The research in this dissertation explored the sources and chemistry of organic nitrogen aerosols in the atmosphere. Two approaches were employed: field measurements and laboratory experiments. In order to characterize atmospheric aerosol, two ambient studies were conducted in Cache Valley in Northern Utah during strong winter inversions of 2004 and 2005. The economy of this region is heavily dependent on agriculture. There is also a fast growing urban population. Urban and agricultural emissions, aided by the valley geography and meteorology, led to high concentrations of fine particles that often exceeded the national ambient air quality standards. Aerosol composition was dominated by ammonium nitrate and organic species. Mass spectra from an aerosol mass spectrometer revealed that the organic ion peaks were consistent with reduced organic nitrogen compounds, typically associated with animal husbandry practices. Although no direct source characterization studies have been undertaken in Cache Valley with an aerosol mass spectrometer, spectra from a study at a swine facility in Ames, Iowa, did not show any evidence of reduced organic nitrogen species. This, combined with temporal and diurnal characteristics of organic aerosol peaks, was a pointer that the organic nitrogen species in Cache Valley likely formed from secondary chemistry. Application of multivariate statistical analyses to the organic aerosol spectra further supported this hypothesis. To quantify organic nitrogen signals observed in ambient studies as well as understand formation chemistry, three categories of laboratory experiments were performed. These were calibration experiments, smog chamber studies, and an analytical method development. Laboratory calibration experiments using standard calibrants indicated that quantifying the signals from organic nitrogen species was dependent on whether they formed through acid-base chemistry or via secondary organic aerosol pathway. Results from smog chamber reactions of amines with ozone, nitrogen oxides, nitrate radical, and nitric acid showed that the secondary organic aerosol pathway was more plausible than acid-base chemistry, thus making the contribution of the organic nitrogen species to the total aerosol mass in Cache Valley significant. Gas phase and aerosol products formed from the smog chamber reactions were identified and used to devise reaction mechanisms. Finally, an ion chromatographic method for detecting and quantifying some key organic nitrogen species in aerosol was developed and tested.

Disertacija skirta smulkiosios aerozolio dalelių frakcijos šaltinių, fizikinių ir cheminių savybių įvertinimui kompleksiškai apjungiant įvairius tyrimo metodus. Darbe susieti elementinės ir organinės anglies koncentracijų pokyčiai su tolimąja oro masių pernaša, įvertinta regiono bei vietinių šaltinių įtaka bendrai aerozolio dalelių taršai. Aprašyti anglies turinčių aerozolio dalelių pasiskirstymai pagal dydį foninėse vietovėse ir miesto aplinkoje. Naudojant aerozolio masių spektrometrą Preilos atmosferos užterštumo tyrimų stotyje buvo identifikuotas biogeninis organinių medžiagų šaltinis, kuris vidutiniškai sudaro 15 % nuo organinių medžiagų masės, tačiau Šiaurės Atlanto oro masėje biogeninių medžiagų indėlis siekia net 50 %. Atlikus kompleksinę aerozolio ir stabiliųjų anglies izotopų masių spektrometrinę analizę buvo nustatyta, kad pirminis anglies turinčio aerozolio dalelių šaltinis mieste yra autotransportas, o Rūgšteliškio foninėje vietovėje – biomasės deginimas. Taip pat buvo nustatyta, kad Vilniuje dominavo antropogeninės antrinės organinės medžiagos (76 %), o Rūgšteliškyje vyravo biogeninės antrinės organinės medžiagos (apie 50%). Vertinant tolimosios oro masių pernašos įtaką vietinės kilmės aerozolio dalelių formavimuisi ir kaitai, buvo nustatyta, kad vulkaninės kilmės aerozolio dalelės turi įtakos submikroninės aerozolio dalelių frakcijos koncentracijai, cheminei sudėčiai ir pasiskirstymui pagal dydį. / The objective of the work was to investigate physical and chemical properties and sources of the atmospheric aerosol particles in the submicron fraction by combining different analytical techniques. The dependence of concentrations of organic and elemental carbon in different air masses was determined and the contribution of regional and local sources to the net aerosol particle pollution was estimated. Analysis of the size distribution of carbonaceous aerosol particles in background and urban areas was performed. Biogenic organic aerosol made up 15 % of the organic aerosol mass at the Preila atmospheric pollution research station, but in the North Atlantic air masses this factor was up to 50 %. Aerosol and stable isotope ratio mass spectrometry has revealed that traffic is the primary source of aerosol particles in the city, while biomass burning is the primary source at the Rūgšteliškis background station. It was determined that secondary anthropogenic organic compounds were dominating (76 %) in Vilnius, while in Rūgšteliškis secondary biogenic organic compounds made up 50 % of the total organic aerosol mass. The influence of the long-range air mass transport on the local origin aerosol particle formation and transformation has been evaluated and it has been shown that volcanic aerosol particles can significantly change the concentration, chemical composition and size distribution of local aerosol particles in the submicron range.

