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Organic aerosol (OA) is a ubiquitous component of atmospheric particulate that influences both human health and global climate. A large fraction of OA is secondary in nature (SOA), being produced by oxidation of volatile organic compounds (VOCs) emitted by biogenic and anthropogenic sources. Despite the integral role of SOA in atmospheric processes, there remains a limited scientific understanding of the chemical and physical changes induced in SOA as it ages in the atmosphere. This thesis describes work done to increase the knowledge of processes and properties of atmospherically relevant SOA. In the work presented in this thesis, I have worked on improving an existing innovative, soft ionization aerosol mass spectrometer and utilized it to establish chemical mechanisms for oxidation of atmospherically relevant organic precursors (i.e., Green Leaf Volatiles). I discovered that SOA formation from cis-3-hexen-1-ol is dominated by oligomer and higher molecular weight products, whereas the acetate functionality in cis-3-hexenylacetate inhibited oligomer formation, resulting in SOA that is dominated by low molecular weight products. One of the most important factors contributing to uncertainties in our estimations of SOA mass in the atmosphere, remains our basic assumption that atmospheric SOA is liquid-like, which we have found to be untrue. Hence, I developed a methodology to estimate the phase state of SOA and identified new parameters that can have significant influence on the phase state of atmospheric aerosol. This simplified method eliminates the need for a Scanning Mobility Particle Sizer (SMPS) and directly measures Bounce Factor (BF) of polydisperse SOA using only one multi-stage cascade Electrostatic Low Pressure Impactor (ELPI). The novel method allows for the real time determination of SOA phase state, permitting studies of the relationship between SOA phase, oxidative formation and chemical aging in the atmosphere. I demonstrated that SOA mass loading (CSOA) influences the phase state significantly. Results show that under nominally identical conditions, the maximum BF decreases by approximately 30% at higher CSOA and suggests that extrapolation of experiments not conducted at atmospherically relevant SOA levels to simulate the chemical properties may not yield results that are relevant to our natural environment. My work has provided a better understanding of the mechanisms of aerosol formation at atmospheric concentrations, which is necessary to understand its physical properties. This improved understanding is fundamental to accurately model aerosol formation in the atmosphere, and subsequently evaluate their large-scale effect on human health and environment.
The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C12 alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NOx levels, such that RO2 + HO2 chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed. Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position. The photooxidation of several C12 alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the effect of molecular structure on SOA yields and photochemical aging. Peroxyhemiacetal formation from the reactions of several multifunctional hydroperoxides and aldehyde intermediates was found to be central to organic growth in all systems, and SOA yields increased with cyclic character of the starting hydrocarbon. All of these studies provide direction for future experiments and modeling in order to lessen outstanding discrepancies between predicted and measured SOA.
Secondary organic aerosol (SOA) is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical and physical processes. Understanding the formation and transformation processes of SOA via aqueous-phase reactions is important for properly presenting its atmospheric evolution pathways in models and for elucidating its climate and health effects. Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the formation and evolution of phenol (C6H6O), guaiacol (C7H8O2; 2-methoxyphenol) and syringol (C8H10O3; 2,6-dimethoxyphenol) and with two major aqueous phase oxidants -- the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (·OH) - and interpret the reaction mechanisms. In addition, given that dissolved organic matter (DOM) is an important component of fog and cloud water and that it can undergo aqueous reactions to form more oxidized, less volatile species, we further investigate the photochemical processing of DOM in fog water to gain insights into the aqueous-phase processing of organic aerosol (OA) in the atmosphere. In Chapter 2, we thoroughly characterize the bulk chemical and molecular compositions of phenolic aqSOA formed at half-life (t[subscript 1/2]), and interpret the formation mechanisms. We find that phenolic aqSOA formed at t[subscript 