This thesis concerns various aspects of the influence of atmospheric particulate matter on the terrestrial system. In Part I, the radiative influence of particulate matter on the production of crops is explored using the CERES crop model. It is known that the presence of aerosols in the atmosphere simultaneously reduces the amount of sunlight reaching the surface and increases the fraction of that light which is diffuse. Reduction of the total amount of sunlight tends to slow the rate of photosynthesis occurring in plants while increasing the fraction which is diffuse tends to increase the net rate of photosynthesis by more evenly distributing sunlight throughout all layers of a plant canopy. The CERES crop model was modified to estimate the influence of both a reduction in total sunlight and an increase in the diffuse fraction. Model simulations were performed for rice, maize and wheat at a variety of locations and found the likely influence of aerosols on crop production to be a 0-10% reduction in yield compared to the base case. In Part II, the concentration and size distribution of water-insoluble aerosols (WIA) is explored. It has been well-established that atmospheric particulate matter influences the planetary radiation budget both directly and indirectly. The magnitude of these influences is related to particle solubility. A new technique was developed to provide these measurements in real-time. This instrumentation was evaluated in a laboratory setting and implemented into several field studies. Results from these sampling campaigns indicate that in areas heavily influenced by motor vehicle traffic, the WIA concentration is dominated by particulate soot. Many episodes of high levels of crustal dust were also observed. At these times, the WIA size distribution shifted toward larger sizes in a characteristic manner. This suggests that this method is useful for detecting insoluble mineral aerosols as well as particulate soot and that examination of the WIA size-distribution may provide a basis to distinguish between the two.

Soot aerosols are well known to be atmospheric constituents, but the hydrophobic nature of fresh soot likely prohibits them from encouraging cloud development. Soot aged through contact with oxygenated organic compounds may become hydrophilic enough to promote water uptake. In this study, the tandem differential mobility analyzer (TDMA) and differential mobility analyzer?aerosol particle mass analyzer (DMA?APM) were employed to measure the changes in morphology and hygroscopicity of soot aerosol particles upon coating with succinic and glutaric acids. The effective densities, fractal dimensions and dynamic shape factors of fresh and coated soot aerosol particles have been determined. Significant size-dependent increases of soot particle mobility diameter, mass, and effective density (?eff) were observed upon coating of aggregates with succinic acid. These properties were restored back to their initial states once the acid was removed by heating, suggesting no restructuring of the soot core had occurred. Coating of soot with glutaric acid, on the other hand, leads to a strong size shrinking with a diameter growth factor ~0.60, even after the acid has been removed by heating suggesting the strong restructuring of the soot agglomerate. The additional 90% RH cycle can evidently enhance the restructuring process. The extinction and scattering properties at 532 nm of soot particles internally mixed with dicarboxylic acids were investigated experimentally using a cavity ring-down spectrometer and an integrating nephelometer, respectively, and the absorption is derived as the difference between extinction and scattering. It was found that the organic coatings significantly affect the optical and microphysical properties of the soot aggregates. The size-dependent amplification factors of light scattering were as much as 3.8 and 1.7 with glutaric and succinic acids coatings, respectively. Additional measurements with soot particles that are first coated with glutaric acid and then heated to remove the coating show that both scattering and absorption are enhanced by irreversible restructuring of soot aggregates to more compact globules. These results reveal the microphysical state of soot aerosol with incomplete restructuring in the atmosphere, and advance the treatment of atmospheric aged soot aerosol in the Mie theory shell-and-core model.

Soot aerosols are known to be an important atmospheric constituent. The physical and chemical properties of soot allows it to act as a precursor of gas-surface heterogeneous reactions, providing active sites for the reduction and oxidation of trace species in the atmosphere, potentially affecting atmospheric composition. In this work the heterogeneous reaction of NO2 on soot leading to nitrous acid (HONO) formation was studied through a series of kinetic uptake experiments and HONO yield measurements. The soot was collected from a diffusion flame using propane and kerosene fuels using two different methods. A low pressure fast-flow reactor coupled to a Chemical Ionization Mass Spectrometer (CIMS) was used to monitor NO2 and HONO signals evolution using atmospheric-level NO2 concentration. HONO yields up to 100 percent were measured and NO2 uptake coefficients varying from 5.6x10-6 to 1.6x10-4 were obtained. Heating soot samples before exposure to NO2 increased HONO yield and the NO2 uptake coefficient on soot due to the removal of the organic fraction from the soot backbone unblocking active sites, which become accessible for the heterogeneous reaction. From the kinetic uptake curves and the effect observed in the HONO yield and NO2 uptake coefficient measurements by heating the soot samples, our results support a complex oxidation-reduction mechanism of reaction. This heterogeneous reaction mechanism involves a combination of competitive adsorptive and reductive centers on soot surface where NO2 is converted into HONO, and the presence of processes on soot where HONO can be decomposed producing other products. Atmospheric soot "aging" effect on the reactivity of soot toward NO2 and HONO yield was studied by coating the soot surface with glutaric acid, succinic acid, sulfuric acid, and pyrene. Glutaric and succinic acid increased both HONO yield and the NO2 uptake coefficients, while sulfuric acid decreased both. However, pyrene did not show any particular trend.

