding of the concentrations, properties, and sources of atmospheric INPs, and should be useful to constrain models of INPs.

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Ice nucleating particles (INPs) in the Arctic can influence climate and precipitation in the region; yet our understanding of the concentrations and sources of INPs in this region remain uncertain. The following dissertation investigates 1) the properties and concentrations of INPs in the sea surface microlayer and bulk seawater samples collected in the Canadian Arctic, and 2) the source region of measured concentrations of INPs in the Canadian Arctic marine boundary layer. All measurements were made in the Canadian Arctic on board the CCGS Amundsen during the summers of 2014 and 2016.INPs were ubiquitous in the microlayer and bulk seawater samples, and were likely heat-labile biological materials between 0.2 and 0.02 μm in diameter. There was a strong negative correlation between salinity and freezing temperatures, and a strong positive correlation between the fraction of meteoric water in each sample and freezing temperatures, possibly due to INPs associated with terrestrial run-off. Spatial patterns of INPs and salinities in 2014 and 2016 were similar. However the concentrations of INPs were higher on average in 2016 compared to 2014, and INP concentrations were enhanced in the microlayer compared to bulk seawater in several samples collected in 2016.Average concentrations of INPs measured in the Canadian Arctic marine boundary layer fell within the range of INP concentrations measured in other marine boundary layer locations. The ratio of measured mineral dust surface area to sea spray surface area ranged from 0.03 to 0.09. Based on these ratios, and the ice active surface site densities of mineral dust and sea spray aerosol determined in previous laboratory studies, mineral dust is a more important contributor to the INP population than sea spray aerosol for the samples analysed. Based on particle dispersion modelling, the source of INPs in the Canadian Arctic marine boundary layer during the summer of 2014 was from continental regions such as the Hudson Bay area, eastern Greenland, or northwestern continental Canada.

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This dissertation studies the silica/water interface using sum frequency generation spectroscopy. The effects of alkali chloride ions and temperature on the hydrogen bonding network at the interface are examined. We observed that the structure of water in the Stern layer depends on the identity of the cation. The ability of a cation to displace the hydration water on silica surface is in the order of Mg²⁺ > Ca²⁺ > Li⁺ > Na⁺, consistent with the trend of the acid dissociation constant of the salt. We conclude that ions with a high pKa, such as Mg²⁺ and Ca²⁺, have a local electrostatic field strong enough to polarize water molecules in the hydration shells of the ions. These partially hydrolyzed water molecules form linkages with the negative charges on the silica, forming solvent shared ion pairs. During freezing of pure water, we observed a transient phase of ice at water/mineral interfaces, which had enhanced IR-visible sum frequency generation intensity for several minutes. Most forms of ice are centrosymmetric but a possible explanation of for the transient phase is the formation of stacking-disordered ice during the freezing process. Stacking-disordered ice, which has only been observed in the bulk ice at temperatures lower than -20 °C, is a random mixture of layers of hexagonal ice and cubic ice. The transient phase at the ice/mineral interface was observed at temperatures as high as -1 °C. This observation suggests that the mineral surface may play a role in promoting the formation of the stacking-disordered ice at the interface. The effect of ions during freezing at the silica/water interface was investigated. Ice is the first phase to form. NaCl·2H₂O forms below the eutectic temperature, indicating that the formation and growth of ice does not push the ions out of the interfacial region. We compared the surface freezing diagram with the bulk equilibrium phase diagram of aqueous sodium chloride solutions. Although the concentration of ions is higher at a charged surface, we observe that freezing point depression at the surface is analogous to freezing point depression for homogeneous freezing and bulk equilibrium phase diagram.