1/2] is highly oxygenated with atomic oxygen-to-carbon ratio (O/C) in the range of 0.85-1.23. Dimers, higher oligomers (up to hexamers), functionalized monomers and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acids are detected. Compared with ·OH-mediated reactions, reactions mediated by 3C* are faster and produce more oligomers and hydroxylated species at t[subscript1/2]. We also find that aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are an important source of secondary brown carbon in the atmosphere, especially in regions impacted by biomass burning. In Chapter 3, we investigate the chemical evolution of phenolic aqSOA via aqueous-phase reactions on the molecular level and interpret the aging mechanisms. Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation. Functionalization and fragmentation become dominant at later stages, forming a variety of functionalized aromatic and ring-opening products with higher carbon oxidation states. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules. In addition, phenolic aqSOA has a wide range of saturation vapor pressures (C*), varying from 10−20 [mu]g m−3 for functionalized phenolic oligomers to 10 [mu]g m−3 for ring-opening species with number of carbon less than 6. The detection of abundant extremely low volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere. Chapter 3 investigates the molecular transformation with aging based on the characterization of three aqSOA filter samples collected at the defined time intervals of the photoreaction. However, the chemical evolution of aqSOA products with hours of illumination at a higher time resolution is largely unknown. In Chapter 4, we investigate the chemical evolution of aqSOA at a 1-min time resolution based on high-resolution aerosol mass spectrometer (AMS) analysis. This is important for understanding the continuous evolution of phenolic aqSOA with aging as well as for elucidating the formation and transformation of different generations of products. Our results suggest that dimer and higher-order oligomers (trimers, tetramers, etc.) are formed continuously during the first 1-2 hours of photoreaction but show a gradual decrease afterwards. Functionalized derivatives grow at a later time and then gradually decrease. Highly oxidized ring-opening species continuously increase over the course of reactions. Positive matrix factorization (PMF) analysis of the AMS spectra of phenolic aqSOA identifies multiple factors, representing different generations of products. The 1st-generation products include dimers, higher-order oligomers and their oxygenated derivatives. The 2nd-generation products include oxygenated monomeric derivatives. The 3rd-generation products include highly oxidized ring-opening species. In Chapter 5, we investigate the evolution of dissolved organic matter (DOM) in fog water. Our results show that the mass concentration of DOM[subscript OA] (i.e., low-volatility DOM in fog water) is enhanced over the course of illumination, with continuous increase of O/C and atomic nitrogen-to-carbon ratio (N/C). The increase of DOM[subscript OA] is due to the incorporation of oxygen- and nitrogen-containing functional groups into the molecules. The aqueous aging of DOM[subscript OA] can be modeled as a linear combination of the dynamic variations of 3 factors using PMF analysis. Factor 1 is chemically similar to the DOM[subscript OA] before illumination, which is quickly reacted away. Factor 2 is representative of an intermediate component, which is first formed and then transformed, and O/C of Factor 2 is intermediate between that of Factor 1 and Factor 3. Factor 3 represents highly oxidized final products, which is continuously formed during illumination. Fog DOM absorbs significantly in the tropospheric sunlight wavelengths, but this absorption behavior stays almost constant over the course of illumination, despite the significant change in chemical composition.
The uncertainties in the aerosol effects on radiative forcing limit our knowledge of climate change, presenting us with an important research challenge. Aerosols in Atmospheric Chemistry introduces basic concepts about the characterization, formation, and impacts of ambient aerosol particles as an introduction to graduate students new to the field. Each chapter also provides an up-to-date synopsis of the latest knowledge of aerosol particles in atmospheric chemistry.
Atmospheric aerosols are an important and a highly complex component of the Earth’s atmosphere that alter the radiative forcing and the chemical composition of the gas phase. These effects have impacts on local air quality and the global climate. Atmospheric Aerosol Chemistry outlines research findings to date in aerosol chemistry and advances in analytical tools used in laboratory settings for studying their surface and bulk reactivity.