Fire models are routinely used to evaluate life safety aspects of building design projects and are being used more often in fire and arson investigations as well as reconstructions of firefighter line-of-duty deaths and injuries. A fire within a compartment effectively leaves behind a record of fire activity and history (i.e., fire signatures). Fire and arson investigators can utilize these fire signatures in the determination of cause and origin during fire reconstruction exercises. Researchers conducting fire experiments can utilize this record of fire activity to better understand the underlying physics. In all of these applications, the fire heat release rate (HRR), location of a fire, and smoke production are important parameters that govern the evolution of thermal conditions within a fire compartment. These input parameters can be a large source of uncertainty in fire models, especially in scenarios in which experimental data or detailed information on fire behavior are not available. To better understand fire behavior indicators related to soot, the deposition of soot onto surfaces was considered. Improvements to a soot deposition submodel were implemented in a computational fluid dynamics (CFD) fire model. To better understand fire behavior indicators related to fire size, an inverse HRR methodology was developed that calculates a transient HRR in a compartment based on measured temperatures resulting from a fire source. To address issues related to the uncertainty of input parameters, an inversion framework was developed that has applications towards fire scene reconstructions. Rather than using point estimates of input parameters, a statistical inversion framework based on the Bayesian inference approach was used to determine probability distributions of input parameters. These probability distributions contain uncertainty information about the input parameters and can be propagated through fire models to obtain uncertainty information about predicted quantities of interest. The Bayesian inference approach was applied to various fire problems and coupled with zone and CFD fire models to extend the physical capability and accuracy of the inversion framework. Example applications include the estimation of both steady-state and transient fire sizes in a compartment, material properties related to pyrolysis, and the location of a fire in a compartment. / text

The steady coflow diffusion flame is a widely used configuration for studying combustion kinetics, flame dynamics, and pollutant formation. In the current work, a set of diluted ethylene-air coflow flames are simulated to study the formation, growth, and oxidation of soot, with a focus on the effects of pressure on soot yield. Firstly, we assess the ability of a high performance CFD solver, coupled with detailed transport and kinetic models, to reproduce experimental measurements, like the temperature field, the species’ concentrations and the soot volume fraction. Fully coupled conservation equations for mass, momentum, energy, and species mass fractions are solved using a low Mach number formulation. Detailed finite rate chemistry describing the formation of Polycyclic Aromatic Hydrocarbons up to cyclopenta[cd]pyrene is used. Soot is modeled using a moment method and the resulting moment transport equations are solved with a Lagrangian numerical scheme. Numerical and experimental results are compared for various pressures. Reasonable agreement is observed for the flame height, temperature, and the concentrations of various species. In each case, the peak soot volume fraction is predicted along the centerline as observed in the experiments. The predicted integrated soot mass at pressures ranging from 4-8 atm, scales as P2.1, in satisfactory agreement with the measured integrated soot pressure scaling (P2.27). Significant differences in the mole fractions of benzene and PAHs, and the predicted soot volume fractions are found, using two well-validated chemical kinetic mechanisms. At 4 atm, one mechanism over-predicts the peak soot volume fraction by a factor of 5, while the other under-predicts it by a factor of 5. A detailed analysis shows that the fuel tube wall temperature has an effect on flame stabilization.

The first goal of this thesis is to validate a detailed co-flow flame soot formation model for high pressure applications. The second goal is to use this detailed model to understand the effect pressure has on soot formation. The third goal is to note any deficiencies in the model, and the fourth is to remedy these issues. The thesis is divided into two research studies. The first study validates the model for high pressure use against ethane-air co-flow diffusion flames from 2 to 15 atm. After validation, the results are used to determine the impact pressure has on the three main soot formation processes. It is determined that the original model could not account for the flame pre-heating effect. The second study addresses this issue by adapting the model to extend below the fuel tube exit plane, and includes conjugate heat transfer (CHT) between the fluid streams and solid fuel tube.

This study employs a novel approach in order to satisfy the need in industry for a computationally inexpensive means to modelling soot formation in engines fuelled by natural gas. The complex geometries found in practical combustion devices along with the requirement to solve turbulent, chemically reacting, and multi-phase flows necessitates this goal. A two-equation model, which tracks soot mass and soot number density, is employed. The goal is to apply this model in engine simulations at Westport Innovations, an industry partner. Experimental data is used to validate the model in various operating conditions. Numerical data obtained from a detailed sectional soot model is also used to augment available validation data, especially with respect to soot formation/oxidation mechanisms. The developed model shows good agreement compared to experimental data and the detailed sectional soot model among all cases considered and will be further tested and applied in Westport’s natural gas engine simulations.

The first goal of this thesis is to validate a detailed co-flow flame soot formation model for high pressure applications. The second goal is to use this detailed model to understand the effect pressure has on soot formation. The third goal is to note any deficiencies in the model, and the fourth is to remedy these issues. The thesis is divided into two research studies. The first study validates the model for high pressure use against ethane-air co-flow diffusion flames from 2 to 15 atm. After validation, the results are used to determine the impact pressure has on the three main soot formation processes. It is determined that the original model could not account for the flame pre-heating effect. The second study addresses this issue by adapting the model to extend below the fuel tube exit plane, and includes conjugate heat transfer (CHT) between the fluid streams and solid fuel tube.

This study employs a novel approach in order to satisfy the need in industry for a computationally inexpensive means to modelling soot formation in engines fuelled by natural gas. The complex geometries found in practical combustion devices along with the requirement to solve turbulent, chemically reacting, and multi-phase flows necessitates this goal. A two-equation model, which tracks soot mass and soot number density, is employed. The goal is to apply this model in engine simulations at Westport Innovations, an industry partner. Experimental data is used to validate the model in various operating conditions. Numerical data obtained from a detailed sectional soot model is also used to augment available validation data, especially with respect to soot formation/oxidation mechanisms. The developed model shows good agreement compared to experimental data and the detailed sectional soot model among all cases considered and will be further tested and applied in Westport’s natural gas engine simulations.

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