Chemical transformations of complex mixtures relevant to atmospheric processes: Laboratory and ambient studies

The study of atmospheric chemistry and chemical transformations, which are relevant to conditions in the ambient atmosphere require the investigation of complex mixtures. In the atmosphere, complex mixtures (e.g. diesel emissions) are continually evolving as a result of physical and chemical transformations. This dissertation examines the transformations of modern diesel emissions (DE) in a series of experiments conducted at the European Outdoor Simulation Chamber (EUPHORE) in Valencia, Spain. Experimental design challenges are addressed, and the development of a NOx removal technology (denuder) is described with results from the application of the newly developed NOx denuder in the most recent EUPHORE campaign (2006). In addition, the data from an ambient aerosol study that examines atmospheric transformation products is presented and discussed.Atmospheric transformations of DE and associated secondary organic aerosol (SOA) production, along with chemical characterization of polar organic compounds (POC) in the EUPHORE experiments, provides a valuable insight on the tranformations of modern DE in environmentally relevant atmospheres. The greatest SOA production occurred in DE with toluene addition experiments (>40%), followed by DE with HCHO (for OH radical generation) experiments. A small amount of SOA (3%) was observed for DE in dark with N2O5 (for NO3 radical production) experiments. Distinct POC formation in light versus dark experiments suggests the role of OH initiated reactions in these chamber atmospheres. A trend of increasing concentrations of dicarboxylic acids in light versus dark experiments was observed when evaluated on a compound group basis. The production of diacids (as a compound group) demonstrates a consistent indicator for photochemical transformation in relation to studies in the ambient atmosphere. The four toluene addition experiments in this study were performed at different [tol]o/[NOx]o ratios and displayed an average SOA %yield (in relation to toluene) of 5.3+/-1.6%, which is compared to past chamber studies that evaluated the impact of [tol]o/[NO x]o on SOA production in more simplified mixtures.Characterization of nitrated polycyclic aromatic hydrocarbons (NPAH, nitroarenes), which have been shown to be mutagenic and/or carcinogenic, was performed on time-intergrated samples from the EUPHORE experiments. NPAH concentrations indicated significant formation and/or degradation was taking place. An inter-experimental comparison showed that distinct gas (2-nitronaphthalene) and particle (2-nitrofluoranthene, 4-nitropyrene) phase NPAH production resulted in light versus dark experiments, and degradation most likely due to photolysis was observed for one of the most abundant NPAH (1-nitropyrene) in the ambient atmosphere. The evaluation of dark experiments in high and low NOx conditions, revealed a significantly higher concentration of gas phase NPAH (mostly due to 1-nitronaphthalene) in high NOx experiments. Electrophilic nitration on chamber surfaces or sampling media can not be ruled out as a possible mechanism for the elevated NPAH concentrations.Chapter 5 presents results from an aerosol sampling study at the Storm Peak Laboratory (SPL) (3210 MSL, 40.45° N, 106.74° W) in the winter of 2007. The unique geographical character of SPL allows for extended observations/sampling of the free tropospheric interface. Of 84 analytes included in the GC-MS method, over 50 individual water extractable POC were present at concentrations greater than 0.1 ngm-3. Diurnal averages over the sampling period revealed a higher total concentration of POC at night, 211 ngm-3 (105-265 ngm-3), versus day, 160 ngm-3 (137-205 ngm -3), which suggests a more aged nighttime aerosol character. During a snow event (Jan. 11-13, 2007), the concentrations of daytime dicarboxylic acids, which may be considered as atmospheric transformation products, were reduced. Lower actinic flux, reduced transport distance, and ice crystal scavenging may explain this variability. Further evaluation of compound ratios (e.g. diacids to monoacids/levoglucosan) and the sampling period dynamics was performed to delineate diurnal aerosol character.