Atmospheric Aerosols is a vital problem in current environmental research due to its importance in atmospheric optics, energetics, radiative transfer studies, chemistry, climate, biology and public health. Aerosols can influence the energy balance of the terrestrial atmosphere, the hydrological cycle, atmospheric dynamics and monsoon circulations. Because of the heterogeneous aerosol field with large spatial and temporal variability and reduction in uncertainties in aerosol quantification is a challenging task in atmospheric sciences. Keeping this in view the present study aims to assess the impact of aerosols on coastal Indian station Visakhapatnam and the adjoining Bay of Bengal. An aerosol is a colloid of fine solid particles or liquid droplets, in air or another gas. Aerosols can be natural or not. Examples of natural aerosols are fog, forest exudates and geyser steam.
The immense chemical complexity of atmospheric organic particulate matter ("aerosol") has left the general field of condensed-phase atmospheric organic chemistry relatively under-developed when compared with either gas-phase chemistry or the formation of inorganic compounds. In this work, we endeavor to improve the general understanding of the narrow class of oxidation reactions that occur at the interface between the particle surface and the gas-phase. The heterogeneous oxidation of pure erythritol (C4H1 00 4 ) and levoglucosan (C6H1 00 5) particles by hydroxyl radical (OH) was studied first in order to evaluate the effects of atmospheric aging on the mass and chemical composition of atmospheric organic aerosol, particularly that resembling fresh secondary organic aerosol (SOA) and biomass-burning organic aerosol (BBOA). In contrast to what is generally observed for the heterogeneous oxidation of reduced organics, substantial volatilization is observed in both systems. As a continuation of the heterogeneous oxidation experiments, we also measure the kinetics and products of the aging of highly oxidized organic aerosol, in which submicron particles composed of model oxidized organics -- 1,2,3,4-butanetetracarboxylic acid (C8H100 8), citric acid (C6 H8 0 7), tartaric acid (C4H6 0 6 ), and Suwannee River fulvic acid -- were oxidized by gas-phase OH in the same flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to studies of the less-oxidized model systems, particle mass did not decrease significantly with heterogeneous oxidation, although substantial chemical transformations were observed and characterized. Lastly, the immense complexity inherent in the formation of SOA -- due primarily to the large number of oxidation steps and reaction pathways involved -- has limited the detailed understanding of its underlying chemistry. In order to simplify this inherent complexity, we give over the last portion of this thesis to a novel technique for the formation of SOA through the photolysis of gas-phase alkyl iodides, which generates organic peroxy radicals of known structure. In contrast to standard OH-initiated oxidation experiments, photolytically initiated oxidation forms a limited number of products via a single reactive step. The system in which the photolytic SOA is formed is also repurposed as a generator of organic aerosol for input into a secondary reaction chamber, where the organic particles undergo additional aging by the heterogeneous oxidation mechanism already discussed. Particles exiting this reactor are observed to have become more dramatically oxidized than comparable systems containing SOA formed by gas-phase alkanes undergoing "normal" photo-oxidation by OH, suggesting simultaneously the utility of gas-phase precursor photolysis as an effective experimental platform for studying directly the chemistry involved in atmospheric aerosol formation and also the possibility that heterogeneous processes may play a more significant role in the atmosphere than what is predicted from chamber experiments. Consideration is given for the application of these results to larger-scale experiments, models, and conceptual frameworks.
