Laminar axisymmetric syngas-air, syngas-methane mixture-air and biogas-air diffusion fames were studied over the pressure range of 5 to 20 atm to investigate the effect of pressure and dilution on soot formation. Spectral soot emission (SSE) optical diagnostic technique was used to measure the soot volume fraction and soot temperature in these flames. The fuel matrix consisted of three syngas fuels, two syngas-methane mixtures and two biogas fuels. In general, soot formation in syngas-methane mixtures and biogas diffusion flames showed strong pressure dependence at lower pressures but this dependence got weaker at elevated pressures. No soot was detected by SSE diagnostic technique in syngas-air flames at all pressures. The suppressive effect of carbon dioxide on soot formation prevailed at all pressures in syngas-methane mixtures and biogas flames.

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

Soot prediction in realistic systems is one of the most challenging problems in theoretical and applied combustion. Soot formation as a chemical process is very complicated and not fully understood up to the moment. The major difficulty stems from the chemical complexity of the soot formation processes as well as its strong coupling with the other thermochemical and fluid processes that occur simultaneously. Soot is a major byproduct of incomplete combustion, having a strong impact on the environment, as well as the combustion efficiency. Therefore, it needs to be predicted in realistic configurations in an accurate and yet computationally efficient way. In the current study, a new soot formation subgrid model is developed and reported here. The new model is designed to be used within the context of the Large Eddy Simulation (LES) framework, combined with Linear Eddy Mixing (LEM) as a subgrid combustion model. The final model can be applied equally to premixed and non-premixed flames over any required geometry and flow conditions in the free, the transition, and the continuum regimes. The soot dynamics is predicted using a Method of Moments approach with Lagrangian Interpolative Closure (MOMIC) for the fractional moments. Since, no prior knowledge of the particles distribution is required, the model is generally applicable. The effect of radiation is introduced as an optically thin model. As a validation the model is first applied to a non-premixed non-sooting flame, then a set of canonically premixed flames. Finally, the model is validated against a non-premixed jet sooting flame. Good results are predicted with reasonable accuracy.

Soot and other products of incomplete combustion play an important role in the chemistry of the atmosphere. As particles are exposed to trace gases, such as ozone, their chemistry and physical properties can be altered leading to changes in their optical properties, as well as their cloud condensation nuclei and ice nucleation abilities. These alterations can lead to changes in the global radiative budget and cloud microphysical processes, which in turn affect the climate. In this study, the chemical and physical changes associated with the oxidation of pyrene, anthracene, and carbon (lampblack) by ozone were investigated. Fourier Transform Infrared Spectroscopy was used to identify oxidation products and track reaction progress for these representative aerosols. A C=O band attributed to a carboxylic acid formation was observed for all three substances, at each level of exposure to ozone - 20 ppm, 40 ppm, and 80 ppm. Second order reaction rate constants ranged from 9.58 x 10-16 cm2 molecules-1 s-1 to 7.71 x 10-13 cm2 molecules-1 s-1. Measurements of water uptake, ice nucleation efficiency, and optical properties were obtained to determine whether any physical changes associated with the oxidation process occurred. Optical measurements show an increase in the ultra-violet absorption of anthracene, but not for pyrene, while an increase in the visible absorption for pyrene was observed, but not for anthracene. Oxidized soot froze at a warmer temperature (-22.8 degrees C) then fresh soot (-25.6 degrees C), showing an increase in ice nucleation efficiency. Our data indicates that oxidation by ozone does alter the chemistry and physical properties of the substances study, leading to possible changes in how they interact with atmospheric processes.

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

Oxidation filters are used to decrease particulate emissions commonly. In this study, design of a particulate trap to produce an alternative, low cost filter has been aimed. An experimental setup has been installed according to standards to carry out tests of these designed filters. Electronic measurement and control systems have been attached to this setup to increase efficiency of experiments. Two filter designs have been used in the experiments. First design consists of aluminum wire cloth. Second design is sheet metal structure, which includes three longitudinal cells. Metal chip is used as filter material. Empty filter tests have been performed firstly, and then experiments have been repeated with aluminum, iron, and copper chip addition in filter. Copper chip test results are better than other metal chip for first experiments. Afterwards, experiments have been repeated with varying copper chip amount. Suitable copper chip amount was determined based on fuel consumption rate of the engine. As a result, designed filter reduce the particulate emissions with high efficiency. Although, carbon monoxide, and carbon dioxide gaseous emissions increase with designed filter, hydro carbon emissions decrease.