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Ice nucleating particles (INPs), which are a small fraction of the total aerosol population, are capable of catalyzing ice formation under atmospheric conditions. INPs may therefore influence the development, albedo, and lifetime of mixed-phase and ice clouds, and ultimately indirectly effect climate. As this aerosol indirect effect represents one of the largest sources of uncertainty in our understating of climate processes, measurements that quantify and characterize the atmospheric INP population are needed. The micro-orifice uniform deposit impactor-droplet freezing technique (MOUDI-DFT) was developed to measure INP concentrations in the atmosphere as a function of size and temperature in the immersion mode. The first campaign using the MOUDI-DFT was conducted in a Colorado forest. The concentrations of INPs and bioparticles were increased and correlated during and following rainfall events, and their size distributions were similar. This indicates that rainfall-associated mechanisms of bioparticle release may influence the abundance and efficiency of INPs in this region. The MOUDI-DFT was next used at a coastal site in Western Canada. INP concentrations were strongly correlated with those of fluorescent bioparticles and the size distributions of these particles were similar, suggesting bioparticles were an important source of INPs during this study. Despite the predominance of marine air masses, no evidence of a marine INP source was found. Six parameterizations of ice nucleation were tested and found to be poor predictors of the measured INP concentrations, identifying a need to develop INP parameterizations appropriate for coastal environments. Finally, size-resolved INP measurements from six ground-level sites in North America and one in Europe were presented, covering Arctic, alpine, coastal, marine, agricultural, and suburban environments. On average, 78 % of INPs were supermicron in size and 53 % were in the coarse mode (> 2.5 micrometers). Large particles were therefore a significant component of the ground-level INP in these diverse locations. The results presented in this dissertation increase our understanding of atmospheric INP concentrations, composition, and size. This information can be used to constrain INP sources, improve modeling of their long-distance transport and related indirect climate effects, and determine the ability of existing instrumentation to capture the full INP population.

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Water droplets in the atmosphere do not freeze homogeneously until -38ºC. Freezing at warmer temperatures requires heterogeneous ice nuclei (IN). Despite the importance of ice in the atmosphere, little is known about the microscopic mechanisms of heterogeneous ice nucleation. This thesis employs molecular dynamics simulations to investigate ice nucleation by silver iodide, kaolinite, potassium feldspar, gibbsite, and a protein. Silver iodide is one of the best known ice nucleating agents. We examined seven surfaces of silver iodide and observed ice nucleation on three surfaces. The surfaces that nucleated ice organized the first layer of water molecules into a configuration resembling ice, such as chair conformed hexagonal rings. Surfaces that do not nucleate ice do not organize water into icelike configurations, such as planar rings. Results suggest lattice mismatch is insufficient in predicting ice nucleation, and a finer atomistic match is required. Finite silver iodide disks and plates were used to probe the relationship between the size of a nucleating surface and maximum temperature of ice nucleation. Larger disks nucleated ice at warmer temperatures than smaller disks by forming larger initial cluster of ice which could reach the critical size easier than homogeneously formed clusters. Kaolinite is a common clay known to nucleate ice. Our simulations investigated both sides of the (001) surface and found both sides able to nucleate ice. The Al-surface was simulated with varying degrees of freedom of motion. An optimum amount of movement was required to nucleate ice as the surface needs to adapt into a configuration favorable to ice. Ice nucleated on the Si-surface via the formation of a novel composite surface structure which facilitated bulk ice nucleation. Potassium feldspar simulations explored three variations of the two primary cleavage planes. All surfaces failed to nucleate ice and density profiles suggest that the surfaces are unlikely to nucleate ice. We succeeded in nucleating ice on gibbsite with prepared surface conformations compatible with ice. Biological IN, such as ice nucleation proteins, are among the most efficient IN. We attempted to simulate ice nucleation via a protein, but were unable to achieve ice nucleation.