Atmospheric organic aerosols have a significant impact on climate and human health. However, our understanding of the physical and chemical properties of these aerosols is inadequate, thus their climate and health influences are poorly constrained. In this study, we investigated the secondary organic aerosol (SOA) formation from OH-initiated oxidation of -pinene. The majority of experiments were conducted in the York University smog chamber. The main objective was to identify the gas and particle phase products with an atmospheric pressure chemical ionization mass spectrometer (APCI-MS/MS). A wide variety of products were identified containing various functional groups including alcohol, aldehyde, carboxylic acid, ketone and nitrate. Following the chemical composition characterization of products, the shape, phase state and density of generated particles were determined. Images from a scanning electron microscope (SEM) revealed that SOA particles from -pinene were commonly spherical in shape, and adopted an amorphous semi-solid/liquid state. Additionally, the density was determined for SOA particles generated from -pinene/OH, nopinone/OH and nopinone/NO3 experiments for the first time using a tapered element oscillating microbalance-scanning mobility particle sizer (TEOM-SMPS) method. Our results showed a correlation between the determined particle density and the particle chemical composition of the respective system. This demonstrates that changes in particle density can be indicative of the changes in chemical composition of particles. We also investigated the chemical aging of oxidation products by exposing them to additional OH radicals or ozone. The observed changes in chemical composition of products and additional SOA mass production during OH-induced aging were attributed to further oxidation of gas phase intermediate products. The NOx dependence of SOA formation from -pinene photooxidation was investigated in the York University smog chamber and the Jlich Plant Atmosphere Chamber (JPAC). Consistent with previous NOx studies, SOA yields increased with increasing [NOx] at low-NOx conditions, whereas increasing [NOx] at high-NOx conditions suppressed the SOA yield. This increase was attributed to an increase of OH concentration. After removing the effect of [OH] on SOA yield in the JPAC, SOA yields only decreased with increasing [NOx]. Finally, the formation mechanisms of identified products were probed based on the information acquired throughout our study.
The "European Experiment on the Transport and Transformation of Environmentally Relevant Trace Constituents over Europe" (EUROTRAC) was established in 1986 to tackle the scientific problem and combine the expertise, knowledge and resources in Europe, in order to apply them over a large region covering the greater part of the continent. EUROTRAC is a coordinated multidisciplinary scientific research project involving field measurements, laboratory studies, instrument development and development of comprehensive computer models for the simulation of the physical and chemical processes in the lower atmosphere.
The products and mechanisms of secondary organic aerosol (SOA) formation from reactions of 1-alkenes, internal alkenes, and 2-methyl-1-alkenes with OH radicals in the presence of NO[subscript x] were investigated in an environmental chamber and the results used to develop quantitative models for SOA formation. Aerosol chemical composition was analyzed using a thermal desorption particle beam mass spectrometer (TDPBMS), and multifunctional organic nitrate products were quantified using a high-performance liquid chromatograph with UV-vis detector and identified using the TDPBMS and 1H NMR. The major products observed in reactions of linear alkenes were [beta]-hydroxynitrates, dihydroxynitrates, cyclic hemiacetals, dihydrofurans, and dimers formed from dihydroxycarbonyls. Trihydroxynitrates and trihydroxycarbonyls were observed in reactions of 2-methyl-1-alkenes, in addition to the products listed above. Dimers were not observed, apparently because electron donation by the additional methyl group (compared to linear 1-alkenes) reduces the driving force for hemiacetal formation. The measured yields of [beta]-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates were used to calculate relative ratios of 1.0:1.9:4.3 for forming primary, secondary, and tertiary [beta]-hydroxyalkyl radicals by OH radical addition to the C=C double bond, and branching ratios of 0.12, 0.15, and 0.25 for forming [beta]-hydroxynitrates from reactions of primary, secondary, and tertiary â-hydroxyperoxy radicals with NO. The trends are consistent with expected relative stabilities of [beta]-hydroxyalkyl radicals and ß-hydroxyperoxy radical-NO complexes. It should be possible to use these values to estimate product yields from similar reactions of other alkenes. Comparison of measured and model-calculated SOA yields showed that in some cases the models provide accurate predictions of SOA yields, but that uncertainties in gas- and particle-phase chemistry and gas-particle partitioning can lead to significant discrepancies. More limited environmental chamber studies were also carried out on SOA formation from reactions of linear alkenes with NO3 radicals. The major products were [beta]-hydroxynitrates, [beta]-carbonylnitrates, dihydroxynitrates, and hydroxy- and oxo- dinitrooxytetrahydrofurans, which had not been observed previously. It was observed that isomerization of [delta]-hydroxycarbonyls to cyclic hemiacetals, followed by dehydration to highly reactive dihydrofurans that can be further oxidized, can be important sources of SOA from reactions of alkenes with OH and NO3 radicals.