The objective of the work was to investigate physical and chemical properties and sources of the atmospheric aerosol particles in the submicron fraction by combining different analytical techniques. The dependence of concentrations of organic and elemental carbon in different air masses was determined and the contribution of regional and local sources to the net aerosol particle pollution was estimated. Analysis of the size distribution of carbonaceous aerosol particles in background and urban areas was performed. Biogenic organic aerosol made up 15 % of the organic aerosol mass at the Preila atmospheric pollution research station, but in the North Atlantic air masses this factor was up to 50 %. Aerosol and stable isotope ratio mass spectrometry has revealed that traffic is the primary source of aerosol particles in the city, while biomass burning is the primary source at the Rūgšteliškis background station. It was determined that secondary anthropogenic organic compounds were dominating (76 %) in Vilnius, while in Rūgšteliškis secondary biogenic organic compounds made up 50 % of the total organic aerosol mass. The influence of the long-range air mass transport on the local origin aerosol particle formation and transformation has been evaluated and it has been shown that volcanic aerosol particles can significantly change the concentration, chemical composition and size distribution of local aerosol particles in the submicron range. / Disertacija skirta smulkiosios aerozolio dalelių frakcijos šaltinių, fizikinių ir cheminių savybių įvertinimui kompleksiškai apjungiant įvairius tyrimo metodus. Darbe susieti elementinės ir organinės anglies koncentracijų pokyčiai su tolimąja oro masių pernaša, įvertinta regiono bei vietinių šaltinių įtaka bendrai aerozolio dalelių taršai. Aprašyti anglies turinčių aerozolio dalelių pasiskirstymai pagal dydį foninėse vietovėse ir miesto aplinkoje. Naudojant aerozolio masių spektrometrą Preilos atmosferos užterštumo tyrimų stotyje buvo identifikuotas biogeninis organinių medžiagų šaltinis, kuris vidutiniškai sudaro 15 % nuo organinių medžiagų masės, tačiau Šiaurės Atlanto oro masėje biogeninių medžiagų indėlis siekia net 50 %. Atlikus kompleksinę aerozolio ir stabiliųjų anglies izotopų masių spektrometrinę analizę buvo nustatyta, kad pirminis anglies turinčio aerozolio dalelių šaltinis mieste yra autotransportas, o Rūgšteliškio foninėje vietovėje – biomasės deginimas. Taip pat buvo nustatyta, kad Vilniuje dominavo antropogeninės antrinės organinės medžiagos (76 %), o Rūgšteliškyje vyravo biogeninės antrinės organinės medžiagos (apie 50%). Vertinant tolimosios oro masių pernašos įtaką vietinės kilmės aerozolio dalelių formavimuisi ir kaitai, buvo nustatyta, kad vulkaninės kilmės aerozolio dalelės turi įtakos submikroninės aerozolio dalelių frakcijos koncentracijai, cheminei sudėčiai ir pasiskirstymui pagal dydį.

Organic aerosols represent one of the main sources of uncertainty affecting attempts to quantify anthropogenic climate change. The diverse physical and chemical properties of organic aerosols and the varied pathways involved in their formation and aging form the basis of this uncertainty, preventing extensive and accurate representation within regional and global scale models. This inability to constrain the radiative forcings produced by organic aerosols within the atmosphere consequently acts as a limitation to the wider objective of providing reliable projections of future climate. Biomass burning constitutes one of the main anthropogenic contributions to the global atmospheric organic aerosol (OA) burden, particularly in tropical regions where the potential for perturbations to the climate system is also enhanced due to higher average levels of solar irradiance. Emissions from biomass burning have been the subject of an intense research focus in recent years, involving a combination of field campaigns and laboratory studies. These experiments have aimed to improve the limited understanding of the processes involved in the evolution of biomass burning organic aerosol (BBOA) and contribute towards the development of more robust parameterisations for climate and chemical transport models. The main objective of this thesis was to use datasets acquired from several different global regions to perform a broad analysis of the BBOA fraction, with the extensive temporal and spatial scales provided by such measurements enabling investigation of a number of key uncertainties, including regional variability in emissions and the role of secondary organic aerosol (SOA) formation in aging smoke plumes. Measurements of BBOA mass concentration obtained using Aerodyne Research Inc. Aerosol Mass Spectrometers (AMS) were used to calculate characteristic ΔOA/ΔCO ratios for different environments, accounting for the effects of dilution and contrasting fire sizes to give a proportional representation of OA production. High levels of variability in average ΔOA/ΔCO were observed both between and within different regions. The scale of this variability consistently exceeded any differences between plumes of different ages, while a widespread absence of any sustained increase in ΔOA/ΔCO with aging indicates that SOA formation does not provide a net increase in OA mass. Despite this lack of OA enhancement, increasing proportions of oxygenated OA components in aged plumes highlight the chemical transformations occurring during the evolution of BBOA, and the additional influence of OA loss through evaporation or deposition. Potential drivers of variability in ΔOA/ΔCO at source, such as changes in fuel types and combustion conditions, were investigated for controlled fires carried out within a combustion chamber. These laboratory experiments revealed a number of complex relationships between BB emissions and source conditions. Although ΔOA/ΔCO was shown to be influenced by both fuel properties and transitions between flaming and smouldering combustion phases, the extent of these effects was limited, while variability between fires exceeded levels observed for ambient measurements. These findings emphasise the complexity of the BBOA lifecycle and the need to address the extensive uncertainties associated with its various constituent processes, in order to improve understanding of eventual climate impacts from biomass burning.

