Investigating water soluble organic aerosols: Sources and evolution

Many studies are being conducted on the different properties of organic aerosols (OA-s) as it is first emitted into the atmosphere and the consequent changes in these characteristics as OA-s age and secondary organic aerosol (SOA) is produced and in turn aged. This thesis attempts to address some of the significant and emerging issues that deal with the formation and transformation of water-soluble organic aerosols in the atmosphere.;First, a proven method for the measurement of gaseous sulfuric acid, negative ion chemical ionization mass spectrometry (CIMS), has been modified for fast and sensitive measurements of particulate phase sulfuric acid (i.e. sulfate). The modifications implemented on this system have also been the subject of preliminary verifications for measurements of aerosol phase oxalic acid (an organic acid).;Second, chemical and physical characteristics of a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS experiment are presented here. A statistical summary of the emission (or enhancement) ratios relative to carbon monoxide is presented for various gaseous and aerosol species. Extensive investigations of fire plume evolutions were undertaken during the second part of this field campaign. For four distinct Boreal fires, where plumes were intercepted by the aircraft over a wide range of down-wind distances, emissions of various compounds and the effect of aging on them were investigated in detail. No clear evidence of production of secondary compounds (e.g., WSOC and OA) was observed. High variability in emissions between the different plumes may have obscured any clear evidence of changes in the mass of various species with increasing plume age. Also, the lack if tropospheric oxidizing species (e.g., O3 and OH) may have contributed to the lack of SOA formation. Individual intercepts of smoke plumes in this study were segregated by source regions. The normalized excess mixing ratios (NEMR-s) of some gaseous and aerosol compounds were compared. The NEMRs of most species had a high degree of variability that tended to obscure any significant differences between various smoke sources; however, some trends were observed.;Smoke plumes associated with long-range transport from Asia and Siberia showed enhanced sulfate and HCN levels. The fire plumes that were influenced by urban emissions (e.g., intercepted over California) had higher levels of CO2, CH4, NOy and toluene. Overall, pronounced differences were observed when comparing the plumes subject to long-range transport to the ones that were intercepted closer to the fire sources (e.g., the plumes intercepted over California and the ones from Canadian Boreal forest fires). Additionally, when comparing the plumes near the fires, the ones that were influenced by urban emissions (some of the plumes encountered over California) displayed more distinct characteristics than the ones that were less or not influenced by urban emissions.;Data from Teflon filters from the Southeastern United States were analyzed. The filter data show that the fraction of water-soluble light absorbing carbonaceous material is larger in biomass burning plumes regardless of the urban or rural location of the collection of the filter. Indeed, the slope of light absorption at 365 nm (Abs365) vs. WSOC was about 3.5 times higher in filters that were influenced by biomass burning plumes. Also, when the filters were separated into biomass burning and non-biomass burning categories, the slopes of Abs365 vs. WSOC for each category were uniform for all the sites where the filters were collected.;Finally, a new method of simultaneous online measurement of water-soluble aerosol light absorption and WSOC has been presented. The results from an online study are in reasonable agreement with filter studies, although the measurements were collected during two different years and using two different techniques. The hourly averages of the online data showed that the morning rush hour production of WSOC coincides with an increase in Abs365. However, there was no corresponding increase in Abs365 for the daytime photochemical production of WSOC.;As new challenges arise in the area of organic aerosols and their production and fate, the results of this thesis can be used to augment our knowledge of the field and provide information that can be useful in future research.