The convective-diffusive transport of sub-micron aerosols in an oscillatory laminar flow within a 2-D single bifurcation is studied, using order-of-magnitude analysis and numerical simulation using a commercial software (FEMLAB®). Based on the similarity between momentum and mass transfer equations, various transient mass transport regimes are classified and scaled according to Strouhal and beta numbers. Results show that the mass transfer rate is highest at the carinal ridge and there is a phase-shift in diffusive transport time if the beta number is greater than one. It is also shown that diffusive mass transfer becomes independent of the oscillating outer flow if the Strouhal number is greater than one. / Singapore-MIT Alliance (SMA)

The characteristics of liquid and solid aerosols have been intensively investigated by means of optical diagnostic techniques. Part I describes the characteristics of liquid aerosol formation formed by heat transfer fluids (HTFs) from bulk liquids. Part II investigates the characteristics of convective transport behavior of solid particles in virtual impactor (VI). The objective of part I is to establish correlations which offer predictions on atomized particle size of HTFs which are widely and commonly used in process industries. There are numerous reports stating that mist explosions formed from leakage cause disastrous accidents in process industries. For safety concerns, the characteristics of mist formation should be known in order to prevent HTFs from catching on fire or exploding. The empirical data on formation of mist are collected by the optical measurement technique, the Fraunhofer diffraction. The Buckingham-PI theorem is applied to establish a correlation between empirical data and representative physical properties of HTFs. Final results of correlations are solved by a statistical method of linear regression. The objective of part II is to investigate the characteristics of convective transport behavior in virtual impactor (VI) which is used to sort polydisperse precursor powder in the process industries of superconductor wire. VI is the device to separate polydisperse particles as a function of particle size by using the difference in inertia between different sizes of particles. To optimize VI performance, the characteristics of convective transport should be identified. This objective is achieved by visualization techniques. The applied visualization techniques are Mie-scattering and laser induced fluorescence (LIF). To investigate analytically, a local Stokes number is introduced in order to offer criteria on predicting the efficiency of VI performance and boundary effect on particle separation. The achieved results can enhance performance and eliminate defects by having knowledge of the behavior of solid particles in VI.

Toluene is one of the most prevalent aromatic volatile organic compounds (VOCs) in the atmosphere and has large secondary organic aerosol (SOA) yields compared to many other aromatic VOCs. Recent photo-oxidation studies highlight that toluene oxidation produces more SOA than observed previously, particularly at low levels of nitrogen oxides (NOx). This study focuses on: 1.) the development of a gas-phase chemical mechanism describing toluene oxidation by hydroxyl radicals (OH); 2.) the prediction of SOA formation from toluene oxidation products; and 3.) the impact of NOx level on SOA formation. The oxidation mechanism, which includes multiple pathways after the initial OH attack, has been incorporated into the Caltech Atmospheric Chemistry Mechanism (CACM). Toluene concentrations simulated in chamber experiments by the updated CACM as a function of time are typically within 5% of observed values for most experiments. Predicted ozone and NO2 concentrations are typically within 15% of the experimental values. The gas-phase mechanism indicates the importance of bicyclic peroxy radical reactions in determining the product distribution and thus the likelihood of SOA formation. A gas-aerosol partitioning model is used in conjunction with the gas-phase mechanism to simulate SOA formation. Predicted SOA concentrations are typically within 15% of the experimental values. Under low NOx conditions, simulation shows that more than 98% of SOA mass is contributed by bicyclic products from reactions between bicyclic peroxy radicals and other peroxy radicals. Increasing NOx levels cause bicyclic peroxy radicals to react with NO or nitrate radical, leading to fragmentation products that are less likely to form SOA. SOA yield dropped from 19.26% with zero initial NOx to 13.27% with 100 ppb initial NO because of the change in the amount of toluene consumed. Composition of NOx also has an impact on SOA yield and formation, showing that NO has a greater impact on SOA yield and formation than NO2.

The purpose of this work was to study the possibility of creating Gd2O3-nanoparticles by spark generation. For this, the Palas GFG 1000 aerosol generator was used with much positive results. The potential possibilities to tune the physical properties of the nanoparticles by varying a set of experimental parameters during the fabrication process have been studied. This was investigated by comparing particles made by two different types of methods: wet chemistry (colloids), which was used in an earlier study, and an aerosol technique (aerosols), that was explored in this study. In this work, the production of 10, 20 and 40 nm particles with a high yield was obtained. Reducing the size even more proved to be troublesome. It was only possible to create a small amount of 5 nm sized particles. The reason for this is still not clear and will have to be further studied. One drawback with the fabrication procedure that was used for this work, the aerosol method, is that the amount of particles that was created is low compared to the amount of particles created by the earlier investigated modified polyol method. In the future this amount can be increased either by connecting several generators in parallel or by increasing the efficiency of the neutralizer. Description of the production and characterization of nanometer sized Gd2O3-particles constitute the main part of this work. Agglomerated particles was created by a vaporization/condensation-method and deposited onto silicon substrates for characterization. SEM studies were made in order to compare concentrations of produced particles made by the aerosol method and by the modified polyol method. For characterization, TEM investigations were made to study particle size, morphology and reshaping behavior before and after sintering was done. By using the results obtained in this work several new projects can be explored. This is very promising for future tries when a full characterization concerning spark gap-distance, gas flow and sintering temperature will be done.