Atmospheric aerosol is an important component of our atmosphere influencing human health, regional and global atmospheric chemistry and climate. The organic component of submicron aerosol contributes around 50% of its mass and is a complex mixture of tens of thousands of compounds. Real-time aerosol mass spectrometry was the major measurement tool used in this work. The Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) can quantitatively measure the chemical composition and size distribution of non-refractory submicron aerosol (NR-PM1). The mass spectra provided by the instrument every few minutes contain information about aerosol sources and processes. This thesis uses the HR-ToF-AMS measurements in two areas of Greece to quantify the contributions of organic aerosol sources to the corresponding organic aerosol levels. Local and regional air pollution sources were monitored and characterized in two sites during intensive campaigns. The first campaign took place during the fall of 2011 (September 24 to October 23) in Finokalia, Crete, a remote-background coastal site without any major human activity. The aim of the study was to quantify the extent of oxidation of the organic aerosol (OA) during autumn, a season neither too hot nor cold, with reduced solar radiation in comparison to summer. The second one took place during the winter of 2012 (February 26 to March 5), in the third major city of Greece, Patras. The measurements were conducted in the campus of the Technological Educational Institute of Patras (TEI), in order to quantify the severity of the wintertime air pollution problem in the area and its sources. The contributions of traffic and residential wood burning were the foci of that study. The Finokalia site is isolated and far away from anthropogenic sources of pollution, making it ideal for the study of organic aerosol coming from different directions, usually exposed to high levels of atmospheric oxidants. The fine PM measured during the Finokalia Atmospheric Measurement Experiment (FAME-11) by the AMS and a Multi Angle Absorption Photometer (MAAP) was mostly ammonium sulfate and bisulfate (60%), organic compounds (34%), and BC (5%). The aerosol sampled originated mainly from Turkey during the first days of the study, but also from Athens and Northern Greece during the last days of the campaign. By performing Positive Matrix Factorization (PMF) analysis on the AMS organic spectra for the whole dataset the organic aerosol (OA) composition could be explained by two components: a low volatility factor (LV-OOA) and a semi-volatile one (SV-OOA). Hydrocarbon-like organic aerosol (HOA) was not present, consistent with the lack of strong local sources. The second field campaign took place in the suburbs of the city of Patras, 4 km away from the city center during the winter of 2012. During this 10-day campaign, organics were responsible for 70% during the day and 80% during the evening of the total PM1. The OA mean concentration during that period was approximately 20 μg m-3 and reaching hourly maximum values as high as 85 μg m-3. Sulfate ions and black carbon followed with 10% and 7% of the PM1. PMF analysis of the organic mass spectra of PM1 explained the OA observations with four sources: cooking (COA), traffic (HOA), biomass burning (BBOA), and oxygenated aerosol (OOA), related to secondary formation and long range transport. On average, BBOA represented 58% of the total OM, followed by OOA with 18%, COA and HOA, with the last two contributing of the same percentage (12%). / --

