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Aerosol mass spectrometers (AMS) are powerful tools in the analysis of the chemical composition of airborne particles, particularly organic aerosols which are gaining increasing attention. However, the advantages of AMS in providing on-line data can be outweighed by the difficulties involved in its use in field measurements at multiple sites. In contrast to the on-line measurement by AMS, a method which involves sample collection on filters followed by subsequent analysis by AMS could significantly broaden the scope of AMS application. We report the application of such an approach to field studies at multiple sites. An AMS was deployed at 5 urban schools to determine the sources of the organic aerosols at the schools directly. PM1 aerosols were also collected on filters at these and 20 other urban schools. The filters were extracted with water and the extract run through a nebulizer to generate the aerosols, which were analysed by an AMS. The mass spectra from the samples collected on filters at the 5 schools were found to have excellent correlations with those obtained directly by AMS, with r2 ranging from 0.89 to 0.98. Filter recoveries varied between the schools from 40 -115%, possibly indicating that this method provides qualitative rather than quantitative information. The stability of the organic aerosols on Teflon filters was demonstrated by analysing samples stored for up to two years. Application of the procedure to the remaining 20 schools showed that secondary organic aerosols were the main source of aerosols at the majority of the schools. Overall, this procedure provides accurate representation of the mass spectra of ambient organic aerosols and could facilitate rapid data acquisition at multiple sites where AMS could not be deployed for logistical reasons.

Long term exposure to vehicle emissions has been associated with harmful health effects. Children are amongst the most susceptible group and schools represent an environment where they can experience significant exposure to vehicle emissions. However, there are limited studies on children’s exposure to vehicle emissions in schools. The aim of this study was to quantify the concentration of organic aerosol and in particular, vehicle emissions that children are exposed to during school hours. Therefore an Aerodyne compact time-of-flight aerosol mass spectrometer (TOF-AMS) was deployed at five urban schools in Brisbane, Australia. The TOF-AMS enabled the chemical composition of the non- refractory (NR-PM1) to be analysed with a high temporal resolution to assess the concentration of vehicle emissions and other organic aerosols during school hours. At each school the organic fraction comprised the majority of NR-PM1 with secondary organic aerosols as the main constitute. At two of the schools, a significant source of the organic aerosol (OA) was slightly aged vehicle emissions from nearby highways. More aged and oxidised OA was observed at the other three schools, which also recorded strong biomass burning influences. Primary emissions were found to dominate the OA at only one school which had an O:C ratio of 0.17, due to fuel powered gardening equipment used near the TOF-AMS. The diurnal cycle of OA concentration varied between schools and was found to be at a minimum during school hours. The major organic component that school children were exposed to during school hours was secondary OA. Peak exposure of school children to HOA occurred during school drop off and pick up times. Unless a school is located near major roads, children are exposed predominately to regional secondary OA as opposed to local emissions during schools hours in urban environments.

This thesis reports a comprehensive study on the physical and chemical properties of airborne particles in Brisbane, especially around schools. The sources and potential toxicity of the particles were identified, enabling an assessment of the contributing factors to children's exposure at school. The results from this thesis give a quantitative estimate of the range of airborne particles that children are exposed to at urban schools with different traffic conditions.

Vehicle emissions have been linked to detrimental health effects with children thought to be more susceptible (See e.g., Ryan et al 2005). In an urban environment a major source of organic aerosols (OA) are vehicle emissions. The ambient concentration of OA is dynamic in nature and the use of an aerosol mass spectrometer can achieve the necessary temporal resolution to capture the daily variation of OA (Jimenez et al 2009). Currently there is a limited understanding of effects of long term exposure to traffic emissions on children’s health. In the present study, we used an aerosol mass spectrometer to monitor OA and determine children’s potential exposure at school to traffic emissions.In this paper, we present the preliminary results of this investigation. The study is a part of a larger project aimed at gaining a holistic picture of the exposure of children to traffic related pollutants, known as UPTECH (www.ilaqh.qut.edu.au/Misc/ UPTECH%20Home.htm).

