Biomass burning (BB) is a globally occurring phenomenon that is understood to produce significant quantities of aerosols that have a broad range of local and global effects on humans and the environment. The quantities and properties of primary BB aerosol emissions are difficult to measure and predict, however, due to the natural complexity of the feedstocks and the evolved species, as well as the potential variability in local conditions. Near-source burn parameters, such as fuel composition, fuel mass loss rate, oxygen availability, burn phase, and dilution conditions, contribute to the complexity of BB and have been identified as factors that influence the quantities and physical, optical, and chemical properties of primary BB aerosols. The research presented in this dissertation seeks to elucidate new insights into the mechanisms of primary aerosol formation in naturally occurring biomass burning events by isolating the influences of near-source burn parameters on lignocellulosic biomass and constituent burning aerosols in a controlled laboratory environment. The produced data sets are well-defined and contribute validation data for current and future state-of-the-art aerosol formation models and submodels, as well as other experimental data. Lignocellulosic biomass and the major constituents of lignocellulosic biomass—hemicellulose, cellulose, and lignin—were pyrolyzed and oxidized using thermogravimetric analyzers (TGAs), and the highly repeatable aerosol emissions were characterized in terms of size-resolved number and mass emission factors, concentrations, size, and volatility. The aerosol emissions formed from biomass constituents were then compared to those of biomass, and a novel aerosol prediction model which utilizes superposition of individual constituent results and lignocellulosic biomass composition was developed to test a hypothesis that biomass burning aerosols can be predicted by lignocellulosic composition and constituent emissions when biomass and constituent aerosols are determined under similar conditions. Results showed that lignin and cellulose contents significantly contribute to BB aerosol formation, whereas hemicellulose contributions are less significant. Furthermore, lignin produced lower volatility aerosols compared to hemicellulose and cellulose. Increased absolute fuel mass loss rate was observed during oxidation compared to pyrolysis, and absolute fuel mass loss rate was found to positively correlate with median aerosol size. Increased oxygen availability during burning decreased mass and number emissions, and trends were attributed to complex influences of combustion chemistry and increased fuel mass loss rate from thermal feedback. In an air environment, aerosol number and mass emissions were found to increase and decrease, respectively, with successive pre-ignition pyrolysis, flaming, and post-flaming (smoldering) burn phases. Flaming combustion produced lower volatility emissions compared to pre-ignition pyrolysis and post-flaming smoldering. Results also showed a significant influence of dilution and thermodenuder (TD) temperature on particle size, number, and distribution, with increased dilution air and TD temperature decreasing total number and mass emissions. Regarding the developed superposition prediction model, simulated results well-predicted particle number and mass emission trends in each investigation. Prediction improvements were observed throughout the evolution of the work presented in this dissertation, and the successes and failures of the superposition model under the applied conditions were analyzed. Overall, the influence of near-source burn parameters on primary aerosol emissions was realized, and the potential of the superposition model to predict primary BB aerosol quantities and properties was demonstrated.