This treatise studied two correlated important issues in atmospheric chemistry: real-time monitoring of ambient air and removal mechanisms of atmospheric hydrocarbons. An analytical system was designed for the purpose of identification and measurement of sub-ppb level hydrocarbons of different reactivities in air samples. This analytical system was then applied to a series of smog-chamber studies which simulated the removal of reactive hydrocarbons from the atmosphere by reaction with hydroxyl radicals. Six representative atmospheric hydrocarbons ( hexane, octane, toluene, m-xylene, a-xylene and mesitylene) were selected for these experiments. The experimental data indicated that the decay of atmospheric hydrocarbons under laboratory conditions is entirely due to reaction with hydroxyl radicals. The conclusion drawn from a time-resolved plume study that aromatic molecules decay much faster than could be accounted for solely by reaction with hydroxyl radicals was not verified; this indicates a difference between laboratory study and the study in the real atmosphere, and some physical factors besides chemical mechanism might take a more significant role in removing aromatics faster from the atmosphere.

The United States Environmental Protection Agency has estimated that over 111 million people reside in areas that exceed the National Ambient Air Quality Standards for ozone. One major source of the chemical precursors (nitrogen dioxides and volatile organic compounds (VOCs)) for ozone are motor vehicles. The overall goal of this research is to improve the knowledge base related to VOC refueling and evaporative emissions from motor vehicles. Refueling, running loss, hot soak, and diurnal loss total and speciated VOC emissions were investigated. A total of 12 uncontrolled refueling events were completed and involved the determination of volumetric flow rates of gasoline vapor during refueling, as well as total and speciated VOC concentrations. Total VOC emissions were compared with two commonly used algorithms. Speciated VOC vapor profiles were compared with two published gasoline vapor profiles and theoretical predictions based on knowledge of liquid composition and environmental conditions. An evaluation of refueling emissions impacts on ozone formation potentials using MIR was completed and results were compared against speciated emissions and MOBILE-based total VOC emissions estimates coupled with a default speciation profile. Refueling VOC emissions and resultant ozone formation potential may be underestimated in existing emission inventories, particularly during the summer ozone season, A model was developed to predict the speciation of VOCs associated with evaporative emissions from motor vehicles. Model-predicted speciation profiles were evaluated using SHED studies. Running loss, hot soak and diurnal emissions were included in each test. Total VOC emissions measured during each test were compared against MOBILE6 predicted emissions. An evaluation of evaporative emissions impacts on ozone formation potentials using MIR was completed, comparing measured and predicted emissions. The measured:predicted speciation results ranged between 0.93 and 1.11 and had an average value of 1.02. For the conditions tested, MOBILE6 underestimated evaporative emissions in 20 of 24 comparisons. MOBILE6-based ozone formation potentials may be underestimated.

This thesis characterizes the ambient fine organic carbon aerosol and investigates its sources through the development and deployment of new measurement techniques. The focus is on organic compounds that are soluble in water (WSOC), which comprise a large fraction of the organic aerosol, yet little has been known about its chemical nature. A method was developed for quantitative on-line measurements of WSOC by using a Particle-into-Liquid Sampler (PILS) to capture ambient particles into a flow of purified water, which is then forced through a liquid filter and the carbonaceous content quantified by a Total Organic Carbon (TOC) analyzer. This system allows for a continuous 6 minute (ground-based) or 3 s integrated measurement (airborne) with a limit of detection of 0.1 microgramsC/m3 and uncertainty of 10%. Furthermore, a new quantitative method was developed to group speciate the WSOC. In the first step, WSOC is separated by use of XAD-8 resin into its hydrophilic (WSOCxp) and hydrophobic (WSOCxr) fractions. This separation can be performed on-line by coupling the XAD-8 column with the PILS-TOC or off-line on WSOC extracted from integrated filter samples. If off-line, a second step involving size-exclusion chromatography (SEC) is used to chromatographically separate by organic functional groups the WSOCxp and recovered hydrophobic fraction (WSOCxrr). During this step, the WSOCxp is further separated into aliphatic acids with less than four carbons, neutrals, and bases. The WSOCxrr can be separated into acids and neutrals. Results showing the capabilities of the PILS-TOC both on the ground at the St. Louis Midwest Supersite and when airborne during the New England Air Quality Study/Intercontinental Transport and Chemical Transformation 2004 mission conducted in the northeastern U.S. will be presented. Ambient results from urban sites where a PILS-TOC was coupled with a XAD-8 column will be discussed. Data from the two-step speciation performed on samples collected from urban Atlanta summer and winter, and biomass burning in rural Georgia in a region of prescribed burning are presented. Finally, WSOC measurements obtained in Atlanta and its surrounding regions from both the speciation measurements and PILS-TOC will be used to investigate the sources of WSOC in the southeastern U.S.

Plants emit a diverse range of biogenic volatile organic compounds (BVOCs) into the atmosphere, of which isoprene is the most abundantly emitted. Isoprene significantly affects biological and atmospheric processes, but the range of isoprene and BVOCs present in bamboos has not been well characterized. In this thesis I explore the range of isoprene emission found in bamboos and relate it to plant morphological and physiological characteristics. In addition, I measure and relate the entire suite of BVOCs present in the bamboos to their fundamental isoprene emission rate. Interspecific variation in isoprene emission documented in a comprehensive survey of bamboos. Two groups of bamboo species were measured in the greenhouse and the field. Elevated photosynthetic rate was significantly correlated with isoprene emission. In the field, dark respiration rate was highest in bamboos that made the least amount of isoprene. The total BVOC suite was significantly influenced by whether or not leaf-level isoprene emission was present. I conclude that bamboos vary with regard to physiology, morphology, and total BVOC suite and that isoprene emission is correlated with these changes, and introduce the bamboos as a novel system for studying the impacts of isoprene emission.

The oxidation of volatile organic compounds (VOCs) plays a role in both regional and global air quality through the formation of secondary organic aerosols (SOA). More than 1000TgC/yr of non-methane VOCs are emitted from biogenic sources (significantly greater than from anthropogenic sources). Despite this magnitude and potential importance for air quality, the body of knowledge around the identities, quantities and oxidation processes of these compounds is still incomplete (e.g., Goldstein & Galbally, 2007; Robinson et al., 2009). Two-dimensional gas chromatography paired with time-of-flight mass spectrometry (GC×GC/TOFMS) is a powerful analytical technique which is explored here for its role in better characterizing biogenic VOCs (BVOCs) and thus SOA precursors. This work presents measurements of BVOCs collected during two field campaigns and analyzed using GC×GC/TOFMS. The first campaign, the Bio-hydro-atmosphere Interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS), took place in a Ponderosa pine forest in Colorado. The second campaign, Particle Investigations at a Northern Ozarks Tower: NOx, Oxidant, Isoprene Research (PINOT NOIR) Study, was conducted in the Ozark region of Missouri. Tens to hundreds of BVOCs were quantified in each set of samples, including primary emissions, atmospheric oxidation products, stress indicators and semi-volatile leaf surface compounds. These findings highlight that there is a largely uncharacterized diversity of BVOCs in ambient samples. Our findings demonstrate that GC×GC can distinguish between compounds with the same molecular weight and similar structures, which have highly variable potentials for production of SOA (Lee et al., 2006). This work represents some of the first analysis of ambient BVOCs with this technology, which is anticipated to contribute greatly to characterization of atmospheric SOA precursors and ultimately, regional and global modeling of SOA and fine particulate matter.