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Aerosols are ubiquitous throughout the Earth’s atmosphere, and secondary organic material (SOM), which is produced from the oxidation of volatile organic compounds, is estimated to constitute a significant fraction of atmospheric aerosol mass. Furthermore, particles containing SOM can cause negative health outcomes, and affect Earth’s climate, both directly by scattering solar radiation, and indirectly by acting as nuclei for cloud droplets.Despite the importance of particles containing SOM, their physical properties, such as viscosity, are poorly constrained. To address this knowledge deficit, a technique to measure the viscosity of small samples of material, similar to that produced in environmental simulation chambers, was developed and validated. This technique was then used to measure the viscosity of SOM produced via the ozonolysis of α-pinene in an environmental simulation chamber. The viscosity of this material was found to depend strongly on the relative humidity (RH) used when measuring viscosity and the concentration of SOM mass at which the SOM was produced. A difference between the viscosity of the water-soluble component of SOM and the total SOM (water-soluble and water-insoluble components) was also observed.The viscosity of saccharides and a tetraol were subsequently measured, with these compounds serving as proxies of highly oxidized components of SOM found in the atmosphere. For saccharides, viscosity was determined to increase by at least four orders of magnitude as molar mass doubled. In addition, the tetraol was determined to have a viscosity at least two orders of magnitude lower than that of SOM produced via the oxidation of isoprene, in which the tetraol has been identified.Finally, literature viscosity data for organic compounds was used to demonstrate that saturation vapour concentration, the mass based equivalent of saturation vapour pressure, is a useful parameter for predicting viscosity, and better than elemental oxygen-to-carbon ratio or molar mass, at least for organic compounds containing only one or two functional groups.The results presented in this dissertation increase our knowledge of the viscosity of SOM, and its dependence on RH, the SOM mass concentration at which the SOM is produced, number of hydroxyl functional groups in the organic molecule, and molar mass.

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Ice nucleation occurs throughout the atmosphere. Some atmospheric ice particles are formed through nucleation on insoluble atmospheric aerosols known as ice nuclei (IN). The abundance and chemical composition of these IN affect the properties of clouds and in turn the radiative balance of the Earth through the indirect effect of IN on climate. The indirect effect of IN on climate is one of the least understood topics in climate change. A better understanding of ice nucleation and better capabilities to parameterize ice nucleation are needed to improve the predictions of the effect of IN on climate. Using a temperature and humidity controlled flow cell coupled to an optical microscope, the ice nucleation properties of three different mineral dust particles are examined in two different freezing modes. Results showed that the freezing ability of supermicron dust particles is lower than that of submicron dust particles of the same type. These freezing results along with literature freezing results of nine biological aerosol particles are used to evaluate different schemes used to parameterize ice nucleation in atmospheric models. These schemes are evaluated based on the ability to reproduce the laboratory freezing results. It was found that a single parameter scheme based on classical nucleation theory was unable to reproduce the freezing results of all particles studied. However, more complex schemes were able to reproduce the freezing results.The results in this thesis can be used by atmospheric modellers to improve predictions of mixed-phase and ice clouds and climate change.

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Black carbon is a subset of the total atmospheric aerosol population that is formed in the incomplete combustion of fossil fuels, biofuels, and biomass. This research focused on the properties of black carbon particles measured in the boundary layer and free troposphere, as well as the activation of black carbon particles by cloud droplets. The primary motivation for this research is to increase our understanding of the properties of black carbon under these different atmospheric conditions.A single particle soot photometer was used to study properties of black carbon particles incorporated into cloud droplets at two field locations: 1) a marine boundary layer site, and 2) a high elevation mountain site. At both sites, a size dependence on the fraction of black carbon incorporated into cloud droplets was observed; and for small (100 nm) diameters, black carbon was efficiently incorporated into droplets. In addition, at the marine boundary layer site, thick coatings were observed on the small diameter black carbon particles that were incorporated into the droplets, which was consistent with theory.The single particle soot photometer was also used at a high elevation mountain site to investigate properties of black carbon from biomass burning and black carbon within the free troposphere. The average mass concentration of black carbon was found to be significantly higher (approximately 9x) during periods of biomass burning than within the free troposphere, yet had similar mass median diameters. Coating thicknesses of black carbon containing particles during the two subsets of data were also investigated. Average coating thicknesses for black carbon core diameters between 140 to 160 nm was 55 nm when sampling in the free troposphere, but approximately 32 nm when sampling air masses influenced by biomass burning. The results presented in this dissertation increase our understanding of the properties of black carbon particles and how they vary as a function of location and type of air mass sampled. This information can be used to further constrain computer models that are used to predict how black carbon can affect climate.