A novel nonintrusive soot diagnostics methodology was developed, validated and applied for in-situ determination of temperature, volume fraction and refractive index of soot aggregates formed inside flames by using near-infrared emission spectrometry. Research was conducted in three main parts, first one addressing development and validation of a comprehensive &quot / direct&quot / model for simulation of line-of-sight radiative emission from axisymmetric sooty flames by coupling sub-models for radiative transfer, radiative properties and optical constants. Radiative property estimation for soot agglomerates was investigated by experimentally validating discrete dipole approximation against microwave measurements and using it as reference to assess applicability of simpler Rayleigh-Debye-Gans approximation for fractal aggregates (RDG-FA). Comparisons between predictions of two methods for soot-like model aggregates demonstrated that radiative property predictions of RDG-FA are acceptably accurate for relatively small soot aggregates encountered in small-scale flames. Part two concerns experimental investigation of an axisymmetric ethylene/air diffusion flame by Fourier Transform Near-Infrared spectroscopy. Measurement of line-of-sight emission intensity spectra was performed along with analyses on calibration, noise, uncertainty and reproducibility. A noise characterization approach was introduced to account for spatial fluctuations which were found to dominate over spectral noise. Final part focuses on development, evaluation and application of an inversion methodology that inputs spectral emission intensity measurements from optically thin flames, removes noise, identifies soot refractive index from spectral gradients and retrieves soot temperature and volume fraction fields by tomographic reconstruction. Validation with simulated data and favorable application to measurements indicate that proposed methodology is a promising option for nonintrusive soot diagnostics in flames.

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The first goal of this thesis is to develop and validate a modeling tool into which fundamental combustion chemistry and aerosol dynamics theory are implemented for investigating soot formation/oxidation in multi-dimensional laminar coflow diffusion flames taking into account soot polydispersity and fractal-like aggregate structure. The second goal is to use the tool to study soot aggregate formation/oxidation in experimentally studied laminar coflow diffusion flames to advance the understanding of soot aggregate formation/oxidation mechanism. The first part of the thesis deals with the large CPU time problem when detailed models are coupled together. Using the domain decomposition method, a high performance parallel flame code is successfully developed. An advanced sectional aerosol dynamics model which can model fractal-like aggregate structure is successfully implemented into the parallel flame code. The performance of the parallel code is demonstrated through its application to the modeling of soot formation/oxidation in a laminar coflow CH4/air diffusion flame. The parallel efficiency reaches as high as 83%. The second part of the thesis numerically explores soot aggregate formation in a laminar coflow C2H4/air diffusion flame using detailed PAH-based combustion chemistry and a PAH-based soot formation/oxidation model. Compared to the measured data, flame temperature, axial velocity, C2H2 and OH concentrations, soot volume fraction, the average diameter and the number density of primary particles are reasonably well predicted. However, it is very challenging to predict effectively the average degree of particle aggregation. To do so, particle-particle and fluid-particle interactions that may cause non-unitary soot coagulation efficiency need to be considered. The original coagulation model is enhanced in this thesis to accommodate soot coagulation efficiency. Different types of soot coagulation efficiency are numerically investigated. It is found that a simple adjustment of soot coagulation efficiency from 100% to 20% provides good predictions on soot aggregate structure as well as flame properties. In the third part of the thesis, the effects of oxidation-driven soot aggregate fragmentation on aggregate structure and soot oxidation rate are studied. Three fragmentation models with different fragmentation patterns are developed and implemented into the sectional aerosol dynamics model. The implementation of oxidation-driven aggregate fragmentation significantly improves the prediction of soot aggregate structure in the soot oxidation region.

The first goal of this thesis is to develop and validate a modeling tool into which fundamental combustion chemistry and aerosol dynamics theory are implemented for investigating soot formation/oxidation in multi-dimensional laminar coflow diffusion flames taking into account soot polydispersity and fractal-like aggregate structure. The second goal is to use the tool to study soot aggregate formation/oxidation in experimentally studied laminar coflow diffusion flames to advance the understanding of soot aggregate formation/oxidation mechanism. The first part of the thesis deals with the large CPU time problem when detailed models are coupled together. Using the domain decomposition method, a high performance parallel flame code is successfully developed. An advanced sectional aerosol dynamics model which can model fractal-like aggregate structure is successfully implemented into the parallel flame code. The performance of the parallel code is demonstrated through its application to the modeling of soot formation/oxidation in a laminar coflow CH4/air diffusion flame. The parallel efficiency reaches as high as 83%. The second part of the thesis numerically explores soot aggregate formation in a laminar coflow C2H4/air diffusion flame using detailed PAH-based combustion chemistry and a PAH-based soot formation/oxidation model. Compared to the measured data, flame temperature, axial velocity, C2H2 and OH concentrations, soot volume fraction, the average diameter and the number density of primary particles are reasonably well predicted. However, it is very challenging to predict effectively the average degree of particle aggregation. To do so, particle-particle and fluid-particle interactions that may cause non-unitary soot coagulation efficiency need to be considered. The original coagulation model is enhanced in this thesis to accommodate soot coagulation efficiency. Different types of soot coagulation efficiency are numerically investigated. It is found that a simple adjustment of soot coagulation efficiency from 100% to 20% provides good predictions on soot aggregate structure as well as flame properties. In the third part of the thesis, the effects of oxidation-driven soot aggregate fragmentation on aggregate structure and soot oxidation rate are studied. Three fragmentation models with different fragmentation patterns are developed and implemented into the sectional aerosol dynamics model. The implementation of oxidation-driven aggregate fragmentation significantly improves the prediction of soot aggregate structure in the soot oxidation region.