Atmospheric aerosols are a highly relevant component of the climate system affecting atmospheric radiative transfer and the hydrological cycle. As opposed to other key atmospheric constituents with climatic relevance, atmospheric aerosol particles are highly heterogeneous in time and space with respect to their size, concentration, chemical composition and physical properties. Many aspects of their life cycle are not understood, making them difficult to represent in climate models and hard to control as a pollutant. Aerosol-cloud interactions in particular are infamous as a major source of uncertainty in future climate predictions. Field measurements are an important source of information for the modeling community and can lead to a better understanding of chemical and microphysical processes. In this study, field data from urban, marine, and arid settings are analyzed and the impact of meteorological conditions on the evolution of aerosol particles while in the atmosphere is investigated. Particular attention is given to organic aerosols, which are a poorly understood component of atmospheric aerosols. Local wind characteristics, solar radiation, relative humidity and the presence or absence of clouds and fog are found to be crucial factors in the transport and chemical evolution of aerosol particles. Organic aerosols in particular are found to be heavily impacted by processes in the liquid phase (cloud droplets and aerosol water). The reported measurements serve to improve the process-level understanding of aerosol evolution in different environments and to inform the modeling community by providing realistic values for input parameters and validation of model calculations.

Nonpolar organic compounds (NPOCs) in ambient particulate matter (PM) commonly include n-alkanes, branched alkanes, hopanes and steranes, and polycyclic aromatic hydrocarbons (PAHs). The recent development of thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) has greatly reduced time and labor in their quantification by eliminating the laborious solvent extraction and sample concentration steps in the traditional approach that relies on solvent extraction. The simplicity of the TD-GCMS methods has afforded us concentration data of NPOCs in more than 90 aerosol samples in two aerosol field studies and 20 vehicular emissions-dominated source samples in Hong Kong over the past few years. In this work, we examine the interspecies relationships between select NPOCs and their concentration ratios to elemental carbon (EC) among the ambient samples and among the source samples. Our analysis indicates that hopanes were mainly from vehicular emissions and they were significantly oxidized in ambient PM. The hopane/EC ratio in ambient samples was on average less than half of the ratio in vehicular emissions-dominated source samples. This highlights the necessity in considering oxidation loss in applying organic tracer data in source apportionment studies. Select PAH/EC ratio-ratio plots reveal that PAHs had diverse sources and vehicular emissions were unlikely a dominant source for PAHs in Hong Kong. Biomass burning and other regional sources likely dominated ambient PAHs in Hong Kong. © 2011 Springer-Verlag.

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow.

Here we report a new method for measuring the heterogeneous chemistry of submicron organic aerosol particles using a continuous flow stirred tank reactor. This approach is designed to quantify the real time heterogeneous kinetics, using a relative rate method, under conditions of low oxidant concentration and long reaction times that more closely mimic the real atmosphere. A general analytical expression, which couples the aerosol chemistry with the flow dynamics in the chamber is developed and applied to the heterogeneous oxidation of squalane particles by hydroxyl radicals (OH) in the presence of O2. The particle phase reaction is monitored via photoionization aerosol mass spectrometry and yields a reactive uptake coefficient of 0.51+-0.10, using OH concentrations of 1-7x108 molec cdot cm-3 and reaction times of 1.5+-3 hours. This uptake coefficient is larger than that found for the reaction carried out under high OH concentrations (~;;1x1010 molec cdot cm-3) and short reaction times in a flow tube reactor. This difference suggests that oxidant concentration and reaction time are not interchangeable quantities in reactions of organic aerosols with radicals. In general, this approach provides a new way to examine how the chemical aging of organic particles measured at short reaction times and high oxidant concentrations in flow tubes might differ from the long reaction times and low oxidant levels found in the real atmosphere.

Isoprene, monoterpenes, β-caryophyllene, and toluene are known to be important secondary organic aerosol (SOA) precursors. In this study, characteristic SOA tracers of these precursors were quantified in ambient samples of PM2.5 taken in Hong Kong and their contributions to SOA were estimated using a tracer-based method. Samples were collected every other day from four sampling sites during a field measurement campaign in the summer of 2006. Fourteen SOA tracers, along with twenty-four other polar oxygenated compounds, were identified and quantified using gas chromatography/ion trap mass spectrometry with prior trimethylsilylation. Concentrations of the individual tracers ranged from a few tenths to a few hundreds ng m-3. The tracer concentrations were found to be one order of magnitude higher on days under regional transport influences due to elevated oxidant levels than on days under mainly local emissions influences. Using the measured SOA tracer concentrations in the ambient aerosols and laboratory-derived tracer mass fractions reported by Kleindienst et al. [2007], we estimated that the average SOA attributable to isoprene, monoterpenes, β-caryophyllene, and toluene was 8.83 μg m-3 on days under regional transport influences versus 0.99 μg m-3 on days under mainly local emissions influences, accounting for approximately 45% and 14%, respectively, of the ambient OC concentrations. The tracer-based estimates indicate that monoterpenes and β-caryophyllene are significant contributors to ambient PM2.5 in the summer, which may be due to the high emissions of these biogenic hydrocarbons in Hong Kong.