Aerosol particles have profound impacts on human health, atmospheric radiation, and cloud microphysics and these impacts are strongly dependent on particle sizes. However, formation and growth of atmospheric particles are currently not well understood. In this work, laboratory and theoretical studies have been performed to investigate the formation and growth of atmospheric particles. The first two parts of the dissertation are a laboratory investigation of new particle formation and growth, and a theoretical study of atmospheric molecular complexes and clusters. The nucleation rate was considerably enhanced in the presence of cis-pinonic acid and ammonia. The composition of the critical cluster was estimated from the dependence of the nucleation rate on the precursor concentration and the time evolution of the clusters was then simulated using molecular dynamic simulations. Results from quantum chemical calculations and quantum theory of atoms in molecules (QTAIM) reveal that formation of strong hydrogen bonding between an organic acid and sulfuric acid is likely responsible for a reduction of the nucleation barrier by modifying the hydrophobic properties of the organic acid and allowing further addition of hydrophilic species (e.g., H2SO4, H2O, and possibly NH3) to the hydrophilic side of the clusters. This promotes growth of the nascent cluster to overcome the nucleation barrier and thus enhances the nucleation in the atmosphere. The last part of this dissertation is the laboratory investigation of heterogeneous interactions of atmospheric carbonyls with sulfuric acid. Direct measurement has been performed to investigate the heterogeneous uptake of atmospheric carbonyls on sulfuric acid. Important parameters have been obtained from the time-dependent or timeindependent uptake profiles. The results indicated that the acid-catalyzed reactions of larger aldehydes (e.g. octanal and 2, 4-hexadienal) in sulfuric acid solution were attributed to aldol condensation in high acidity. However such reactions do not contribute much to secondary organic aerosol (SOA) formation due to the low acidity under tropospheric conditions. On the other hand, heterogeneous reactions of light dicarbonyl such as methylglyoxal likely contribute to SOA formation in slightly acidic media. The reactions of methylglyoxal in the atmospheric aerosol-phase involve hydration and subsequent polymerization, which are dependent on the hygroscopicity, rather than the acidity of the aerosols.

This study explored different chemical characterization methods of agricultural and urban airborne particulate matter. Three different field campaigns are discussed. For the agricultural aerosols, measurement of the chemical composition of size-resolved agricultural aerosols collected from a ground site at the nominally downwind and upwind edge of a feedlot in West Texas were reported. High volume cascade impactor samplers were used for the collection of the particles, and two major analytical methods were applied to characterize different components of the aerosols, ion chromatography (IC ) was used to measure ionic composition with the main targets being ammonium (NH4 ), nitrate (NO3 -), and sulfate (SO4 2-), direct thermal desorption gas chromatography-mass spectrometry/flame ionization detection (GC-MS/FID) methodology was used to identify and quantify organic compounds in the aerosol particles. For the urban aerosols, I report the measurement of mass, and the chemical composition of size-resolved aerosols collected from two different locations in Houston, analyzed by the thermal desorption GC-MS/FID method. The investigation of single particle composition using RM is reported as well: RM and chemical mapping techniques have been applied for the qualitative analysis of components in the samples of air particulate matter collected in downtown Houston.

The characteristics of liquid and solid aerosols have been intensively investigated by means of optical diagnostic techniques. Part I describes the characteristics of liquid aerosol formation formed by heat transfer fluids (HTFs) from bulk liquids. Part II investigates the characteristics of convective transport behavior of solid particles in virtual impactor (VI). The objective of part I is to establish correlations which offer predictions on atomized particle size of HTFs which are widely and commonly used in process industries. There are numerous reports stating that mist explosions formed from leakage cause disastrous accidents in process industries. For safety concerns, the characteristics of mist formation should be known in order to prevent HTFs from catching on fire or exploding. The empirical data on formation of mist are collected by the optical measurement technique, the Fraunhofer diffraction. The Buckingham-PI theorem is applied to establish a correlation between empirical data and representative physical properties of HTFs. Final results of correlations are solved by a statistical method of linear regression. The objective of part II is to investigate the characteristics of convective transport behavior in virtual impactor (VI) which is used to sort polydisperse precursor powder in the process industries of superconductor wire. VI is the device to separate polydisperse particles as a function of particle size by using the difference in inertia between different sizes of particles. To optimize VI performance, the characteristics of convective transport should be identified. This objective is achieved by visualization techniques. The applied visualization techniques are Mie-scattering and laser induced fluorescence (LIF). To investigate analytically, a local Stokes number is introduced in order to offer criteria on predicting the efficiency of VI performance and boundary effect on particle separation. The achieved results can enhance performance and eliminate defects by having knowledge of the behavior of solid particles in VI.