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Aerosol particles containing both organic material and inorganic salts are abundant in the atmosphere. These particles may undergo phase transitions when the relative humidity fluctuates between high and low values in the atmosphere. This dissertation focuses on liquid-liquid phase separation in atmospherically relevant mixed organic-inorganic salt particles. Liquid-liquid phase separation has potentially important implications in chemical and physical processes in the atmosphere. A humidity and temperature controlled flow cell coupled to either an optical, fluorescence, or Raman microscope was used to study the occurrence of liquid-liquid phase separation and the phase separation relative humidity (SRH) of particles containing atmospherically relevant organic species mixed with inorganic salts. Organic species in the particles studied include single organic species, such as carboxylic acids, alcohols, and oxidized aromatic compounds, as well as complex laboratory-produced secondary organic material. Material directly collected from the atmospheric environment was also studied. In this dissertation, the effects of oxygen-to-carbon elemental ratio (O:C) of the organic species, salt types, molecular weight of the organic species, and temperature on the occurrence of liquid-liquid phase separation and SRH were studies. The oxygenic-to-carbon elemental ratio was a useful parameter for predicting liquid-liquid phase separation and SRH. Liquid-liquid phase separation did not depend strongly on the molecular weight of the organic species or temperature. The correlation between SRH and O:C in particles containing organic species mixed with different salts were qualitatively similar. Results of this research will help improve the understanding of liquid-liquid phase separation in the atmospheric aerosols, and may, in turn, improve simulations and predictions of atmospheric chemistry and climate.

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In the atmosphere, ice can form on solid aerosol particles called ice nuclei. This research focuses on the ice nucleation properties of mineral dusts and biological particles. The motivation for this research is two-fold. First, ice nucleation on these aerosols may influence cloud formation, cloud reflectivity and precipitation patterns in what is an indirect climate effect. This effect is one of the largest uncertainties in current climate models. Second, ice nucleation may be an important removal mechanism for these particles from the atmosphere and may influence their long-distance transport. Currently, ice nucleation is represented in a simplistic manner or not at all in models used to predict the long-distance transport of aerosols.A temperature and humidity controlled flow cell coupled to an optical microscope was used to study the ice nucleation properties of four mineral dusts, eighteen fungal spores, and six bacteria. It was found that acidic coatings reduce the ice nucleating ability of the mineral dusts. The fungal spores showed a wide range of ice nucleating properties and there was no inherent difference in the ice nucleation ability of spores belonging to different taxonomic groups. Four of the bacteria studied were very poor ice nuclei and the fifth bacterium was an excellent ice nucleus.The results from the flow cell experiments on fungal spores were used to describe ice nucleation in two modeling studies that simulated atmospheric transport. One study found that a significant fraction of large fungal spores (20 micrometers in diameter) can reach high altitudes where they could act as ice nuclei. The other study focused on smaller spores (3 to 8 micrometers) and found that ice nucleation on these spores effects their long-distance transport to polar and marine regions.The laboratory results were used to show that mineral dusts are more important than the fungal spores or bacteria that were studied on a global annual scale. These results can be used to improve parameterizations of ice nucleation on mineral dusts and biological particles in future modeling studies investigating the indirect effect of aerosols on climate or the long-distance transport of aerosols in the atmosphere.

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Aerosol particles are ubiquitous throughout the atmosphere and play an important role in human health, climate, and the chemistry of the atmosphere. A significant mass fraction of these particles is composed of organic species, which remain poorly characterized due to the number and diversity of species present. This thesis describes the development and characterization of two versions of a new single particle mass spectrometer with a 3D ion trap for organic aerosol studies.Version I combines CO₂ laser desorption and electron impact ionization in an ion trap. Mass spectra obtained for four species are comparable to NIST EI spectra. Tandem mass spectrometry studies are also demonstrated. The effects of vaporization energy, ionization delay time, and electron pulse width on the mass spectra and fragmentation patterns are examined. The detection limit of the instrument is found to be ~1x10⁸ molecules (350 nm diameter particle) for 2,4-dihydroxybenzoic acid. Version II integrates CO₂ laser desorption and tunable VUV ionization in an ion trap and was used for a detailed study of oleyl alcohol, oleic acid and mixtures thereof. Both the degree of fragmentation in the mass spectra and the translational energy of the vaporized molecules are found to vary as a function of desorption energy in the pure particles and as a function of composition in the mixed particles. These changes can be described by the energy absorbed per particle during desorption. We show that these effects hinder the quantitative response of the instrument and have important implications for other two step laser desorption/ionization systems.The final part of this thesis presents preliminary results from atmospherically relevant particles. Mass spectra of cigarette sidestream smoke, fulvic acid, meat cooking, and ammonium bisulfate aerosols are collected using both versions of the instrument. The two step desorption/ionization process only worked for two types of aerosols, while CO₂ only mass spectra were obtained for all four aerosol types. The suitability of CO₂ desorption strongly depended on particle composition, which will affect the applicability of the technique to atmospherically realistic aerosols. The results also suggest that CO₂ only laser desorption/ionization may be useful for field studies.