Atmospheric aerosols play an important role in atmospheric processes. These aerosol particles can affect climate through scattering, transmission and absorption of radiation as well as acting as cloud condensation nuclei. It has recently been found that fatty acids reside on the surfaces of marine and continental aerosols. In this research, an attempt has been made to understand the structures and properties of such organic coated aerosols using Molecular Dynamics simulation. The model particle consisted of a water droplet coated with fatty acid. The density profile (using both Coarse-Grained and Atomistic/United atom models) demonstrated that such aerosol particles have an inverted micelle structure consisting of an aqueous core and with the hydrophobic hydrocarbon tails exposed to the atmosphere. For smaller chains, with the organic molecules directed radially outwards from the water - organic interface) the normal pressure profile showed that the organic coating is under tension resulting in a 'negative' surface tension. As a result, such particles would have an inverse Kelvin vapor pressure effect and would be able to process water vapor despite the hydrophobic surface. Following the work on surface tension, the rate of water uptake by coated aerosols was computed. It was found that the sticking coefficient of water vapor on such particles was about a sixth of that on pure water droplets. This may seem to imply that the net condensation rate is lower, but we also need to take into account the evaporation of water from such particles. With a significant reduction in the evaporation rate (the coating lends greater stability to the particle resulting in reduced evaporation rate), the equilibrium vapor pressure of water on such particles reduced, resulting in a "net water attractor". Thus if such structures were created in sufficient concentration, they might be important contributors in the cloud condensation process. Next the effect of longer Fatty acid molecules

Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are ( 1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/ mass spectrometry; ( 2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and ( 3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at similar to 110 ng m(-3) during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.

The organic compound tracers of atmospheric particulate matter, as well as organic carbon (OC) and elemental carbon (EC), have been characterized for samples acquired during the ACEAsia campaign from Gosan, Jeju Island, Korea; Sapporo, Japan, and Chichi-jima Island in the western North Pacific, as well as on the NOAA R/V Ronald H. Brown. Total extracts were analyzed by GC-MS to determine both polar and aliphatic compounds. Total particles, organic matter and lipid and saccharide compounds were high during the Asian dust episode (early April 2001) compared to levels at other times. The organic matter can be apportioned to seven emission sources and to significant oxidation producing secondary products during long-range transport. Terrestrial natural background compounds are vascular plant wax lipids derived from direct emission and as part of desert sand dust. Fossil fuel utilization is obvious and derives from petroleum product and coal combustion emissions. Saccharides are a major polar (water-soluble) carbonaceous fraction derived from soil resuspension (agricultural activities). Biomass burning smoke is evident in all samples and seasons. It contributes up to 13% of the total compound mass as water-soluble constituents. Burning of refuse is another source of organic particles. Varying levels of marine-derived lipids are superimposed during aerosol transport over the ocean. Secondary oxidation products increase with increasing transport distance and time. The ACEAsia aerosols are comprised not only of desert dust, but also of soil dust, smoke from biomass and refuse burning, and emissions from fossil fuels use in urban areas.

Atmospheric oxidation of monoterpenes contributes to formation of tropospheric ozone and secondary organic aerosol, but their products are poorly characterized. In this work, we report a series of outdoor smog chamber experiments to investigate both gaseous and particulate products in the ozone oxidation of four monoterpenes: alpha-pinene, beta-pinene, Delta(3)-carene, and sabinene. More than ten oxygenated products are detected and identified in each monoterpene/O-3 reaction by coupling derivatization techniques and GC/MS detection. A denuder/filter pack sampling system is used to separate and simultaneously collect gas and aerosol samples. The identified products, consisting of compounds containing carbonyl, hydroxyl, and carboxyl functional groups, are estimated to account for about 34-50%, 57%, 29-67%, and 24% of the reacted carbon mass for beta-pinene, sabinene, alpha-pinene, and Delta(3)-carene, respectively. The identified individual products account for > 83%, similar to 100%, > 90%, and 61% of the aerosol mass produced in the ozone reaction of beta-pinene, sabinene, alpha-pinene, and Delta(3)-carene. The uncertainty in the yield data is estimated to be similar to +/- 50%. Many of the products partition between gas and aerosol phases, and their gas-aerosol partitioning coefficients are determined and reported here. Reaction schemes are suggested to account for the products observed.