During the summer of 2002, a modified tandem differential mobility analyzer (TDMA) was used to examine the size-resolved hydration state of the ambient aerosol in Southeast Texas. Although there were slight variations in the measured properties over the course of the study, the deliquescent particles observed were almost always present as metastable aqueous solutions. A relative humidity (RH) scanning TDMA system was used to measure the deliquescence/crystallization properties of ambient aerosol populations in the same region. During August, sampling was conducted at a rural site in College Station, and in September at an urban site near the Houston ship channel. Measurements from both sites indicate cyclical changes in the composition of the soluble fraction of the aerosol, which are not strongly linked to the local aerosol source. The observations show that as temperature increases and RH decreases, the hysteresis loop describing the RH-dependence of aerosol hygroscopic growth collapses. It is proposed that this collapse is due to a decrease in the ammonium to sulfate ratio in the aerosol particles, which coincides with increasing temperature and decreasing RH. This cyclical change in aerosol acidity may influence secondary organic aerosol (SOA) production and may exaggerate the impact of the aerosol on human health. The compositional changes also result in a daily cycle in crystallization RH that is in phase with that of the ambient RH, which reduces the probability that hygroscopic particles will crystallize in the afternoon when the ambient RH is a minimum. During June and July of 2004 airborne measurements of size-resolved aerosol hygroscopic properties were made near Monterey, California. These were used to examine the change in soluble mass after the aerosol had been processed by cloud. The calculated change in soluble mass after cloud-processing ranged from 0.66 g m-3 to 1.40 g m-3. Model calculations showed these values to be within the theoretical bounds for the aerosols measured. Mass light-scattering efficiencies were calculated from both an averaged aerosol size distribution and from distributions modified to reflect the effects of cloud. These calculations show that the increase in mass light-scattering efficiency should be between 6% and 14%.

Two-week sampling periods during the spring, summer, and fall of 2003, and the winter of 2004 were conducted utilizing a tandem differential mobility analyzer (TDMA) and, during the spring and summer, an aerodynamic particle sizer (APS), to characterize the seasonal variability of the Big Bend regions aerosol optical properties. Mass extinction efficiencies and relative humidity scattering enhancement factors were calculated for both externally and internally mixed aerosol populations for all size distributions collected, in an effort to possibly improve upon the default EPA mass extinction efficiencies used for all Class 1 areas across the United States. The mass extinction efficiencies calculated differed to some extent form the default values employed by the EPA. Sulfate, nitrate, and light absorbing carbon (LAC) exhibited a strong dependence on assumed mixing state, while, additionally, sulfate was also dependent on the assumed dominant aerosol. Seasonal variability was seen with all particle types, excluding LAC, with sulfate mass extinction efficiencies displaying the greatest variability with season. Calculated back trajectories indicated that air masses originating from the southeast had elevated mass extinction efficiencies, while, conversely, air masses originating from the southwest and northwest had the smallest mass extinction efficiencies.

An investigation of the high spectral resolution signatures and radiative forcing of tropospheric aerosol in the thermal infrared was conducted. To do so and to support advanced modeling of optical properties, a high spectral resolution library of atmospheric aerosol optical constants was developed. This library includes new optical constants of sulfate-nitrate-ammonium aqueous solutions and the collection of a broad range of existing optical constants for aerosol components, particularly mineral optical constants. The mineral optical constants were used to model and study infrared dust optical signatures as a function of composition, size, shape and mixing state. In particular, spherical and non-spherical optical models of dust particles were examined and compared to high spectral resolution laboratory extinction measurements. Then the performance of some of the most common effective medium approximations for internal mixtures was examined by modeling the optical constants of the newly determined sulfate-nitrate-ammonium mixtures. The optical signature analysis was applied to airborne and satellite high spectral resolution thermal infrared radiance data impacted by Saharan dust events. A new technique to retrieve dust microphysical properties from the dust spectral signature was developed and compared to a standard technique. The microphysics retrieved from this new technique and from a standard technique were then used to investigate the effects of dust on radiative forcing and cooling rates in the thermal IR.