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Grand canonical Monte Carlo calculations are used to determine water adsorption and structure on kaolinite surfaces, with and without the presence of trench-like defects, as a function of relative humidity (RH), at 235 K and 298 K. Both basal planes (the Al- and Si-surfaces), as well as two edge-like, defect free surfaces are considered. The trenches simulated are rectangular in geometry, and have a fixed depth and varying width. Thegeneral force field CLAYFF is used together with the SPC/E and TIP5P-E models for water. At both 235 K and 298 K, the edges, Al-surface, and trenches adsorb water at sub-saturation, in the atmospherically relevant pressure range. The Si-surface remains dry up to saturation. Both edges and the Al-surface adsorb water up to monolayercoverage. Adsorption on the Al-surface exhibits properties of a first-order process with evidence of collective behavior, whereas adsorption on the edges is essentially continuous and appears dominated by strong water lattice interactions. Only next to the Al-surface, were hexagonal rings observed in the water layer. However, they did not match hexagonal ice Ih. The results obtained using trenches show that the granularity of the surfaces can play a major role in the adsorption of multiple layers of water over a large range of RH. Our calculations suggest that water adsorption in trenches, and possibly in other similar defects, can offer an explanation of the large water coverages reported experimentally. Related to ice, the very dense, proton ordered, ferroelectric structures found in the trenches at235 K do not correspond to any recognizable form of bulk ice. We speculate how these structures might aid ice nucleation and growth, and suggest how this possibility could be further explored with simulations and experiments.

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No abstract available.

Atmospheric particles play a crucial role in climate, visibility, air pollution, and human health. Reactions between gas-phase molecules and particles (heterogeneous reactions) affect not only the particle composition and morphology, but also the composition of the atmosphere. This thesis investigates the heterogeneous chemistry of organic mixtures and inorganic solutions coated with organic monolayers as proxies for atmospheric particles. The first topic of interest was the reaction between N₂0₅ and aqueous inorganic solutions coated with organic monolayers. The goal of this work was to better understand how organic monolayers on aqueous particles affect the mass transport and kinetics of N₂0₅ uptake by aqueous aerosols, and consequently what effectthe monolayer can have on predicted concentrations of N₂0₅ in the atmosphere.To investigate heterogeneous reactions of inorganic solutions coated with an organic monolayer a new rectangular channel flow reactor was developed. This newly developed flow reactor was described in detail and validated. Subsequently, the new flow reactor was used to study the reactive uptake of N₂0₅ on sulfuric acid solutions in the presence of a variety of 1- and 2-component monolayers with varying functional groups, solubilities, chain lengths, surface pressures, and molecular surface areas. Reactive uptake of N₂0₅ on aqueous sulfuric acid solutions was found to correlate most strongly with the molecular surface area or packing density of the monolayer. These results provide a good foundation for determining the influence of monolayers on heterogeneous reactions in the atmosphere, and highlight the need for characterization of monolayer surface properties of organic monolayers present on atmospheric particles.The second topic of interest was reactions between 0₃ and proxies for meat cooking aerosols with the goal to better understand the effect of the phase and microstructure of the mixtures on the lifetime of oleic acid (OA) in atmospheric particles. The reactive uptake of 0₃ was approximately 1 order of magnitude slower on binarysolid-liquid mixtures and multicomponent mixtures that closely represent compositions of meat-cooking aerosols compared to the liquid solutions. Lifetimes up to 75 min were obtained for these mixtures.

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