Atmospheric aerosols have adverse effects on human health, air quality, and visibility and frequently result in severe pollution events, particularly in urban areas. However, the sources of aerosols and the processes governing their behaviour in the atmosphere, including those which lead to high concentrations, are not well understood thus limit our ability to accurately assess and forecast air quality. Presented here are the first long-term chemical composition measurements from an urban environment using an Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS). Organic aerosols (OA) were observed to account for a significant fraction (44%) of the total non-refractory submicron mass during 2012 at the urban background site in North Kensington, London, followed by nitrate (28%), sulphate (14%), ammonium (13%), and chloride (1%). The sources and components of OA were determined using Positive Matrix Factorisation (PMF) and attributed as hydrocarbon-like OA (HOA), cooking OA (COA), solid fuel OA (SFOA), type 1 oxygenated OA (OOA1), and type 2 oxygenated OA (OOA2), where HOA, COA, and SFOA were observed to be of equal importance across the year. The concentration of secondary OA increased during the summer yet the extent of oxidation, as defined by the oxygen content, showed no variability during the year. The main factors governing the diurnal, monthly, and seasonal trends observed in all organic and inorganic species were meteorological conditions, specific nature of the sources, and availability of precursors. Regional and transboundary pollution influenced total aerosol concentrations and high concentration events were observed to be governed by different factors depending on season. High-Resolution ToF-AMS measurements were used to further probe OA behaviour, where two SFOA factors were derived from PMF analysis in winter, which likely represent differences in burn conditions. In the summer an OA factor was identified, likely of primary origin, which was observed to be strongly associated with organic nitrates and anthropogenic emissions. This work uses instruments and techniques that have not previously been used in this way in an urban environment, where the results further the understanding of the chemical components of urban aerosols. Aerosol sources are likely to change in the future with increases in solid fuel burning as vehicular emissions decrease, with significant implications on air quality and health. Thus it is important to understand aerosol sources and behaviour in order to develop effective pollution abatement strategies.

Atmospheric fine particulate matter (PM2.5), which is mostly formed in the atmosphere from precursor gases, contributes to numerous environmental and health concerns. Quantifying the ambient concentrations of PM2.5 and precursor gases can be challenging. Hence, many scientific questions about the formation, chemical composition, and gas/particle partitioning of PM2.5 remain unanswered. Ambient Ion Monitor - Ion Chromatography (AIM-IC) was characterized and utilized to measure the water-soluble composition of PM2.5 (dominated by pNH4+, pSO42-, and pNO3-) and associated precursor gases (dominated by NH3(g), SO2(g), and HNO3(g)) during two field campaigns. The AIM-IC detection limits for hourly sampling were determined to be 3 - 45 ng m-3. The response time for “sticky” gases was significantly improved with a nylon denuder membrane. A novel inlet configuration for the AIM-IC, which minimizes sampling inlet losses and carryover in sample analyses, was implemented. Measurements from the BAQS-Met 2007 campaign were utilized to assess the accuracy of the AURAMS model and investigate gas/particle partitioning in SW Ontario. Due to high sulphate levels, NH3(g) was the limiting chemical factor in the formation and gas/particle partitioning of PM2.5. The errors in the predictions of relative humidity and free ammonia were responsible for the poor agreement iii between modelled and measured pNO3- values. The AIM-IC measurements from the CalNex 2010 study were compared to the CMAQ model and utilized to investigate the gas/particle partitioning in Bakersfield, CA. Very high NH3(g) concentrations were observed, and the formation and partitioning of PM2.5 was limited by HNO3(g) and H2SO4. Evidence of rapid removal of HNO3(g) by interactions with super-micron dust particles, and possibly with the alkaline surface was found. CMAQ exhibited significant biases in the predicted concentrations of pSO42-, NH3(g) and HNO3(g).

Atmospheric fine particulate matter (PM2.5), which is mostly formed in the atmosphere from precursor gases, contributes to numerous environmental and health concerns. Quantifying the ambient concentrations of PM2.5 and precursor gases can be challenging. Hence, many scientific questions about the formation, chemical composition, and gas/particle partitioning of PM2.5 remain unanswered. Ambient Ion Monitor - Ion Chromatography (AIM-IC) was characterized and utilized to measure the water-soluble composition of PM2.5 (dominated by pNH4+, pSO42-, and pNO3-) and associated precursor gases (dominated by NH3(g), SO2(g), and HNO3(g)) during two field campaigns. The AIM-IC detection limits for hourly sampling were determined to be 3 - 45 ng m-3. The response time for “sticky” gases was significantly improved with a nylon denuder membrane. A novel inlet configuration for the AIM-IC, which minimizes sampling inlet losses and carryover in sample analyses, was implemented. Measurements from the BAQS-Met 2007 campaign were utilized to assess the accuracy of the AURAMS model and investigate gas/particle partitioning in SW Ontario. Due to high sulphate levels, NH3(g) was the limiting chemical factor in the formation and gas/particle partitioning of PM2.5. The errors in the predictions of relative humidity and free ammonia were responsible for the poor agreement iii between modelled and measured pNO3- values. The AIM-IC measurements from the CalNex 2010 study were compared to the CMAQ model and utilized to investigate the gas/particle partitioning in Bakersfield, CA. Very high NH3(g) concentrations were observed, and the formation and partitioning of PM2.5 was limited by HNO3(g) and H2SO4. Evidence of rapid removal of HNO3(g) by interactions with super-micron dust particles, and possibly with the alkaline surface was found. CMAQ exhibited significant biases in the predicted concentrations of pSO42-, NH3(g) and HNO3(g).